Compacted disintegrant
The disintegrant granulate of claim 1 having
granulate for compression-
molded articles, its
production and its use
US 6303560 B1
ABSTRACT
A compacted granulate and a method for making
the same, comprises 60-99 wt.-% of a water-
insoluble, water-swellable cellulose and
optionally at least one water-swellable
polysaccharide derivative, 1-40 wt.-% of at least
one polymeric binder of a polymer or a
copolymer of (meth)acrylic acid and/or salts
thereof, and at least one liquid surfactant, in
which the granulate has a water content of from
2 to 8 wt.-%. These granulates are useful as
disintegrants for detergent tablets, cleaner
tablets, water-softening tablets, and stain
removing salt tablets
CLAIMS(35)
What is claimed is:
1. A compacted disintegrant granulate for
tablets, consisting of:
A) 60-99 wt.-% of a water-insoluble cellulose
which is swellable in water;
B) 1-40 wt.-% of at least one polymeric binder of
a polymer or a copolymer of (meth)acrylic acid
and/or salts thereof;
C) 0-7 wt.-% of at least one liquid surfactant
which forms a gel with water,
wherein the sum of A), B) and C) amounts to
100 wt.-%, and the disintegrant granulate has a
moisture content of from 2 to 8 wt.-%.
2.
1-15 wt.-% of polymeric binder and from 0.1 to
3.5 wt.-% of the surfactant.
3. The disintegrant granulate of claim 1, wherein
the surfactant is at least one member selected
from the group consisting of non-ionic, anionic,
and amphoteric surfactants, and mixtures
thereof.
4. The disintegrant granulate of claim 1, wherein
the surfactant is at least one surfactant selected
from the group consisting of fatty alcohol
ethoxylates having from 3 to 15 mol of ethylene
oxide, fatty alcohol sulfates, linear
alkylbenzenesulfonates, alkyl ether sulfates,
alkylpolyglycosides, and mixtures thereof.
5. The disintegrant granulate of claim 1, wherein
the granulate has a moisture content of from 3 to
5 wt.-%.
6. The disintegrant granulate of claim 1 having
at least one regenerated cellulose.
7. The disintegrant granulate of claim 1, wherein
prior to compacting, the cellulose is present in
the form of finely divided particles having particle
sizes between 0.03 and 3 mm.
8. The disintegrant granulate of claim 1, wherein
the polymeric binder is selected from the group
consisting of homopolymers of (meth)acrylic
acid and copolymers of (meth)acrylic acid with at
least one of ethylenically unsaturated
dicarboxylic acids, unsaturated dicarboxylic acid
anhydrides, ethylenically unsaturated sulfonic
acids, acrylic esters, vinyl esters, vinyl ethers,
saponification products of vinyl ethers,
crosslinkers, graft base materials based on
polyhydroxy compounds, and mixtures thereof.
9. The disintegrant granulate of claim 1, wherein
the granulate has a particle size of from 0.05 to
3 mm.
10. The disintegrant granulate of claim 1,
wherein the granulate has a particle size of from
0.1 to 1.5 mm.
11. The disintegrant granulate of claim 1,
wherein the granulate has a porosity of from 800
to 1000 ml/kg.
12. The disintegrant granulate of claim 1,
wherein the granulate has a bulk density of from
250 g/l to 400 g/l.
13. A process for manufacturing the disintegrant
granulates of claim 1 comprising:
mixing the components of the granulate to form
a primary mixture,
16. The process of claim 13, wherein the
moisture content after drying is 3-5 wt.-%.
17. A tablet comprising the disintegrant
granulate of claim 1.
18. The tablet of claim 17 having a breaking
strength of up to 80 N and a tablet disintegration
time of up to 15 seconds.
19. A compacted disintegrant granulate for
tablets, consisting of:
A) 60-99 wt.-% of a water-insoluble cellulose
which is swellable in water and at least one
modified water-swellable polysaccharide
derivative;
B) 1-40 wt.-% of at least one polymeric binder of
a polymer or a copolymer of (meth)acrylic acid
and/or salts thereof;

adjusting primary mixture to a moisture content C) 0-7 wt.-% of at least one liquid surfactant
of from 10 to 80 wt.-%, which forms a gel with water,

compacting the primary mixture, wherein the sum of A), B) and C) amounts to
100 wt.-%, and the disintegrant granulate has a
drying the compacted primary mixture to a
moisture content of from 2 to 8 wt.-%.
moisture content of from 2 to 8 wt.-%, and
20. The disintegrant granulate of claim 19,
optionally, milling and screening the dried,
wherein the granulate has a moisture content of
compacted primary mixture to a desired grain
from 3 to 5 wt.-%.
size distribution.
21. The disintegrant granulate of claim 19,
14. The process of claim 13, wherein said
wherein the amount of water-swellable
compacting is carried out using at least one of
polysaccharide derivative is from 5 to 50 wt.-%
rollers under friction, roller or cube presses,
of the amount of cellulose present in the
extruders, ring matrix presses, and pelletizing
granulate.
presses.
22. The disintegrant granulate of claim 19,
15. The process of claim 13, wherein said
wherein the water-swellable polysaccharide
compacting is effected to a moisture content of
derivatives are polysaccharides selected from
from 20 to 40 wt.-% using ring matrix or
the group consisting of cellulose derivatives,
pelletizing presses.
starch derivatives and polygalactomannan
derivatives, said derivatives having anionic
groups, and/or non-ionic groups, and/or modified
by physical and/or chemical crosslinking.
23. The disintegrant granulate of claim 22,
wherein said polysaccharide derivatives are
selected from the group consisting of
carboxymethylcellulose, carboxymethylstarch,
hydroxyalkylcellulose, hydroxyalkylstarch,
alkylcellulose, guar meal and locust bean seed
meal, and mixtures thereof.
24. The disintegrant granulate of claim 19,
wherein prior to compacting, the cellulose and
polysaccharide derivatives are present in the
form of finely divided particles having particle
sizes between 0.03 and 3 mm.
25. The disintegrant granulate of claim 19,
wherein the granulate has a particle size of from
0.1 to 1.5 mm.
26. The disintegrant granulate of claim 19,
wherein the granulate has a porosity of from 800
to 1000 ml/kg.
27. A compacted disintegrant granulate for
tablets, consisting of:
A) 60 -99 wt.-% of a water-insoluble cellulose
which is swellable in water,
D) 1-40,wt.-% of at leas one polymeric binder,
wherein the sum of A) and D) amounts to 100
wt.-%, wherein the disintegrant granulate has a
moisture content of from 2 to 8 wt.-%, and the
polymeric binder D) is a polymer surfactant.
28. The disintegrant granulate of claim 27,
wherein the granulate has a moisture content of
from 3 to 5 wt.-%.
29. The disintegrant granulate of claim 27,
wherein the granulate has a particle size of from
0.1 to 1.5 mm.
30. The disintegrant granulate of claim 27,
wherein the granulate has a porosity of from 800
to 1000 ml/kg.
31. The disintegrate granulate of claim 27,
wherein the polymer surfactants have a polymer
backbone of alkylene oxide moieties.
32. A compacted disintegrant granulate for
tablets, consisting of:
A) 60-99 wt.-% of a water-insoluble cellulose
which is swellable in water and at least one
modified water-swellable polysaecharide
derivative,
D) 1-40 wt.-% of at least one polymeric binder,
wherein the sum of A) and D) amounts to 100
wt.-%, wherein the disintegrant granulate has a
moisture content of from 2 to 8 wt.-%, and the
polymeric binder D) is a polymer surfactant.
33. The disintegrant granulate of claim 32,
wherein the granulate has a moisture content of
from 3 to 5 wt.-%.
34. The disintegrant granulate of claim 32,
wherein said polysaccharide derivatives are
selected from the group consisting of
carboxymethylcellulose, carboxymethylstarch,
hydroxyalkylcellulose, hydroxyalkylstarch,
alkylcellulose, guar meal and locust bean seed
meal, and mixtures thereof.
35. The disintegrant granulate of claim 32,
wherein the granulate has a porosity of from 800
to 1000 ml/kg.
DESCRIPTION
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to disintegrant granulate
compositions of cellulose and optionally
cellulose/starch derivatives, polymeric binders
and gel-forming surfactants, as well as methods
for making these compositions. These
disintegrant granulate compositions are suitable,
for example, as disintegrants for detergent
tablets and granulates.
Disintegrants for tablets or granulates are
auxiliary agents which promote the
disintegration of tablets or granulates upon
contact with liquids, particularly water. The
purpose of the disintegrant is to cause and
enhance both the disintegration of tablets into
coarse fragments, as well as the subsequent
disintegration of the coarse fragments into
smaller particles. In the case of detergent tablets
or granulates, the use of a disintegrant ultimately
results in the dissolution and/or dispersion of all
of the detergent components.
Tablets are produced by compressing a starting
granulate using, such that the bulk density of the
granulate, which is about 900 g/l in compact
detergents, for example, rises to 1200 g/l after
tabletting. As a rule, such tablets, which have
higher densities than the starting granulate,
have poorer solubility and reproducibility
compared to the starting granulate. The addition
of disintegrants promotes the desired rapid
dissolution, or disintegration and dissolution of
such tablets.
Depending on the composition of detergents and
cleaners, the molding pressures required in
tabletting can vary. Thus, the type of builder
used, e.g. phosphate, zeolite, disilicate or
layered silicate, may require various different
molding pressures, so that tablets having
varying hardness or compactness are formed. In
order to safely protect the tablets against
external mechanical impact, e.g. against
breaking during transportation or when dropped,
they should have a strength of 50 N or more.
Two ways of introducing a detergent tablet into a
washing machine are normally possible: placing
the tablet into the wash-in chamber of the
washing machine, or into the washing drum of
the washing machine. The requirements for
tablet disintegration will vary depending on
where the tablet is introduced into the washing
machine.
Introduction into the wash-in chamber is the
easiest method for the user and provides a
higher quality washing process. However, this
method places exceedingly high demands on
the disintegration rate of the tablet. Specifically,
the first step of tablet disintegration into coarse
fragments must proceed very quickly because
otherwise, tablet residues remain in the wash-in
chamber and will not be utilized in washing. In
modem washing machines, a time period of
about 30 seconds normally is available for
content of the tablets to be washed into the
washing drum of the washing machine, via the
wash-in chamber. In addition, this disintegration
must occur within this 30 second period in both
hot or cold wash-in water. When the detergent
tablet is placed directly into the washing drum,
the conditions for tablet disintegration are quite
different because both mechanical friction and
increasing water temperatures assist in the
tablet dissolving process
This problem of highly compacted moldings
having long disintegration times is well-known in
the field of pharmaceutical preparations. A large
number of compounds and mixtures are known
as tablet disintegrants in pharmaceutical
practice. Several modes of operation have been
discussed for tablet disintegrants, such as
evolution of gas bubbles (effervescent powders),
mutual repulsion of particles, transport of water
(wicking effect), and a swelling/expansion due to
absorption of water.
Many compounds which undergo massive
swelling upon exposure to water are known.
However, the swelling rate of these compounds
is frequently is too slow to be of practical use. In
addition to swelling rate and swelling volume of
such compounds, the swelling pressure is of
particular importance. There are various known
methods for measuring these properties. It is
possible to measure the expansion with no
counter-pressure, and also to measure the
swelling pressure with no expansion. Combined
methods of measuring, wherein both the
swelling pressure and the expansion are
detected, are particularly suited in making
predictions as to the suitability of disintegrants in
tablets. One such method is the measurement of
the swelling kinetics of the disintegrant, where
the time dependence of the expansion under
load of a disintegrant is determined. Hence, both
swelling pressure and expansion are included in
the results. Products suitable as disintegrants
are also known to undergo either linear or non-
linear expansion during the swelling process.
Owing to their more rapid effect, disintegrants
which undergo nonlinear swelling are markedly
superior to disintegrants which undergo linear
swelling.
2. Discussion of the Background
As can be inferred from the statements in WO
98/55575 regarding the prior art, the
disintegrants known in the production of drug
tablets may also be used in the field of
detergents and cleaners.
DE-OS 2,251,249 describes rapidly
disintegrating drug tablets, for example, which
are produced by compressing a drug granulate
and a disintegrant granulate. The use of granular
starting materials results in a porous tablet
structure. A starch-based disintegrant granulate
having a particle size of from 2.0 to 0.3 mm is
used as an example.
DE-OS 2,355,204 reports drug tablets which for
tablet stability reasons are compressed from
granular starting components adjusted to a
moisture content of less than 2%, prior to
compression.
U.S. Pat. No. 3,629,393 claims drug tablets with
delayed release of the active ingredient, which
are compressed from granular components,
including granular disintegrants comprised of
high molecular weight water-swellable
compounds such as cellulose derivatives. The
examples describe granulate dimensions of
around 0.84 mm.
U.S. Pat. No. 4,072,535 describes the use of
disintegrants made of pre-compacted starch in
pharmaceuticals and detergents. The grain size
of the compacted material is from 0.05 mm to
0.42 mm, the moisture content is reported to be
9-16%, preferably 11-13%. The disintegration
times of the exemplary tablets are around
several minutes.
DE-OS 2,321,693 reports detergent tablets
containing from 1 to 25 wt.-% of fibrous cellulose
as disintegrant. In the examples, tablets
containing compacted cellulose granulates have
astrength of from 15 to 19 N.
EP 0,170,791 describes tablet-shaped detergent
additives compressed from granulate
components, having from 1 to 5 wt.-% of
granulate tablet disintegrants based on
crosslinked polyvinylpyrrolidone and/or cellulose
ethers. The granulate should be free of dusty
components. The tablets have breaking
strengths of from 50 to 120 N and long
dissolution times of several minutes.
WO 98/40463 reports moldings having detergent
or cleaning activity, which are produced using a
disintegrant granulate having a high adsorptive
capacity for water and a grain size distribution in
which at least 90 wt.-% of the grains have a
particle size of 0.2 mm to 3 mm. The fraction of
dust particles having a particle size <0. 1 mm is
below 1 %. The disintegrant granulate contains
at least 20 wt.-% of disintegrants such as starch,
starch derivatives, cellulose, and cellulose
derivatives. According to the teaching of this
patent, the presence of anionic or non-ionic
surfactants has a negative effect on the tablet
disintegration time. The granulate is produced in
a conventional fashion, such as by spray drying,
superheated steam drying of aqueous
formulations, or by granulating, pelletizing,
extrusion, or roll compacting of powdered
components. There is no detailed processing
data as to the granulation process or other
processing steps following granulation to form
the disintegrant granulate. The detergent tablet
produced as an example includes a disintegrant
based on compacted cellulose made of
thermomechanically treated wood material and
has a tablet hardness of 45 N. Tablets having
higher strength, i.e. more than 50 N, were not
described.
WO 98/55575 describes an auxiliary agent
granulate for moldings having detergent and
cleaning activity. The claimed auxiliary agent
granulates include from 10 to 95 wt.-% of
cellulose having a particle size below 0.1 mm
and from 5 to 90 wt.-% of microcrystalline
cellulose. According to the Examples, the
celluloses in the auxiliary agent granulates are
partially combined with carboxymethylcellulose,
N,N,N,N-tetraacetylethylenediamine (TAED)
and citric acid/bicarbonate. The grain size of
more than 90 wt.-% of the compacted material is
from 0.3 to 2.0 mm, and 0.2 mm in less than 5
wt.-% of the compacted material. There are no
dusty components. Roller compaction of the dry
pre-mixture is the preferred method of
production. WO 98/55575 does not provide
detailed processing data for the production of
the granulate. The examples show that
detergent tablets which have the auxiliary agent
granulates, have low strengths of 35 N or less.
More stable, more highly compacted tablets
having higher strengths of at least 50 N are not
described.
The unpublished European Patent Applications
98 121 397.8 and 98 121 392.9 claim
cellulose/cellulose derivatives and starch/starch
derivatives, respectively, together with thickening
surfactants and fine particulate polymers of
(meth)acrylic acid in a compacted, granulate
form as a disintegrant granulate component of
detergents and cleaners, softeners, and stain
removing salts produced in the form of tablets.
The granulates have non-linear swelling kinetics
such thatwith respect to the overall swelling
processa massive increase in volume occurs
during the initial phase of the swelling process.
This reference does not describe the dissolution
behavior of the tablets in the wash-in chamber of
a washing machine.
The patent application WO 98/40462 describes
a pellet made of powdered and/or granulate
ingredients, particularly detergent ingredients,
and includes particles of a cellulose-containing
material, which may also be present in
compacted form, acting as a disintegrant.
Particularly preferred cellulose components
include pulps treated by thermomechanical
(TMP) and chemithermomechanical (CTAP)
processes. The particle size of the compacted
disintegrant may range from 0.2 to 6 mm.
Surfactants may also be added to the pellet via
the cellulose component, for example at a level
of 0.5 to 5% of surfactant/pellet. This
corresponds to a surfactant content of about
1445 wt.-% in the cellulose disintegrant, based
on the reported 3 to 6%/pellet concentrations of
cellulose disintegrant in the compacted
granulate. This reference does not provide
detailed process or technical information
regarding the production of the disintegrant
granulate or its function in the pellet.
According to EP 0,750,662 B1, the production of
cleaning tablets having high breaking strength
and storage stability is possible when the
components of the mixture are first made
hydrophobic, and the tablets are then produced
without water. These tablets do not include any
disintegrant granulates and have breaking
strengths of >150 N, but they exhibit highly
delayed dissolution behavior.
The prior art also includes the products
marketed by the company Degussa AG,
designated Elcema G250 and Elcema G400,
which consist of pure compacted cellulose, and
have been used as tablet disintegrants since
1971. These products are produced using dry
granulation and have a particle size of from 0.03
up to 0.40 mm. The moisture content is less than
about 6%.
SUMMARY OF THE INVENTION
It is therefore the object of the invention to
provide a disintegrant granulate for tablets which
is superior compared to the prior art. In
particular, this granulate should undergo rapid
and massive swelling in such a way that tablets
produced therewith are largely dissolved in the
wash-in chamber of washing machines during
the short water wash-in period.
Furthermore, the disintegrant granulate should
have high abrasion strength, and its
effectiveness should not be limited by amounts
of fines and particularly dust inevitably arising
during its production process. Moreover, in
tablets having high strengths of more than 50 N,
the disintegrants should ensure a combination of
good disintegrating effect and good solubility,
and ageing phenomena in the form of an
attenuation of properties should be small when
storing the tablets for several weeks. In addition,
a process for the production of said disintegrant
granulates and their use in tablets for washing
and cleaning processes is provided.
DETAILED DESCRIPTION OF THE INVENTION
The object of the present invention is
accomplished by means of a compacted
disintegrant granulate for tablets, constituted of:
A) 60-99 wt.-% of a cellulose which is insoluble
in water and swellable in water, and optionally,
other modified water-swellable polysaccharide
derivatives;
B) 1-40 wt.-% of at least one polymeric binder in
the form of a polymer product or a copolymer
product of (meth)acrylic acid and/or salts
thereof;
C) 0-7 wt.-% of at least one a liquid surfactant
forming a gel with water;
wherein the sum of A), B) and C) amounts to
100 wt.-%, characterized in that the disintegrant
granulate has a moisture content of from 2 to 8
wt.-%.
Surprisingly, the disintegrant compacted
products were found more effective when having
a specific water content. According to the
teaching of prior art and practical experience, a
water content in the final granulate which is as
low as possible might have been expected to
provide the best swelling effect.
Component A:
A water-insoluble, swellable cellulose may be
used. Fibrils of native cellulose having a
maximum length of 0.30 mm were found
particularly suitable. Both microcrystalline and
amorphous, fmely particulate cellulose and
mixtures thereof can be used. 2V The finely
particulate cellulose preferably has bulk weights
of from 40 g/l to 300 g/l, and includes bulk
weights of 50, 60, 70, 80, 90, 100, 110, 120,
130, 140, 150, 160, 170, 180, 190, 200, 210,
220, 230, 240, 250, 260, 270, 280, and 290 g/l,
more preferably from 65 g/l to 170 g/l, inclusive
of all values and subranges therebetween.
When using types which have already been
granulated, their bulk weight is higher and can
be from 350 g/l to 550 g/l in an advantageous
embodiment, including bulk weights of 360,370,
380, 390, 400,410,420, 430, 440, 450,460, 470,
480, 490, 500, 510, 520, 530, and 540 l,
inclusive of all values and subranges
therebetween. Typically, the bulk weights of the
cellulose derivatives range from 50 g/l to 1000
g/l, including bulk weights of 100, 150, 200, 250,
300, 350, 400, 450, 500, 550, 600, 650, 700,
750, 800, 850, 900, and 950 l, inclusive of all
values and subranges therebetween, preferably
from 100 g/l to 800 g/l.
The particle size of the finely particulate
cellulose preferably is between 0.030 mm and
0.20 mm, including 0.040, 0.050, 0.060, 0.070,
0.080, 0.090, 0.10, 0.1 1, 0.12, 0.13, 0.14, 0.15,
0.16, 0.17, 0.18, and 0.19 mm, inclusive of all
values and subranges therebetween, and the
preferred average particle size in granulated
types is between 0.350 mm and 0.800 mm,
including 0.400, 0.450, 0.500, 0.550, 0.600,
0.650, 0.700, and 0.750 mm, inclusive of all
values and subranges therebetween. The
particle size of the finely particulate cellulose
derivatives preferably is from 0.030 mm to 3.0
mm, including 0.040, 0.050, 0.060, 0.070, 0.080,
0.090, 0.100, 0.150, 0.200, 0.250, 0.300, 0.350,
0.400, 0.450, 0.500, 0.550, 0.600, 0.650, 0.700,
0.750, 0.800, 0.850, 0.900, 0.950, 1.0, 1.1, 1.2,
1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3,
2.4, 2.5, 2.6, 2.7, 2.8, and 2.9 mm, inclusive of
all values and subranges therebetween.
The amount of cellulose in the disintegrant
granulate is between 60 and 99 wt.-%, including
65, 70, 75, 80, 85, 90, and 95 wt.-%, inclusive of
all values and subranges therebetween,
preferably between 60 and 95 wt.-%.
In a particular embodiment of the invention,
regenerated celluloses such as viscose are also
used. Regenerated celluloses in a powdered
form are especially remarkable for their good
water absorption. The viscose powder can be
produced from cut viscose fibers or by
precipitation of dissolved viscose. For example,
low molecular weight cellulose degraded by
electron beam is also suitable in the production
of the disintegrant granulate. In an
advantageous embodiment, plasticized
regenerated fibers are used. For example,
glycerol is a typical plasticizer for these
products.
In an advantageous embodiment, the granulates
according to the invention may include water-
swellable polysaccharides derivatives, including
water-swellable cellulose derivatives such as
cellulose ethers and cellulose esters, and water-
swellable starch or starch derivatives, as well as
polygalactomannans. For example, such water-
swellable polysaccharide derivatives may
include ionically modified celluloses and
starches such as carboxymethyl-modified
cellulose and carboxymethyl-modified starch,
nonionically modified celluloses and starches
like alkoxylated celluloses and starches such as
hydroxpropyl- and hydroxyethylstarch or
hydroxpropyl- and hydroxyethylcellulose, and
alkyl-etherified products such as
methylcellulose, as well as mixed modified
celluloses and starches, modified as described
above, optionally combined with a crosslinking
modification step. Also, suitable starches are
cold-swelling starches formed by mechanically
or chemically degrading the starch grain. Above
all, these include swelling starches made by
extruder and roller drying processes, as well as
products modified enzymatically, by oxidation or
acid degradation. Chemically derivatized
starches preferably contain substituents linked in
sufficient number to the polysaccharide chains
by ester and ether groups.
Starches modified with ionic substituents such
as carboxylate, hydroxyalkyl or phosphate
groups were found particularly advantageous
and therefore, they are preferred. Also, the use
of slightly pre-crosslinked starches was found
beneficial in improving the swelling behavior. As
a result of their good cold water swellability,
alkaline-treated starches may also be used.
In an advantageous embodiment, a combination
of cellulose and cellulose derivatives and/or
starch and/or starch derivatives has proven
successful. The quantity ratios may vary within
wide limits, and the percentage of cellulose
derivatives and/or starch and/or starch
derivatives preferably is from 0.1 to 85 wt.-%,
more preferably from 5 to 50 wt.-%, relative to
the combination.
Component B:
Polymers or copolymers of (meth)acrylic acid or
mixtures of such polymers or copolymers are
used as binders in the granulate. The polymer
products are selected from the group of
homopolymers of (meth)acrylic acid, from the
group of copolymers with the following monomer
components: ethylenically unsaturated
dicarboxylic acids and/or anhydrides thereof,
and/or ethylenically unsaturated sulfonic acids
and/or acrylic esters and/or vinyl esters and/or
vinyl ethers or saponification products thereof,
and/or crosslinkers and/or graft base materials
based on polyhydroxy compounds.
Non-crosslinked polymers or copolymers of
(meth)acrylic acid having weight average
molecular weights of from 5,000 to 70,000 were
found particularly suitable, including molecular
weights of 6,000, 7,000, 8,000, 9,000, 10,000,
15,000, 20,000, 25,000, 30,000, 35,000, 40,000,
45,000, 50,000, 55,000, 60,000, and 65,000,
inclusive of all values and subranges
therebetween. These copolymers preferably are
copolymers of (meth)acrylic acid and
ethylenically unsaturated dicarboxylic acids or
anhydrides thereof, such as maleic acid or
maleic anhydride, and contain e.g. from 40 to 90
wt.-% of (meth)acrylic acid and from 60 to 1 0
wt.-% of maleic acid or maleic anhydride, the
relative molecular weight of which, based on
free acid, ranging between 3,000 and 100,000,
preferably from 3,000 to 70,000, and more
preferably from 5,000 to 50,000. Likewise, ter-
and quaterpolymeric polycarboxylates
constituted of (meth)acrylic acid, maleic acid and
optionally, completely or partially saponified vinyl
alcohol derivatives, or those constituted of
(meth)acrylic acid, ethylenically unsaturated
sulfonic acids and polyhydroxy units such as
sugar derivatives, or those constituted of
(meth)acrylic acid, maleic acid, vinyl alcohol
derivatives, and monomers containing sulfonic
acid groups were found to be well-suited
binders. Examples of suitable polymer products
can be seen in the patent specifications DE 43
00 772, DE 42 21 371, and WO 95/17444.
In production, the polymeric binders preferably
are employed in the form of their aqueous
solutions, but may also be used in the form of
finely particulate powders. The binder e
polymers preferably are present in a partially or
completely neutralized form, with salt formation
preferably being effected using cations of alkali
metals, ammonia and amines or 152 mixtures
thereof. The percentage of polymers/copolymers
in the disintegrant is between 1 and 40 wt.-%,
including 2, 3, 4, 5, 10, 15,20,25, 30, and 35 wt.-
%, inclusive of all values and subranges
therebetween, preferably between 1 and 20 wt.-
%, and more preferably between 5 and 15 wt.-
%. Polymer percentages above 15% in the
disintegrant result in harder disintegrant
granulates, while polymer amounts below 1%
tend to form soft granulates which are less
resistant to abrasion.
Crosslinked polymers of (meth)acrylic acid are
also suitable polymer binders. They are
preferably used as finely particulate powders
and preferably have an average particle size of
from 0.045 mm to 0.150 mm, including 0.050,
0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085,
0.090, 0.095, 0.100, 0.110, 0.120, 0.130, and
0.140 mm, inclusive of all values and subranges
therebetween, and preferably are employed at
0.1 to 10 wt.-%, including 0.2, 0.3, 0.4, 0.5, 0.6,
0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, and 9 wt.-%,
inclusive of all values and subranges
therebetween. While particles having an
average particle size of more than 0.150 mm
also provide good disintegrant granulates, they
give rise to swelled bodies visible as particles
when dissolving the tablets produced using said
granulates, which bodies, e.g. in case of textile
washings, undergo undesirable, clearly visible
deposition on the textile material.
A special embodiment of the invention is
represented by the combination of soluble
poly(meth)acrylate homo- and copolymers and
the previously mentioned finely particulate,
crosslinked polymer particles.
The so-called polymer surfactants are also
suitable co-binders which, at the same time,
have surfactant characteristics. These are
understood to be reaction products which, in
addition to the typical polymer structures of the
above-mentioned binder polymers, have
structural elements which provide a surfactant
effect. For example such polymer surfactants
may include graft polymers with alkoxylated fatty
alcohol, or carboxylate-containing polymers
including methoxyalkylene oxide monomer units,
and also, maleic acid/vinyl ether/long-chain fatty
amine copolymers, as well as semiamides of
maleic acid copolymers and copolymers of
acrylic acid and long-chain acrylates. In a
preferred embodiment, the polymer surfactants
contain alkylene oxide units. The polymer
surfactants can be present in amounts of up to
30 wt.-% in the disintegrant granulate.
In the production of the disintegrant granulates
according to the invention, the above-mentioned
polymer surfactants were found suitable when
used alone, with no polymeric binder component
and with no surfactant component present. The
required amounts of polymer surfactant in the
disintegrant granulate range from 1 to 40 wt.-%,
including 2, 3, 4, 5, 10, 15, 20, 25, 30, and 35
wt.-%, inclusive of all values and subranges
therebetween, preferably from 5 to 20 wt.-%.
Accordingly, the present object is also
accomplished by means of a compacted
disintegrant granulate for tablets, constituted of
A) 60-99 wt.-% of a water-insoluble cellulose
which is swellable in water, and optionally, other
modified water-swellable polysaccharide
derivatives;
D) 1-40 wt.-% of at least one polymeric binder;
wherein the sum of A) and D) amounts to 100
wt.-%, characterized in that the disintegrant
granulate has a moisture content of from 2 to 8
wt.-%, and the polymeric binder D) is a polymer
surfactant
Component C:
As another ingredient, the disintegrant granulate
includes one or more liquid surfactants forming
gels with water, selected from the group of non-
ionic, anionic or amphoteric surfactants present
in amounts of up to 7 wt.-%, including 0, 0.5, 1,
1.5, 2, 2.5, and 3 wt.-%, inclusive of all values
and subranges therebetween, preferably up to
3.5 wt.-%. An excessively high surfactant
content in the disintegrant results in poorer
swelling properties in addition to increased
abrasion in the tablets produced therewith.
For example, the non-ionic surfactants can be
alkylpolyglucosides, fatty acid alkylolamides,
fatty acid polyethyleneglycol esters, fatty amine
oxyethylates, fatty alcohol ethoxylates having 3-
15 mol ethylene oxide or propylene oxide, fatty
acid glycerides, sorbitan esters, saccharose
esters, e.g. saccharose palmitate, pentaerythritol
partial esters which may also be ethoxylated, as
well as alkylphenol polyethyleneglycol ethers or
phenol polyethyleneglycol ethers.
For example, the anionic surfactants can be
alkyl sulfates, linear and branched
alkylbenzenesulfonates, alkylglycerol ethers,
fatty alcohol polyethyleneglycol ether sulfates,
paraffinsulfonates, -olefinsulfonates,
sulfosuccinates, phosphoric esters, or fatty
alcohol ether carboxylates.
For example, the amphoteric surfactants can be
coconut fatty acid amidopropylbetaine, modified
imidazolines, or fatty acid amide derivatives
having a betaine structure.
In a preferred embodiment of the invention,
mixtures of surfactants are employed, and in
another preferred embodiment, only non-ionic
surfactants are used.
The granulate compact according to the
invention is remarkable for its particular swelling
kinetics, i.e., the expansion as a function of time
does not vary in a linear fashion but rather,
reaches a very high level after only a very short
time. In this case, the swelling behavior within
the first 10 seconds after contact with water is of
particular interest. Within the 2 to 8 wt.-% range
of water content according to the invention,
there is an unexpectedly high volume
expansion, a high expansion rate, and a high
swelling pressure. This combination of
properties results in short tablet disintegration
times and a very good wash-in behavior in the
dosing chambers of washing machines, for
tablets containing the compacted disintegrant
granulates of the present invention. In the wash-
in tests, the superior effect of the agents
according to the invention is seen in the fact that
nearly all the tablets are disintegrated and
washed away.
The specific water-absorbing capacity of the
granulate according to the invention is very high
and can be determined gravimetrically. The
water absorption determined in this way is
preferably from 500 to 2000%, including 600,
700, 800, 900, 1000, 1100, 1200, 1300, 1400,
1500, 1600, 1700, 1800, and 1900%, inclusive
of all values and subranges therebetween.
Surprisingly, it has also been found that a
specific amount of dust, which, according to the
teaching of prior art, should not be present in
granulates for detergent and cleaner tablets,
does not represent an interference in the
disintegrant compacted product of the invention
and, in addition, contributes to good storage
stability of the tablets produced. Amounts of fine
dust having up to 10 wt-%, preferably up to 8
wt.-% of particles less than 0.1 mm in size may
be present in the disintegrant granulates of the
invention.
Compared to prior art products, the absorption
of liquid (also referred to as specific porosity) of
the disintegrant according to the invention is
markedly increased, being in a range of more
than 750 ml/kg, preferably in a range of from
800 to 1000 ml/kg. Such a high liquid absorption
has a significant effect on the swelling
performance and the transport of water in the
disintegrant. On an average, prior art products
have liquid absorption values of about 600
ml/kg.
Initially, the production of the disintegrant
granulates of the invention is effected by mixing
the granulate components according to the
invention, using conventional mixing procedures.
For example, mixers by the companies Vomm,
Ldige, Schugi, Eirich, Henschel, or Fukae may
be used. In this first step of mixing and
granulating, precompounds are produced using
agglomeration processes. These precompounds
form a flowable material having a water content
between 10 and 80 wt.-%. The required water
content in the primary mixture depends on the
compacting means which is used. A water
content of at least 10%, preferably 20% is
required to achieve good compacting and to
ensure high liquid absorption in the subsequent
dry granulate. With water contents between 60
and 80 wt.-%, care must be taken to prevent
water from being pressed out of the mixture
during the compressing process in certain
compacting apparatus such as a ring matrix
press, while these phenomena are not observed
in extruders. Ultimately, the compacting
technique must be adapted to the water content
of the primary mixture. In ring matrix presses
and pelletizing presses, a water content of from
20 to 60 wt.-%, including 25, 30, 35, 40, 45, 50,
and 55 wt.-%, inclusive of all values and
subranges therebetween, preferably from 20 to
40 wt.-% was found beneficial. Also, for
economic reasons as well, the water content of
the precompound should not be higher than
required, because this water has to be removed
in the subsequent drying process with input of
energy.
In the next step, these precompounds are
subjected to mechanical compacting. Final
compacting is essential for the swelling and
water absorbing behavior of the granulate
according to the invention. Compacting using
pressure may be effected in various ways. The
products can be compacted e.g. in a smooth or
patterned fashion between two working surfaces
in roller compactors. The compacted product
discharges in the form of a strand. Compacting
methods in matrices using plugs or pad rollers
result in compacted product forms such as
tablets or briquettes. Roller compactors,
extruders, roller or cube presses, as well as
granulating presses may be used as compacting
machines.
Compacting using a pelletizing press was found
particularly suitable, and by means of a suitable
process control, granulates are obtained which
can be dried without further size reduction. For
example, suitable pelletizing presses are
produced by the companies Amandus Kahl and
Fitzpatrick. As a result of compacting, a
disintegrant granulate preferably is produced
which has a bulk density of from 100 g/l to 500
g/l, more preferably from 150 g/l to 450 g/l, with
250 g/l to 400 g/l being particularly preferred.
Because of the particularly good swelling
properties, it was found beneficial to maintain a
bulk density limit of 400 g/l at maximum.
Surprisingly, the granulates were found to have
high abrasion resistance even at such bulk
densities.
The coarse, compacted particles are reduced in
size, where e.g. mills, chippers or roller mills are
suitable. Size reduction may be effected prior to
or after drying, where the granulates of the
invention preferably are adjusted to a particle
size distribution of from 0.05 to 3 mm, more
preferably from 0.1 to 1.5 mm.
The removal of dust fractions below 0.1 mm can
be performed using common screening units, for
example. Because dust percentages of up to 10
wt.-% do not represent an interference in most
cases when using the granulates of the
invention, their removal is often unnecessary.
The water content according to the invention,
being 2-8 wt.-%, preferably 2.5-7 wt.-%, and
more preferably 3-5 wt.-%, is adjusted during the
drying process. To this end, conventional dryers
such as roller dryers (temperatures of e.g. 95-
120 C.) or fluid bed dryers (temperatures of e.g.
70-100 C.) are suitable.
The invention encompasses the use of these
compacted granulates as disintegrants for
compressed moldings, e.g. tablets, cubes, balls
and the like. The use as disintegrants for cleaner
formulations, detergent formulations, stain
removing salts, softeners in tablet or cube form
is particularly preferred.
The moldings contain the disintegrant granulates
according to the invention in amounts of from
0.5 wt.-% to 15 wt.-%/o, including 1, 1.5, 2, 2.5,
3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5,
10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, and
14.5 wt.-%, inclusive of all subranges and values
therebetween, preferably from 3 wt.-% to 8 wt.-
%, and more preferably from 4 wt.-% to 7 wt.-%.
The moldings of the invention have sufficient
stability and strength and enable safe handling,
packaging and storage. Upon contact with water,
however, they should undergo rapid
disintegration, so that the other components of
the molding may have the desired effect.
Sufficient stability to mechanical exposure is
present for moldings at a breaking strength of
from 50 N or higher. The granulates according to
the invention impart excellent disintegration and
dissolution characteristics to these highly
compacted moldings. Such disintegration and
dissolution characteristics are otherwise present
only in moldings of low strength.
As a rule, the moldings for detergent
formulations include builders, bleaching agents
and bleaching activators, surfactants, tabletting
aids, disintegrants, and other conventional
additives and auxiliary agents.
Polyphosphates, pyrophosphates,
metaphosphates or phosphonates, layered
silicates, amorphous silicates, amorphous
disilicates, and zeolite are possible as builders.
Further components of the builder system can
be fillers such as alkali carbonates,
bicarbonates, e.g. sodium carbonate or sodium
hydrogen carbonate, sesquicarbonates, sodium
sulfate, magnesium sulfate, or citrate, citric acid,
succinic acid, tartaric acid, and malic acid. Co-
builders and dispersants frequently are also
used as auxiliary builders. These co-builders or
dispersants can be polyacrylic acids and sodium
salts thereof.
Copolymers of (meth)acrylic acid and maleic
acid, terpolymers and quaterpolymers of
(meth)acrylic acid, maleic acid, vinyl alcohol and
vinyl compounds containing sulfo groups may
also be used. In particular, ter- and
quaterpolymeric polycarboxylates produced from
(meth)acrylic acid, maleic acid and vinyl alcohol
or vinyl alcohol derivatives (such as described in
DE 43 00 772 C2), or those produced from
(meth)acrylic acid, 2-alkylallylsulfonic acid and
sugar derivatives (such as described in DE 42
21 381 C1), or those produced from
(meth)acrylic acid, maleic acid, vinyl alcohol
derivatives and monomers having sulfonic acid
groups (described in DE 195 16 957 A) are also
preferred.
Polyethyleneglycol and/or polypropyleneglycol
having a molecular weight of from 900 to 30,000
are used as additional components, as well as
carboxylated polysaccharides, polyaspartates
and polyglutamate. Mixtures including various
organic builders such as citric acid are also
possible.
Conventional bleaching agents to be used are
sodium perborate tetrahydrate and sodium
perborate monohydrate, sodium percarbonate,
peroxypyrophosphates, citrate perhydrates, as
well as peracid salts which form H2O2, peracids,
as well as perbenzoates, peroxyphthalates,
diperazelaic acid and diperdodecanedioic acids.
The content of bleaching agents in the tablets
preferably is 10-60 wt.-%, and particularly 15-50
wt.-%. Activators may be incorporated to
achieve a good bleaching effect when washing
at 60 C. and below.
Suitable bleaching activators are N-acyl and O-
acyl compounds which form organic peracids
with H2O2, preferably N,N-tetraacylated
diamines, carboxylic anhydrides and esters of
polyols, such as glucose pentaacetate.
Furthermore, acetylated mixtures of sorbitol and
mannitol can be used. N,N,N,N-
tetraacetylethylenediamine (TAED), 1,5-diacetyl-
2,4-dioxo-hexahydro-1,2,5-triazine (DADHTI)
and acetylated sorbitolmannitol mixtures
(SORMAN) are particularly suited as bleaching
activators.
In addition to non-ionic, anionic and amphoteric
surfactants, cationic surfactants may also be
present in detergent formulations, e.g.
quaternary ammonium compounds having C8-
C6 N-alkyl or N-alkenyl groups and N-
substituents such as methyl, hydroxyethyl or
hydroxypropyl groups.
Also, tabletting aids are optionally used, e.g.
polyalkyleneglycols and magnesium stearate.
Examples of other conventional detergent
additives and auxiliary agents are enzymes,
magnesium silicates, aluminum aluminates,
benzotriazole, glycerol, magnesium stearate,
polyalkylene glycols, hexametaphosphate,
phosphonates, bentonites, soil release
polymers, and carboxymethylcelluloses.
As a rule, dishwasher tablets as an embodiment
of detergent formulations contain
polyphosphates, pyrophosphates,
metaphosphates, or phosphonates, layered
silicates, amorphous silicates, amorphous
disilicates, and zeolites as builders, as well as
fillers such as sodium carbonate, sodium sulfate,
magnesium sulfate, sodium hydrogen
carbonate, citrate, and citric acid, succinic acid,
tartac acid, and malic acid. Frequently, co-
builders and dispersants are co-used as
auxiliary builders. Such co-builders or
dispersants can be polyacrylic acids or
copolymers with polyactylic acid and sodium
salts thereof.
Conventional bleaching agents are sodium
perborate tetrahydrate and sodium perborate
monohydrate, sodium percarbonate,
peroxypyrophosphates, citrate perhydrates, as
well as peracid salts which form H2O2, peracids,
such as perbenzoates, peroxyphthalates,
diperazelaic acid, and diperdodecanedioic acids.
The content of bleaching agents in the tablets
preferably is 10-60 wt.-%, including 15, 20, 25,
30, 35, 40, 45, 50, and 55 wt.-%, inclusive of a
values and subranges therebetween, particularly
15-50 wt.-%. Likewise, low-foam non-ionic
surfactants of the polyalkyleneglycol and
alkylpolyglucciside types are employed.
Similarly, examples of other common cleaner
additives and auxiliary agents are enzymes,
magnesium silicates, aluminum aluminates,
benzotriazole, glycerol, magnesium stearate,
polyalkyleneglycols, hexametaphosphate, and
phosphonates. As a rule, water-softening tablets
are comprised of builders such as layered
silicates, amorphous silicates, amorphous
disilicates and zeolites, and fillers such as
sodium carbonate, sodium sulfate, magnesium
sulfate, sodium hydrogen carbonate, citrate, and
citric acid.
Frequently, co-builders and dispersants are used
as auxiliary builders. Such co-builders or
dispersants can be polyacrylic acids or
copolymers with polyacrylic acid and the sodium
salts thereof.
Likewise, low-foam non-ionic surfactants of the
polyalkyleneglycol and alkylpolyglucoside types
are employed.
Examples of other common detergent additives
and auxiliary agents are magnesium silicates,
polyalkyleneglycols and phosphonates.
In a preferred embodiment, the disintegrant
granulates of the invention permit the production
of detergent tablets having disintegration times
of up to 15 s at a tablet breaking strength of up
to 80 N.
With reference to the embodiments, the
invention will be illustrated in more detail below.
All figures are by weight, unless otherwise
stated in individual cases.
Testing Methods
Determination of the Specific Water-Absorbing
Capacity
The specific water-absorbing capacity of the
granulate according to the invention can be
determined gravimetrically as follows:
A defined amount of granulate (e.g. 2.00 g) is
welded in a thin paper bag, such as a tea bag,
and immersed in a vessel containing an excess
of distilled water. After a 3 minute immersion
time, the bag is taken out of the water and
suspended for 10 minutes to drain. The bag is
weighed, and the water absorption in the
presence and absence of granulate is
determined from the weight difference of wet
bags containing the granulate, compared to wet
bags which do not contained the granulate.
Determination of the Swelling Kinetics
To determine the swelling rate and swelling
height under load, 3.00 g of granulate is placed
in a cylindrical plastic vessel having an inner
diameter of 60 mm and covered with a water-
permeable fleece. Depending on the bulk
weight, the layer thickness of the granulate is 1-
3 mm. A movable piston having a through-
boxing and a weight of 58 g is placed on the
fleece and connected to a path measuring
instrument which records the path of the piston
as a function of time. The granulate is caused to
swell by adding 70 ml of water, and the shift of
the piston thus induced (path) is determined as
a function of time and evaluated graphically.
Determination of Liquid Absorption (Specific
Porosity)
The specific porosity of the disintegrant
granulate is determined using a well-known
standard method of determining the porosity
level of solids. The principle of said method is as
follows:
The solid is completely soaked with di-n-butyl
phthalate (DBP) and subsequently, the liquid
absorbed in the pores after a defined period of
time under defined conditions is removed by
centrifuging. The amount of absorbed DBP is
regarded as a measure for the porosity of the
solid.

Procedure:

3 g of sample is weighed in a commercially

available, tared G3 glass filter crucible and 10 ml
of DBP is added. These crucibles are placed in a
beaker lined with filter paper at its bottom.
Precisely after 5 minutes, the glass filter
crucibles are weighed, subsequently placed in
Teflon holders and centrifuged for 5 minutes at
1800 rpm. Following centrifuging, the crucibles
are removed from the Teflon holders and
weighed again.

The porosity is calculated according to the

following
formula: P = ( M2 - M1 ) 1000 Density E P =
Absorbing capacity in ml DBP per kg of solid
(porosity) M2 = weight, in grams, of crucible
with moist sample after
Method of Determining the Tablet Disintegration
centrifuging M1 = weight, in grams, of crucible
Time
with dry sample with
solvent Density = 1.050 g / ml DB A tablet for washing and cleaning having a
P E = initial weight of sample in grams content of 5% disintegrant is used in the test.
500 ml of soft water having a temperature of 23
C. is placed in a beaker, equipped with a metal
screen having a mesh width of 4 mm mounted at
a height of 10 cm. A magnetic stirring bar in the
beaker is set in motion at about 200 rpm, and a
tablet is placed on top of the screen. The time
from the beginning of tablet addition until tablet
disintegration is measured using a stopwatch.
Disintegration is reached when all the tablet
fragments have fallen through the screen.

Testing Conditions for Wash-In Tests on

Detergent Tablets in Washing Machines:
Three tablets are placed in line in the wash-in
chamber of a washing machine. The washing
machine is connected to a 5 bar tap water
pressure line and started using the 60 C.
normal program. The wash-in time is 30
seconds, where the machine takes up water
only once. The test is performed four times in
total, so that 12 tablets are employed. The
remaining tablets are counted after each wash-
in process. The total amount of tablets which
have not been washed in is reported.
Determination of the Tablet Breaking Strength
To determine the tablet breaking strength, a type
TB30/TBH30MD tablet breaking strength tester
by Erweka Company is used, where the
breaking strength is determined using a strain
gauge having a force measuring capsule. The
measuring accuracy is 1 N. Following
appropriate programming, the tablet is placed in
the measuring device and the measuring
procedure is started. The instrument indicates
the breaking strength value.
Abrasion Test for Disintegrant Granulates
100 g of dried disintegrant granulate having a
particle size of >1 mm is placed in a 500 ml
beaker. A metal dissolver disc 3.5 cm in
diameter and connected to a stirrer motor is
immersed in the granulate. The stirrer motor is
adjusted to 800 rpm, and stirring is effected for
one minute, where the granulate undergoes
more or less significant abrasion. After this time,
the grain fraction percentage having <1 mm is
determined using screen analysis. The fraction
having <1 mm is reported as a percentage of the
total amount.
EXAMPLE
Having generally described this invention, a
further understanding can be obtained by
reference to certain specific examples which are
provided herein for purposes of illustration.
Examples M1-M7 and Comparative Examples
C1-C5
The disintegrants used in the Examples were
produced by wet-compacting on a pelletizing
press supplied by the Amandus Kabl Company.
The compression level was adjusted to be 1:3.
The water content of the mixtures prior to
compressing can be inferred from Table 1.
Following compacting, the granulates were dried
to the indicated moisture content on a roller
dryer from Babcock Company. Comparative
Example C5 was produced without additional
water on a WP 150 roller press from
Alexanderwerke. The molding pressure was
adjusted to 1.1 tons/cm2 . The granulates were
reduced on a friction chipper. Drying was
effected on a belt dryer.
The granulates have particle sizes between 0.3
and 2 mm, and the dust fraction below 0.1 mm is
reported in the Table.
TABLE 1
Formulations in % by weight used to
produce disintegrants, and properties of the
granulates
Disinteg C1 C3 C4 C M M M M M M M
rant 5 1 2 3 4 5 6 7
Cellulos 50 50 50 80 50 50 45 50 47 40 50
e*
Linear 12 12 12 20 12 12 10 10 12 10
PAA** .5 .5 .5 .5 .5 .5
Crosslin 2
ked
TABLE 1 Absorption of Liquid (Specific Porosity)
PAA***
CMC### 15 5 10 20 When comparing Example M2 according to the
Nio 0. 0. 0. 0 0. 0. 0. 0. 0 0. invention with Comparative Example C2, there
surfacta 5 5 5 5 5 5 5 5 were significant dissimilarities in the absorption
nt##
of liquid, which resulted from the compacting
Polymer 12.
process and the moisture content during
surfacta 5
nt# compacting. When using the moisture content
Water 37 37 37 0 37 37 29 29 30 29 37. according to the invention during compacting
used for .5 .5 .5 .5 5 and drying (M2), the result was 950 ml/kg
compact absorption of DBP, while the sample C2 which
ing (wt. had been dry-compacted and thus, compressed
%) in its capillary structure, gave an absorption of
Bulk 32 33 33 30 33 33 33 33 33 33 33 only 600 ml/kg DBP.
density 5 0 5 0 5 5 5 5 5 5 5
(g/l)
Thus, it is found that the absorbing capacity of
Moistur 18 10 1 3 6 4 3 3 4 5 3
the disintegrant granulate of the invention is
e (wt.
%) significantly increased compared to the
Dust 2 4 8 5 7 8 6 5 5 5 7 comparative product.
percent.
(wt. %) Example 1

% figures relate to the commercial form of The strength and wash-in tests of a detergent
the components including the usual water tablet containing phosphate and using the
content. granulates of the above-mentioned Examples
*Cellulose having a fiber length of 150 m, are as follows:
**Linear polycarboxylate having an average
molecular weight of 40,000. TABLE 2
***Crosslinked polycarboxylate having an
average molecular weight of about 2 Composition of the detergent tablet
million. Amount of raw material in % by weight
#
Polymer surfactant of acrylic acid/maleic
acid with 10 wt. % of grafted alkyl
polyglycoside.
## Sodium 35
Fatty alcohol surfactant (C12/14, EO =
tripolyphosphate
4.7).
### Sodium percarbonate 19
Carboxymethylcellulose
TAED 4
A roller-compacted cellulose from the
company Degussa AG, having the trade Fatty alcohol sulfate 14
name Elcema G 250 (5% moisture, bulk Linear 4
density 400 g/l), was used as Comparative alkylbenzenesulfonate
Example C2. Soda 8
TABLE 2 TABLE 3

Composition of the detergent tablet Disintegra Moistu Wash Streng Disintegrati

Amount of raw material in % by weight nt re -in th on
test
Defoamer, optical 6 of (%) (table [N] time [s]
brightener, CMC, Example ts not
phosphonate disint.
Microcrystalline 2 )
cellulose (200 m)
Enzyme mix 1 M6 5 0 59 7
Fatty alcohol ethoxylate 2 M7 3 0 58 9
C 12/14, EO = 4,7)
Disintegrant formulation 5
according to Table 3 shows that both the composition andin
Examples C1-C5 and cases having the same compositionthe
M1-M7 moisture content of the disintegrant granulate
have a significant effect on the tablet
disintegration time. Indeed, disintegrants having
Table 3 shows the strength and the results of the preferred content of 3-5 wt.-% of water, such
wash-in tests of each detergent tablet, using as in M2, exhibit the best tablet disintegration
various disintegrants. times. By additionally incorporating other
suitable swellable substances as disintegrant
TABLE 3
component, the disintegration properties can be
enhanced even further.
Disintegra Moistu Wash Streng Disintegrati
nt re -in th on
test Table 4 shows the effect of storage time (4
of (%) (table [N] time [s] weeks at 40 C/60% humidity, closed
Example ts not receptacle) on the wash-in behavior of tablets
disint. including disintegrants.
)
TABLE 4

C1 18 10 61 50 Phosphate-containing detergent tablet

C2 5 10 58 52 according to Table 2
C3 10 6 60 40 Moisture Swelling
M1 6 1 62 12 of kinetics
M2 4 0 65 9 disintegra Wash-in after 3
C4 1 3 58 25 nt test seconds
M3 3 0 57 8 (tablet)
M4 3 1 63 10 Example [%] immediate after 4 [mm
ly weeks ]
M5 4 1 58 9
TABLE 4 TABLE 5
Zeolite P 39 36
C4 1 3 3 0.85
M1 6 1 1 0.90 Fatty alcohol 4 7
M2 4 0 1 0.97 ethoxylate (C12/14,
C3 10 6 7 0.80 EO = 4.7)
C1 18 10 11 0.45 Sodium percarbonate 16 16

C2 6 10 11 0.47
TAED 4 4
M3 3 0 2.0
Fatty alcohol sulfate 10 11
M4 3 1 1.7

M5 4 1 1.6
Linear 3 3
M6 5 0 2.2
alkylbenzenesulfonate
Soda 4 4
Defoamer, optical 5 5
Table 4 shows that the inventive moisture brightener, CMC,
content in the disintegrant granulate results in phosphonate
superior properties of the tablets produced Enzyme mix 1 1
therewith in the important wash-in test, and that Microcrystalline 4 4
the swellability, having values of 0.9 and more, is cellulose (200 m)
superior to that of comparative products. Disintegrant 5 5
formulation according
Tablets having the disintegrant according to the to
invention show good storage stability. In addition
Examples C1, C2, M6,
M7
to cellulose, tablets according to M3-M6 also
Sodium citrate 5 5
include cellulose derivatives, and as a result,
have further improved swelling kinetics.
TABLE 5.1
Example 2
Formulation Disintegrant Wash- Strength
in test [N]
The strength and wash-in tests of detergent
tablets free of phosphate using the granulates of
the above-mentioned Examples are as follows: a) M6 1 57
b) M6 0 51
TABLE 5
a) M7 0 73
b) M7 0 59
Granulate of Example M6/M7 in zeolite-
Commercial 1 30
based detergent formulations
tablet
Amount of raw
Commercial 11 80
material in % by
tablet
weight
a) C1 10 58
Formulation a) b)
a) C2 12 59
TABLE 5.1 TABLE 6.1

Formulation Disintegrant Wash- Strength Formulation Wash-in test Strength [N]

in test [N]
a) 0 65
b) 1 60

In this case as well, the comparative granulates

C1 and C2 exhibit a significantly poorer
properties compared to the inventive product of
Example M6/M7. Commercially available tablets
show varying dissolving behavior. Tablets having
low strength undergo more rapid dissolution
than those having high strength
TABLE 6
The granulate of Example M3 resulted in
excellent disintegration times of tablets
containing disilicate.
Example 3
Compressed moldings to be used as stain
removing salt having the following composition:

Granulate of Example M3 in disilicate- TABLE 7

based detergent formulations
Amount of raw material in % by Amount of raw material in % by weight
weight
Formulation a) b)
Soda-disilicate 20
Amorphous disilicate 36 30 cogranulate
Soda 41
Fatty alcohol ethoxylate 2 7 Non-ionic surfactant 4
Fatty alcohol sulfate 11 15 TAED 7
Enzyme mix 1
Linear alkylbenzenesulfonate 4 2 Sodium percarbonate 24
Sodium percarbonate 16 16 Disintegrant 3
formulation
TAED 4 4 according to
Acrylate-maleate copolymer 3 Example M2 or C2
Soda 7 4
Sodium citrate 5 5
Microcrystalline Cellulose (200 m) 4 4 Softener, having the following composition
Defoamer, optical brightener, CMC, 5 4
phosphonate TABLE 8
Enzyme mix 1 1
Disintegrant formulation according to 5 5 Amount of raw material in % by weight
Example M3
TABLE 8 TABLE 10

Amount of raw material in % by weight Stain Water Machine

removing dish-
Zeolite 15 Property salt softener washing
Sodium hydrogen 32 agent
carbonate Composition accordg. accordg. accordg.
Citric acid 20 to a) to b) to c)
Polycarboxylate 17
Layer silicate 8
Processing aid 5 Strength [N] 175 210 185
Disintegrant 3 Disintegration 225 145 245
formulation according time [s]
to with
Example M2 or C2 disintegrant
C2
Disintegration 85 68 58
time [s]
Machine dishwashing agent, having the
with
following composition
disintegrant
M2
TABLE 9

Amount of raw material in % by weight

The tablet disintegration time of highly
compacted tablets including the disintegrant of
the invention is superior to that of comparative
Soda-silicate 20
cogranulate products.
Tripolyphosphate 35
Soda 20 Examples 4 and C7
Sodium perborate 12
TAED 4 Effect of High Surfactant Content on the

Enzyme mix 2 Properties of Disintegrant Granulates

Processing aid 3
Perfume, dyes 2 A granulate according to the invention (M2)

Disintegrant 2 having a content of nonionic surfactant of 0.5

formulation according wt.-% is compared with a granulate of same
to formulation and manufacturing technology,
Example M2 or C2 wherein the nonionic surfactant content has
been increased to 12 wt.-% (C7).

Results regarding the strength and disintegration

time of cleaning tablets.
The following Table 11 shows the swelling The priority document of the present application,
kinetics of both granulates after a swelling time European patent application EP 99 106 370.2
of 3.5 and 10 seconds. filed Mar. 29, 1999, is incorporated herein by
reference.
TABLE 11
PATENT CITATIONS
Path of swelling [mm] after
Example 3 s 5 s 10 s P
F u
C
i b
M2 0.97 1.0 1.1 it
l li
e
C7 0.33 0.42 0.44 d
i c
T
n a
P Appl it
g ti
a icant l
o
t e
The abrasion of the two samples M2 and C7 d n
e
a d
was compared in another test. n
t a
t
e t
TABLE 12 e
Tab
Abrasion test on samples M2 and C7 Henkel
let
US Feb Ma Komm
Example Grain fraction <1 con
590 1, y 4, anditge
mm in % by tain
039 199 199 sellsch
weight ing
9* 5 9 aft Auf
buil
Aktien
M2 10 ders
C7 35 Lever
Brother Cle
s ani
US Jun Apr
The results indicate that disintegrant granulates Compa ng
605 4, 18,
ny co
having a surfactant content outside the design 154 199 200
Divisio mp
according to the invention have significantly 5* 8 0
n Of osit
poorer characteristics both in swelling behavior Conop ions
and abrasion resistance. co, Inc.
* Cited by examiner
Obviously, numerous modifications and REFERENCED BY
variations of the present invention are possible
in light of the above teachings. It is therefore to
be understood that within the scope of the
appended claims, the invention may be
practiced otherwise than as specifically
described herein.
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*
tabl
ets
* Cited by examiner
CLASSIFICATIONS

U.S.
510/446, 510/224, 510/473, 5
Classi
10/298, 510/113, 510/340, 51
ficati
0/294
on
Intern
ationa
l C11D7/44, C11D17/06, C11D
Classi 3/22, C11D3/37, C11D17/00
ficati
on
Coop
erativ
e C11D3/222, C11D17/0073, C
Classi 11D3/3761, C11D17/06
ficati
on
Europ C11D17/00H8T, C11D17/06,
ean C11D3/22E, C11D3/37C6B
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t
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Photocatalyst article, anti-
fogging, anti-soiling
articles, and production
method of anti-fogging,
anti-soiling articles
US 6576344 B1
ABSTRACT

A photocatalyst article exhibits high

photocatalytic activity even in environments
illuminated by weak ultraviolet light or visible
light, expresses excellent anti-fogging and anti-
soiling properties, and retains good anti-fogging
and anti-soiling performance over long periods
and therefore has a high utilization value as an
anti-fogging, anti-soiling article. The
photocatalyst article contains an oxide
semiconductor and a compound which contains
at least one type of element selected from the
group comprised of Mg, Sc, V, Cr, Mn, Y, Nb,
Mo, Ru, W, and Re, at a content such that the
ratio (A/B) of the number of metal atoms of the
abovementioned element (A) to the number of
atoms of metal that comprise the
abovementioned oxide semiconductor (B) will be
about 0.20 to 2.

IMAGES(17)

CLAIMS(26)
What is claimed is:
1. A photocatalyst article consisting of a metallic
compound containing at least one type of
element (A) selected from the group consisting
of: magnesium, scandium, vanadium, chromium,
manganese, yttrium, niobium, molybdenum,
ruthenium, tungsten, and rhenium; and a metal
oxide semiconductor (B); at a content whereby
the ratio (A/B) of the number of metal atoms of
said element (A) to the number of atoms of
metal that comprise said metal oxide
semiconductor (B) is 0.20 to 2.
2. A photocatalyst article consisting of a metallic
compound containing at least one type of
element (A) selected from the group consisting
of: magnesium, scandium, vanadium, chromium,
manganese, yttrium, niobium, molybdenum,
ruthenium, tungsten, and rhenium; and a metal
oxide semiconductor (B); at a content whereby
the ratio (A/B) of the number of metal atoms of
said element (A) to the number of atoms of
metal that comprise said metal oxide
semiconductor (B) is 0.20 to 2; and 10 to 80
weight % of silicon oxide.
3. The photocatalyst article as set forth in claim
1 or 2, wherein said oxide semiconductor is
titanium oxide microparticles.
4. The photocatalyst article as set forth in claim
3, wherein said titanium oxide microparticles
have an average particle diameter of 2 to 120
nm.
5. The photocatalyst article as set forth in claim
1, wherein said at least one type of element is
selected from the group comprised of vanadium,
niobium, and molybdenum.
6. An anti-fogging, anti-soiling article comprising
a thin film formed on a substrate surface, the
thin film consisting of:
(1) a compound, containing at least one type of
element (A) selected from the group consisting
of: magnesium, scandium, vanadium, chromium,
manganese, yttrium, niobium, molybdenum,
ruthenium, tungsten, and rhenium, and
(2) a metal oxide semiconductor (B);
wherein the content ratio (A/B) of the number of
metal atoms of said element (A) to the number
of atoms of metal that comprises said metal
oxide semiconductor (B) is 0.20 to 2.
7. An anti-fogging, anti-soiling article comprising
a thin film formed on a substrate surface, the
thin film consisting of:
(1) a compound, containing at least one element
(A) selected from the group consisting of:
magnesium, scandium, vanadium, chromium,
manganese, yttrium, niobium, molybdenum,
ruthenium, tungsten, and rhenium; and,
(2) a metal oxide semiconductor (B),
silicon oxide, aluminum oxide, titanium oxide,
zirconium oxide, and cerium oxide.
15. The anti-fogging, anti-soiling article as set
forth in claim 13 or 14, wherein said alkali-
blocking film is a film having silicon oxide as the
main component thereof.

wherein the content ratio (A/B) of the number of
metal atoms of said element (A) to the number
of atoms of metal that comprise said metal oxide
semiconductor (B) is 0.20 to 2; and,
(3) 10 to 80 weight % of silicon oxide.
8. The anti-fogging, anti-soiling article as set
forth in claim 6 or 7, wherein said oxide
semiconductor is titanium oxide microparticles.
16. The anti-fogging, anti-soiling article as set
forth in claim 13, wherein said alkali-blocking
film has a thickness of 5 to 300 nm.
17. The anti-fogging, anti-soiling article as set
forth in claim 6, wherein an overcoat layer,
comprised of at least one type of metal oxide
selected from the group consisting of: silicon
oxide, aluminum oxide, titanium oxide, zirconium
oxide; and cerium oxide, is formed on top of said

9. The anti-fogging, anti-soiling article as set thin film.

forth in claim 8, wherein said titanium oxide

18. The anti-fogging, anti-soiling article as set
microparticles have an average particle diameter
forth in claim 17, wherein said overcoat layer
of 2 to 120 nm.
has silicon oxide as the main component.

10. The anti-fogging, anti-soiling article as set

19. The anti-fogging, anti-soiling article as set
forth in claim 6, wherein said at least one type of
forth in claim 17 or 18, wherein said overcoat
element is selected from the group consisting of:
layer has an average thickness of 0.1 to 50 nm.
vanadium, niobium, and molybdenum.
20. The anti-fogging, anti-soiling article as set
11. The anti-fogging, anti-soiling article as set
forth in claim 17, wherein said overcoat layer is
forth in claim 6, wherein said thin film has a
a porous body with a porosity of 1 to 50%.
thickness of 2 to 500 nm.
21. The anti-fogging, anti-soiling article as set
12. The anti-fogging, anti-soiling article as set
forth in claim 17, wherein said overcoat layer
forth in claim 6, wherein said substrate is glass.
contains silica microparticles at a content of 5 to

13. The anti-fogging, anti-soiling article as set 80 weight %.

forth in claim 12, wherein said substrate is glass

22. The anti-fogging, anti-soiling article as set
with an alkali-blocking film.
forth in claim 21, wherein at least part of said

14. The anti-fogging, anti-soiling article as set silica microparticles are chain-like silica

forth in claim 13, wherein said alkali-blocking microparticles.

film is comprised of at least one type of metal

oxide selected from the group consisting of:
23. The anti-fogging, anti-soiling article as set
forth in claim 22, wherein said chain-like silica
microparticles have a diameter of 10 to 20 nm
and a length of 40 to 300 nm.
24. The anti-fogging, anti-soiling article as set
forth in claim 6, wherein an organic substance
adhesion prevention layer is formed on top of
said thin film or on top of said overcoat layer.
25. The anti-fogging, anti-soiling article as set
forth in claim 24, wherein said organic
substance adhesion prevention layer is
comprised of a silicon oxide layer or an
organosilane, which contains at least one type of
functional group selected from the group
consisting of: polyalkylene oxide groups, alkyl
groups, alkenyl groups, and aryl groups in the
molecule, or a hydrolysate of such an
organosilane.
26. The anti-fogging, anti-soiling article as set
forth in claim 24 or 25, wherein said organic
substance adhesion prevention layer has an
average of 0.5 to 5 molecular layers in the
thickness direction.
DESCRIPTION
This application is a continuation of copending
application International Application
PCT/JP99/05304 filed on Sep. 28, 1999 and
which designated the U.S.
FIELD OF THE ART
The present invention concerns anti-fogging,
anti-soiling articles, wherein an anti-fogging film
or anti-soiling film is formed on the surface of a
substrate, such as glass, ceramic, plastic, or
metal, etc., methods of producing such articles,
and compositions for forming such articles. In
particular, the present invention concerns anti-
fogging, anti-soiling articles, which are suitable
as window glass, mirrors, lenses, air conditioner
heat exchanger fins, biological materials, film
sheets, showcases, etc., that are used for
construction, vehicles, optical parts, industrial
use, agricultural use, goods for daily use, and
residential and medical purposes, provide good
anti-fogging or anti-soiling performance over
long periods, and in particular exhibit their
performance under weak ultraviolet light or
visible light, the methods of producing such
articles, and compositions for forming such
articles.
BACKGROUND ART
Since priorly, there have been strong needs for
anti-fogging, anti-soiling glass plates, mainly in
the fields of automobiles and construction.
Especially with automobiles, the addition of anti-
fogging properties to window glass is becoming
an important issue from the standpoint of safe
driving.
Since priorly, various anti-fogging coatings for
glass articles have been examined. These
include, for example, a coating of an organic
and/or inorganic thin film containing a surfactant
(Laid-open Japanese Patent Publication
(Koukai) No. Hei 7-117202; first method), a
coating of hydrophilic polymer (Japanese Patent
Publication (Koukoku) No. Shou 61-9264;
second method), and a coating of an organic-
inorganic complex film containing an organic
hydrophilic functional group (Laid-open
Japanese Patent Publication (Koukai) No. Hei 6-
220428; third method), etc.
Also recently, anti-fogging, anti-soiling articles
have been proposed in which titanium oxide,
which is an oxide semiconductor that acts as a
photocatalyst, is coated onto the surface of a
substrate (Japanese Patent No. 2756474; fourth
method 4). This method makes use of the
phenomenon wherein the titanium oxide on the
glass surface absorbs ultraviolet light and the
organic substance adsorbed on the glass
surface is oxidized and decomposed efficiently
by the energy of the absorbed ultraviolet light to
provide a clean surface with significant
hydrophilic properties. Also, since the entire anti-
fogging, anti-soiling articles is made of inorganic
substances in terms of material, it is excellent in
mechanical strength, and even when dirt
becomes attached, the surface can be made
clean again and the hydrophilic surface can be
revived once it is exposed to ultraviolet light. As
long as the surface retains hydrophilic
properties, it will be difficult for black, lipophilic
dirt, which is the type of dirt encountered in
urban settings, to become attached, and any
attached dirt will be removed readily by rain (see
for example, Toshiki Komatsuzawa and
Toshikazu Nakaiye, New Anti-soiling Coatings,
Coating Technology, Jan., 1995, 94-99 (1995);
Shoichi Tanaka, Degradation by Soiling and
Anti-soiling Coating Technologies (Industrial
Coatings), Coating Technology, Oct., 1996 extra
issue, 95-102 (1995)). So-called self-cleaning
properties are thus provided, enabling use as
anti-soiling material.
In such methods using titanium oxide, the
photocatalytic activity of the titanium oxide may
be pointed out as an important factor that
determines anti-fogging and anti-soiling
performance. Methods for improving the
photocatalytic activity of titanium oxide include a
method in which titanium oxide is made to carry
a precious metal (see for example, Catalyst Vol.
19 No. 5, 334-350 (1977)), a method in which
titanium oxide is made to carry a vanadium
compound (see for example, Laid-open
Japanese Patent Publication No. Hei 7-275704),
a method in which niobium is dissolved in
titanium oxide (see for example, Laid-open
Japanese Patent Publication No. Hei 9-267037),
a method in which titanium oxide is doped with
fluorine (see for example, International Patent
Publication WO 98/05413).
Also, methods for obtaining titanium oxide that
exhibit photocatalytic activity under illumination
by visible light include a method for doping a
minute amount of dopant selected from the
group comprised of vanadium, chromium,
manganese, iron, cobalt, nickel, and copper
(Laid-open Japanese Patent Publication No. Hei
9-192496) and a method in which a minute
amount of metal ion, selected from the group
comprised of chromium, vanadium, copper, iron,
magnesium, silver, palladium, nickel,
manganese, and platinum, is injected into a
titanium oxide crystal. (Laid-open Japanese
Patent Publication No. Hei 9-262482).
With the abovementioned first method, although
the initial performance is excellent, since the
surfactant is consumed gradually, it has the
disadvantage of being short in life.
Although the second method is an effective
means depending on the application, it cannot
be applied to glass for automobiles, buildings,
etc., with which a relatively large mechanical
strength is required.
Although the third method was proposed so that
both anti-fogging performance and mechanical
strength will be provided at the same time, both
types of performance are limited with this
method. Also with this method, the anti-fogging
performance drops significantly once dirt, etc.,
become attached.
Though the fourth method in principle has
features that cannot be realized by the other
methods, since the intensity of ultraviolet light in
the interior of a vehicle or building is extremely
weak, anti-fogging article that can be put to
practical use have not yet been obtained by this
method. Also with anti-soiling articles, there are
problems wherein use is difficult at locations
where the intensity of ultraviolet light is weak.
On the other hand, compositions and article
obtained by the abovementioned prior arts that
purport to improve the photocatalytic activity of
titanium oxide upon ultraviolet light illumination
or the expression of photocatalytic activity under
visible light illumination do not exhibit adequate
anti-fogging performance under illumination of
weak ultraviolet light or visible light, and since
the improvement of hydrophilicity is also
inadequate, it cannot be said that such
compositions and article are improved
significantly in anti-fogging and anti-soiling
performance over ordinary titanium oxide.
The present invention has been made in view of
the prior arts and an article thereof is to provide
compositions, which express excellent anti-
fogging and anti-soiling properties even under
environments of weak ultraviolet light or visible
light and can maintain good anti-fogging and
anti-soiling performance over long periods, and
anti-fogging, anti-soiling articles with excellent
anti-fogging and anti-soiling performance that
can be used, for example, in window glass for
automobiles and buildings, mirrors, optical parts,
as well as glasses, etc.
DISCLOSURE OF THE INVENTION
As a result of diligent examination towards
achieving the above article, the present
inventors have found that (1) by adding a
significantly large amount of a specific metal
compound to titanium oxide or other oxide
semiconductor, the hydrophilicity is improved by
illumination of weak ultraviolet light or visible
light, (2) by adding silicon oxide to this
composition, the anti-fogging and anti-soiling
performance is improved further, and (3) the
performance is improved further if the titanium
oxide takes the form of microparticles.
The present inventors also found that (4) when
an overcoat layer comprised of metal oxide is
formed after forming such a composition as a
thin film on a substrate, the anti-fogging and
anti-soiling properties are improved and/or (5) by
forming an organic substance adhesion
prevention layer comprised of a silicon oxide
layer or an organosilane layer, the anti-fogging
and anti-soiling performance is improved, and
have thus come to complete the present
invention.
That is, the present invention provides in a
photocatalyst article including oxide
semiconductors, a photocatalyst article
characterized in containing a compound, which
contains at least one type of element selected
from the group comprised of Mg (magnesium),
Sc (scandium), V (vanadium), Cr (chromium),
Mn (manganese), Y (yttrium), Nb (niobium), Mo
(molybdenum), Ru (ruthenium), W (tungsten),
and Re (rhenium), at a content whereby the ratio
(A/B) of the number of metal atoms of the
abovementioned element (A) to the number of
atoms of metal that comprises the oxide
semiconductor (B) will be 0.1 to 2. Examples of
oxide semiconductors that may be used include
metal oxide semiconductors, such as TiO2, ZnO,
SnO2, SrTiO3, WO3, Bi2O3, Fe2O3, In2O3, MoO2,
etc. Among these, titanium oxide (TiO2), which is
high in catalytic activity and exhibits excellent
physicochemical stability, is used preferably. In
the case where WO3 (or MoO2) is used as the
oxide semiconductor, a compound besides the
oxide of W (or Mo) is used as the
abovementioned compound.
The present invention also provides an anti-
fogging, anti-soiling articles with which a thin
film, which contains
(1) at least one type of element selected from
the group comprised of Mg, Sc, V, Cr, Mn, Y, Nb,
Mo, Ru, W, and Re and
(2) an oxide semiconductor at contents such that
the ratio (A/B) of the number of metal atoms of
the abovementioned element (A) to the number
of atoms of metal that comprises the oxide
semiconductor (B) will be 0.1 to 2, is formed on
the surface of a substrate.
The photocatalyst article of the present invention
may take on any form, such as powder, fiber,
flakes, film, coating, plate-like members, etc.
When the minimum dimension or film thickness
of the photocatalyst article exceeds 500 nm, the
portion that exceeds this dimension (the deep
part measured from the surface) will be lowered
in photoactive catalytic action. Thus, the
minimum dimension or film thickness of the
photocatalyst article is preferably 2 to 2000 nm.
This photocatalyst article can be produced
favorably by a sol-gel method.
The case where a photocatalyst thin film, which
contains titanium oxide as the oxide
semiconductor, is coated onto a substrate
surface shall now be described.
Three conditions must be met simultaneously in
order to obtain excellent anti-fogging and anti-
soiling functions using a photocatalyst. One is
that the organic material, which becomes
adsorbed onto the surface of the photocatalyst
film and causes fogging and soiling, will be
oxidized and decomposed efficiently (high
photocatalytic activity). The second condition is
that organic material will not become adsorbed
onto the surface readily (adsorption prevention
property). The third condition, which is especially
required of anti-fogging property, is that the
apparent contact angle of an attached water
drop is small (low contact angle). Only when the
above three conditions are satisfied can good
anti-fogging and anti-soiling properties be
expressed over long periods.
A high photocatalytic activity cannot be obtained
by simply coating a titanium oxide film or other
photocatalyst film directly onto the surface of a
glass substrate. This is because Na ions and
other alkali metal ions which diffuse from inside
a glass substrate contain alkali metals to the
exterior in the process of heat treatment and
combine chemically with the titanium oxide to
lower the crystallinity of the titanium oxide in the
film. When a glass material containing an alkali
metal is to be used as the substrate, a silicon
oxide film or other alkali-blocking film is provided
on the glass substrate to prevent the above-
described lowering of crystallinity of the titanium
oxide film, and the photocatalyst film containing
titanium oxide is then coated above this alkali-
blocking film.
[Alkali-Blocking Film]
A film of a composition with a single component
or multiple components, selected from the group
comprised of silicon oxide, aluminum oxide,
titanium oxide, zirconium oxide, and cerium
oxide, is favorably used as the above-described
alkali-blocking film. Among these, a film, having
a single component of silicon oxide (silica) or
multiple components with silicon oxide as the
main component, is preferable, and a two-
component metal oxide film of silicon oxide and
zirconium oxide is even more preferable. A metal
oxide having silicon oxide as the main
component is preferable since it will be low in
the refractive index and enable film formation
without considerably degrading the optical
properties of the glass plate. Further, a two-
component metal oxide of silicon oxide and
zirconium oxide is even more preferable since
the alkali-blocking performance is extremely
high and an oxide with a zirconium oxide content
of 1 weight % or more and 30 weight % or less
is especially preferable.
When this content is less than 1 weight %, the
alkali-blocking performance improvement effect
will not differ much from that of silicon oxide
alone, and when the content is higher than 30
weight %, not only will the alkali-blocking
performance improvement effect not increase
further but since there will be a tendency for the
reflectance to increase due to the increased
refractive index, the control of the optical
properties of the glass plate will be difficult.
The thickness of the above-described alkali-
blocking film is preferably 5 nm or more and 300
nm or less. When the thickness is less than 5
nm, the alkali-blocking effect will not be effective,
and a thickness of more than 300 nm is not
preferable since interference colors due to the
film will become significantly visible and control
of the optical properties of the glass plate will be
difficult.
The above-described alkali-blocking film can be
formed by a known method. Examples include
sol-gel methods (for example, Yuji Yamamoto,
Kannichi Kamiya, Sumio Tsukuribana, Ceramics
Association Journal, 90, 328-333 (1982)), liquid-
phase precipitation methods (for example,
Japanese Patent Publication No. Hei 1-59210,
Japanese Patent Publication No. Hei 4-13301),
vacuum film-forming methods (vacuum vapor
deposition, sputtering), baking and spray coating
methods (for example, Laid-open Japanese
Patent Publication No. Sho 53-124523, Laid-
open Japanese Patent Publication No. Sho 56-
96749), CVD methods (for example Laid-open
Japanese Patent Publication No. Sho 55-90441,
Laid-open Japanese Patent Publication No. Hei
1-201046, Laid-open Japanese Patent
Publication No. Hei 5-208849), etc.
[Photocatalyst Film]
The photocatalyst film contains (1) a compound
containing at least one type of element selected
from among Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru,
W, and Re and (2) an oxide semiconductor and
preferably contains (3) silica as well.
As the abovementioned oxide semiconductor,
titanium oxide is preferably used from the
standpoint of high catalytic activity and excellent
physicochemical stability. The following
description shall concern the case where
titanium oxide is used as the oxide
semiconductor.
Compounds that may be used as the compound
containing at least one type of element selected
from among Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru,
W, and Re include chlorides, nitrates, sulfates,
acetylacetone compounds, ammonium salts,
phosphates, hydroxides, ortho-acids, iso-
polyacids, hetero-polyacids, ortho-acid salts, iso-
polyacid salts, hetero-polyacid salts, oxides,
etc., of the respective metals. Among the above
elements, V, Nb, and Mo are preferably used.
In a photocatalyst film, the ratio (A/B) of the
number of metal atoms of the abovementioned
compound (A) to the number of atoms of Ti (B)
is greater than or equal to 0.20 and less than or
equal to 2. When this ratio is less than 0.20,
anti-fogging and anti-soiling performance will not
be exhibited by illumination of weak ultraviolet
light or visible light, and a ratio that is greater
than 2 is not preferable since the transparency
of the thin film will then be low and the durability
will be lowered as well. In order to shorten the
period for the exhibition of anti-fogging and anti-
soiling properties, the abovementioned ratio is
preferably 0.3 or more, and in order to keep the
haze of the film at a low level, the ratio is
preferably less than or equal to 1.0.
When the ratio (A/B) of the number of metal
atoms of the abovementioned compound (A) to
the number of atoms of Ti (B) is greater than or
equal to 0.20 and less than or equal to 2, the
abovementioned compound tends to exist in
aggregated form and the abovementioned
compound forms a type of junction interface with
the titanium oxide crystal. Since the separation
of positive holes and electrons resulting from
illumination of light is promoted at this interface,
hydrophilicity is exhibited even under weak
ultraviolet light. It is furthermore considered that
hydrophilicity is exhibited even under visible light
illumination due to the effective injection of
charges, that arise in the abovementioned
compound due to visible light illumination, into
the titanium oxide. It can thus be said that an
article in which only a minute amount of the
compound is added or a uniform solid solution,
which does not have an effective junction
interface of the abovementioned compound and
titanium oxide, will not exhibit anti-fogging and
anti-soiling properties under illumination by weak
ultraviolet light or visible light.
Though the photocatalyst film of the present
invention is made using ordinary thin-film
production methods, among such methods, sol-
gel methods are preferably applied.
The coating solution for forming the
photocatalyst film on the substrate is prepared
by mixing the abovementioned compound
containing at least one type of element selected
from among Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru,
W, and Re, the titanium oxide raw material, and
the silicon oxide or silica compound in a solvent
and if necessary, adding water, an acid catalyst,
a stabilizer, and a dispersing agent.
Hydrolyzable, condensation-polymerizable
organic titanium compounds, titanium
tetrachloride, hydrolysates of such compounds,
and titanium oxide, titanium oxide colloids, and
titanium oxide microparticles, which are obtained
by heat treatment of the aforementioned
compounds may be used favorably as the raw
material for the titanium oxide microparticles that
are to be made to exist within the film. Also,
commercially available suspensions in which
titanium oxide microparticles are dispersed in a
silica binder may be used readily and thus
favorably. Examples of commercially available
suspensions include ST-K01 (made by Ishihara
Sangyo Co., Ltd., titanium oxide content: 8
weight %, silica binder content: 2 weight %) and
CA-62 (made by Taki Chemical Ltd., titanium
oxide content: 6 weight %, silica binder content:
1.5 weight %).
Titanium alkoxides, such as the methoxide,
ethoxide, propoxide, butoxide, etc., of titanium,
may be used favorably in a solitary form or as a
mixture as the abovementioned hydrolyzable,
condensation-polymerizable organic titanium
compound.
Acetylacetone is preferably added as a stabilizer
for stabilizing an abovementioned organic
titanium compound, titanium tetrachloride, or a
hydrolysate of such a compound and forming a
thin film of good external appearance. In terms
of the number of moles, acetylacetone is
preferably added at an amount that is two times
that of the Ti in the abovementioned organic
titanium compound, titanium tetrachloride, or
hydrolysate thereof.
The abovementioned titanium oxide
microparticles preferably have an average
particle diameter of 2 nm or more and 120 nm or
less. If the average particle diameter is less than
2 nm, the photocatalytic activity will be
inadequate and the anti-fogging and anti-soiling
properties will not be very good. An average
particle diameter greater than 120 nm is
unfavorable since the transparency of the thin
film will then be low and the film will have a high
haze factor. The most favorable particle
diameter is 8 nm or more and 80 nm or less, and
high transparency and high anti-fogging and
anti-soiling performance will be secured within
this range.
A favorable content of silica to be contained in
the photocatalyst film is 10 weight % or more
and 80 weight % or less, preferably 20 weight %
or more and 60 weight % or less, and more
preferably 30 weight % or more and 50 weight %
or less. When this content is less than 10 weight
%, though the photocatalytic action itself will not
be lowered, the anti-fogging and anti-soiling
performance will be short in endurance, and
when the content is greater than 80 weight %,
since the titanium content oxide will be low, the
anti-fogging and anti-soiling performance will
tend not to be exhibited by illumination of light.
Hydrolyzable and condensation-polymerizable
organosilicon compounds, chlorosilyl-group-
containing compounds, hydrolysates of such
compounds, and silicon oxide, colloidal silica,
silica microparticles, etc., obtained by heat
treatment of the aforementioned compounds are
used favorably as the silica (silicon oxide) in the
film. In this case, an organosilicon compound or
a chlorosilyl-group-containing compound may be
used in solitary form or these may be mixed
together. The silica in the film does not have to
exist in the form of complete SiO2 and may exist
in a form bonded to an alkoxyl group, hydroxyl
group, etc.
Silicon alkoxides, such as the methoxide,
ethoxide, propoxide, butoxide, etc., of silicon,
may be used favorably in a solitary form or as a
mixture as the abovementioned hydrolyzable,
condensation-polymerizable organosilicon
compound, and high molecular weight type alkyl
silicates, such as Ethyl Silicate 40, made by
Colcoat K.K. and MS56, made by Mitsubishi
Chemical, Ltd. may also be used. Commercially
available alkoxysilane hydrolysate solutions,
such as HAS-10, made by Colcoat K.K.,
Ceramica G-91 and G-92-6, made by Nippan Though the solvent of the solution, that contains
Lab. Corp., and Atoron NSI-500,made by
Nippon Soda Co., Ltd., etc., may be used as the
abovementioned hydrolysate of organosilicon
compound.
The abovementioned chlorosilyl-group-
containing compound is a compound having at
least one chlorosilyl group (SiClnX3-n, where n
is 1, 2, or 3,is hydrogen or an alkyl group,
alkoxy group, or acyloxy group with 1 to 10
carbon atoms) in the molecule. Among such
compounds, those with at least two chlorine
atoms are preferable and chlorosilanes, in which
at least two of the hydrogen atoms in silane,
SinH2n+2 (where n is an integer from 1 to 5), have
been replaced by chlorine and the other
hydrogens have been replaced by an
abovementioned alkyl group, alkoxy group, or
acyloxy group, and condensation polymers of
such chlorosilanes are preferable. Examples
include tetrachlorosilane (silicon tetrachloride,
SiCl4), trichlorosilane (SiHCl3),
trichloromonomethylsilane (SiCH3Cl3),
dichlorosilane (SiH2Cl2), and Cl(SiCl2O)n
SiCl3 (where n is an integer from 1 to 10). The
hydrolysates of the abovementioned chlorosilyl-
group-containing compounds may also be used
and one or several from among such
compounds may be used in combination. The
most preferable chlorosilyl-group-containing
compound is tetrachlorosilane. Since the
chlorosilyl group is extremely high in reactivity, a
dense coated film can be formed through self-
condensation or condensation reaction with the
substrate surface and a film that can adequately
withstand practical use may be obtained even by
drying at a low temperature (room temperature
to 250 C.) in some cases.
the abovementioned organosilicon compound,
or chlorosilyl-group-containing compound or a
hydrolysate of such a compound, can basically
be any solvent as long as it can practically
dissolve the abovementioned organosilicon
compound or chlorosilyl-group-containing
compound or hydrolysate of such a compound,
methanol, ethanol, propanol, butanol, and other
alcohols are most preferable and the total
concentration of the abovementioned
organosilicon compound, chlorosilyl-group-
containing compound, and hydrolysate of such a
compound in the solvent should be 0.001 to 30
weight %.
Water is necessary for the hydrolysis of the
abovementioned organosilicon compounds. The
water may either be acidic or neutral, but in
order to promote hydrolysis, water that is made
acidic with hydrochloric acid, nitric acid, sulfuric
acid, acetic acid, citric acid, sulphonic acid, etc.,
which have a catalytic effect, is preferably used.
Although the added amount of acid is not limited
in particular, a mole ratio, with respect to the
organosilicon compound, of 0.001 to 20 is
preferable. A mole ratio of added acid of less
than 0.001 is not preferable since the hydrolysis
of the organosilicon compound will not be
promoted adequately and a mole ratio of more
than 20 is not preferable in terms of handling
because the acidity of the solution will be too
high. In terms of just hydrolysis, the upper limit
of the mole ratio, with respect to the
organosilicon compound, of the added acid is 2.
The degree of progress of hydrolysis will not
change much when the amount of acid is
increased further. However, with the addition of
more acid, the strength of the film may increase
significantly and a film that can adequately
withstand practical use even upon drying at a
low temperature (room temperature to 250 C.)
may be obtained in some cases.
The coating solution with which an increase of
strength of the photocatalyst film may be seen
preferably has a composition such that the
concentration of the compound containing at
least one type of element selected from among
Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W, and Re is
0.0002 to 30 weight %, the concentration of the
raw material of the titanium oxide microparticles
is 0.0002 to 30 weight %, the concentration of
silicon oxide as calculated from the
organosilicon compound or hydrolysate thereof
is 0.001 weight % or more and 3 weight % or
less, the acid concentration is 0.001 moles/L or
more and 1 mole/L or less, and the water
content is 0.001 weight % or more and 10
weight % or less. A more preferable composition
is such that the concentration of the
abovementioned metal oxide is 0.01 weight % or
more and 0.6 weight % or less, the
abovementioned acid concentration is 0.01
moles/L or more and 0.3 moles/L or less, and
the abovementioned water content is 0.001
weight % or more and 3 weight % or less.
Nitric acid or hydrochloric acid is preferably used
as the acid in this case, and an acid with a
concentration that is 0.3 times or more than that
of the water content is preferably used. That is, if
an acid is to be used in the form of aqueous
solution, the solution is preferably a high-
concentration acid with a concentration of 23.1%
or more. When an acid is to be used in the form
of an ethanol solution, if for example the ethanol
solution contains 0.5 weight % of water, the
concentration of the acid in the ethanol solution
is preferably 0.15 weight % or more.
The mole ratio, with respect to the
abovementioned organosilicon compound, of the
added amount of water necessary for hydrolysis
of the organosilicon compound is preferably 0.1
to 100. When the mole ratio of the added
amount of water is less than 0.1, the hydrolysis
of the organometallic compound will not be
promoted adequately and a mole ratio of more
than 100 is not preferable since the stability of
the solution will tend to be low.
When an abovementioned chlorosilyl-group-
containing compound is to be used, the water
and acid do not have to be added necessarily.
Even when no additional water or acid is added
at all, the hydrolysis will progress due to the
water contained in the solvent or the water
contained in the atmosphere. Also the
hydrochloric acid in the solution will dissociate in
accompaniment with this hydrolysis, and this will
cause the hydrolysis to progress further.
However, there is no problem in adding
additional water or acid.
The abovementioned organosilicon compound
or chlorosilyl-group-containing compound is
dissolved in the solvent, the catalyst and water
are added, and hydrolysis is carried out for 5
minutes to 2 days at a fixed temperature
between 10 C. and the boiling point of the
solution. The hydrolyzable, condensation-
polymerizable organic titanium compound,
titanium tetrachloride, hydrolysate of such a
compound, or titanium oxide, titanium oxide
colloid, or titanium oxide microparticles, are
obtained by heat treatment of an
aforementioned compound and, where
necessary, the stabilizer and dispersing agent
are added, and the reaction is continued, if
necessary, at a fixed temperature between 10
C. and the boiling point of the solution for 5
minutes to 2 days. The solution of a compound
containing at least one type of element selected
from among Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru,
W, and Re is then added to obtain the coating
solution for forming the photocatalyst film. A
catalyst and water do not have to be added in
particular if a chlorosilyl-group-containing
compound is to be used. The titanium oxide
microparticles and the compound containing at
least one type of element selected from among
Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W, and Re
may be added prior to the above-described
hydrolysis process. There are no particular
restrictions in the order in which these are added
and mixed. Also, in order to omit the hydrolysis
of the organosilicon compound, an
abovementioned commercially available solution
of organosilicon compound hydrolysate may be
used. The coating solution that is obtained may
thereafter be diluted with a suitable solvent in
accordance with the coating method.
The photocatalyst film may be formed on the
substrate by applying the above-described
coating solution for forming the photocatalyst
film onto the substrate and then performing
drying, and where necessary, heat treatment.
Examples of the substrate in the present
invention include transparent or non-transparent
plate-like members, fibers, powders, films,
flakes, and various other formed articles, etc.
that are made of glass, ceramic, plastic, or
metal, etc. In the case where a plastic substrate
or other substrate which has only a few
hydrophilic groups on the substrate surface is to
be used, the above-described coating is
preferably performed after making the surface
hydrophilic in advance by being subjected to
plasma treatment or corona discharge
treatment, or by making the substrate surface
hydrophilic by illuminating with ultraviolet rays of
a wavelength in the vicinity of 200 to 300 nm in
an atmosphere containing oxygen.
Though depending on the conditions of
attachment of dirt on the substrate, the above-
described coating solution for forming the
photocatalyst film may be repelled and be
obstructed from being coated uniformly, this
situation may be improved upon by performing
washing or surface modification of the substrate
surface. Washing and surface modification
methods include degreasing washing with
alcohol, acetone, hexane, or other organic
solvents, washing with an alkali or acid, methods
of polishing the surface with a polishing agent,
ultrasonic washing and other washing methods,
and surface modification methods, such as
ultraviolet ray illumination treatment, ultraviolet
ray ozone treatment, plasma treatment, corona
discharge treatment, heat treatment, etc.
A known technique may be used as the method
for coating, and though not restricted in
particular, examples include methods using a
spin coater, roll coater, spray coater, curtain
coater or other device, methods, such as the
dipping and drawing method (dip coating
method), the flow application method (flow
coating method), and various printing methods,
such as screen printing, gravure printing, and
curved surface printing.
After forming the above-described photocatalyst
film on the substrate, the substrate is dried at a
temperature between room temperature and
150 C. for 1 minute to 2 hours and thereafter
heat treated if necessary at a temperature
between 350 C. and the heat resistance
temperature of the substrate in order to achieve
densification, improvement of the crystallinity of
titanium oxide, or conversion of the added
compounds into oxides. The heat resistance
temperature of the substrate refers to the upper
limit temperature at which the characteristics of
the substrate can be retained for practical
purposes, and refers, for example, to the
softening point or devitrification point (normally,
600 to 700 C.) in the case of a glass substrate
or, for example, to the glass transition point,
crystallization temperature, or decomposition
point in the case of a plastic substrate. Though
the heat treatment conditions will be restricted
according to the type of substrate, in the case of
a glass substrate, heat treatment is preferably
carried out at 350 to 650 C. for 5 minutes to 2
hours.
The thickness of the photocatalyst film is
preferably 2 to 500 nm. A thickness of less than
2 nm is not preferable since light cannot be
absorbed adequately and anti-fogging and anti-
soiling performance will be low.
A thickness of more than 500 nm is not
preferable since the light carrier that is formed
inside the film will not diffuse to the outer surface
of the film, thus causing the photocatalytic
activity to drop, the anti-fogging and anti-soiling
performance to drop, and interference colors to
be significantly visible. When the thickness is
less than 20 nm, the retention of anti-fogging
and anti-soiling performance when light is not
shone will tend to be low and when the
thickness is greater than 200 nm, the wear
resistance will tend to be low. Thus the thickness
of the photocatalyst film is more preferably 20 to
200 nm.
[Overcoat Layer]
With the present invention, anti-fogging and anti-
soiling performance are further improved by the
formation of an overcoat layer on top of the
above-described photocatalyst film.
The abovementioned overcoat layer is a thin film
comprised of at least one type of metal oxide
selected from among silicon oxide, aluminum
oxide, titanium oxide, zirconium oxide, and
cerium oxide and preferably contains 50 weight
% or more of silicon oxide.
The coating of the overcoat layer may be formed
by applying, onto the substrate on which the
above-described photocatalyst film has been
formed, a solution containing at least one type of
compound selected from the group comprised of
hydrolyzable, condensation-polymerizable
organometallic compounds of silicon, aluminum,
titanium, zirconium, and cerium, chlorosilyl-
group-containing compounds, and hydrolysates
of such compounds or a solution obtained by
adding silica microparticles to an
abovementioned solution. The abovementioned
silica microparticles are preferably used in the
form of a solvent-dispersed sol (colloidal
solution).
Examples of silica sols include commercially
available water-dispersed sols, such as
Snowtex-OL, Snowtex-O, Snowtex-OUP, dispersing agent may be added. The dispersing
and Snowtex-UP, made by Nissan Chemical
Industries, K.K., and commercially available
organic-solvent-dispersed silica sols, such as
IPA-ST and XBA-ST, made by Nissan
Chemical Industries, K.K.
Chain-like microparticles are preferable as the
above-described silica microparticles. By using
microparticles of chain-like shape, the overcoat
layer surface will be of an uneven profile that is
intertwined in three-dimensions, and an uneven
surface profile of high anti-fogging performance
and high anti-fogging property retention can thus
be formed. Examples of chain-like colloids
include Snowtex-OUP and Snowtex-UP,
which are silica sols made by Nissan Chemical
Industries, K.K., and these have a diameter of
10 to 20 nm and a length of 40 to 300 nm.
Though the dispersing medium for the
abovementioned silica microparticles is not
limited in particular as long as the silica
microparticles are practically dispersed in a
stable manner, a single or mixed medium of
water, methanol, ethanol, propanol, etc., is
preferable and water is especially preferable.
Water and such lower alcohols mix readily with
solutions containing the abovementioned
organometallic compounds and are preferable
since they can be removed readily by drying
during film formation or by heat treatment after
film formation. Among the above, water is most
preferable in terms of the production
environment.
In adding the abovementioned silica
microparticles to the solution containing the
abovementioned organometallic compound or
chlorosilyl-group-containing compound, a
agent is not restricted in particular, and for
example, electrolytes, such as sodium
phosphate, sodium hexametaphosphate,
potassium pyrophosphate, aluminum chloride,
and iron chloride, various surfactants, various
organic polymers, silane coupling agents,
titanium coupling agents, and other substances
that are generally used as dispersing agents
may be used. The amount added is normally
0.01 to 5 weight % with respect to the
abovementioned silica microparticles.
Though the abovementioned hydrolyzable,
condensation-polymerizable organometallic
compound, that is to be contained solitarily or
along with the abovementioned silica
microparticles in the coating solution for forming
the overcoat layer, may basically be any
compound that can undergo hydrolytic
degradation and dehydration condensation,
metal alkoxides and metal chelates are
preferable.
As specific examples of metal alkoxides, the
methoxide, ethoxide, propoxide, butoxide, etc.,
of silicon, aluminum, zirconium, titanium, or
cerium may be used favorably in a solitary or
mixed form. As examples of metal chelates, the
acetylacetate chelate of silicon, aluminum,
zirconium, titanium, etc., may be used favorably.
Silicon alkoxides that may be used include high
molecular weight type alkyl silicates, such as
Ethyl Silicate 40, made by Colcoat K.K., Ltd.
and MS56, made by Mitsubishi Chemical Ltd.
Silicon alkoxide hydrolysates that may be used
include commercially available alkoxysilane
hydrolysate solutions, such as HAS-10, made
by Colcoat K.K., Ltd., Ceramica G-91 and
Ceramica G-92-6, made by Nippan Lab. Corp.,
and Atoron NSI-500, made by Nippon Soda
Co., Ltd.
The chlorosilyl-group-containing compound, that
is to be contained solitarily or along with the
abovementioned silica microparticles in the
coating solution for forming the overcoat layer, is
a compound having at least one chlorosilyl
group (SiClnX3-n, where n is 1, 2, or 3,is
hydrogen or an alkyl group, alkoxy group, or
acyloxy group with 1 to 10 carbon atoms) in the
molecule. Among such compounds, those with
at least two chlorine atoms are preferable and
chlorosilanes, in which at least two of the
hydrogen atoms in silane, SinH2n+2 (where n is an
integer from 1 to 5), have been replaced by
chlorine and the other hydrogens have been
replaced by an abovementioned alkyl group,
alkoxy group, or acyloxy group, and
condensation polymers of such chlorosilanes
are preferable.
Examples include tetrachlorosilane (silicon
tetrachloride, SiCl4), trichlorosilane (SiHCl3),
trichloromonomethylsilane (SiCH3Cl3),
dichlorosilane (SiH2Cl2), and Cl(SiCl2O)n
SiCl3 (where n is an integer from 1 to 10). The
hydrolysates of the above chlorosilyl-group-
containing compounds may also be used and
these may be used solitarily or several such
compounds may be used in combination. The
most preferable chlorosilyl-group-containing
compound is tetrachlorosilane. Since the
chlorosilyl group is extremely high in reactivity, a
coat of high wear resistance can be formed
through self-condensation or condensation
reaction with the substrate surface and a film
that can adequately withstand practical use even
upon drying at a low temperature (room
temperature to 250 C.) may be obtained in
some cases.
The solvent of the solution, that contains an
abovementioned organometallic compound or
chlorosilyl-group-containing compound or
hydrolysate of such a compound, can basically
be any solvent as long as it can practically
dissolve the abovementioned organometallic
compound or chlorosilyl-group-containing
compound or hydrolysate of such a compound.
To be more specific, methanol, ethanol,
propanol, butanol, and other alcohols are most
preferable and the total concentration of the
abovementioned organometallic compound,
chlorosilyl-group-containing compound, and
hydrolysate of such a compound in the solvent
may be 0.00001 to 30 weight %.
Water is necessary for the hydrolysis of the
abovementioned organometallic compounds.
The water may either be acidic or neutral, but in
order to promote hydrolysis, water that is made
acidic with hydrochloric acid, nitric acid, sulfuric
acid, acetic acid, citric acid, sulphonic acid, etc.,
which have a catalytic effect, is preferably used.
The mole ratio, with respect to the
abovementioned organometallic compound, of
the added amount of water necessary for
hydrolysis of the organometallic compound is
preferably 0.1 to 100. When the mole ratio of the
added amount of water is less than 0.1, the
hydrolysis of the organometallic compound is
not promoted adequately and a mole ratio of
more than 100 is not preferable since the
stability of the solution will tend to be low.
Although the added amount of acid is not limited
in particular, a mole ratio, with respect to the
organometallic compound, of 0.001 to 20 is
preferable. A mole ratio of added acid of less
than 0.001 is not preferable since the hydrolysis
of the organometallic compound will not be
promoted adequately and a mole ratio of more
than 20 is not preferable in terms of handling
because the acidity of the solution will be too
high. In terms of just hydrolysis, the upper limit
of the mole ratio, with respect to the
organometallic compound, of the added acid is
2. The degree of progress of hydrolysis will not
change much when the amount of acid is
increased further. However, with the addition of
more acid, the strength of the film may increase
significantly and a film that can adequately
withstand practical use even upon drying at a
low temperature (room temperature to 250 C.)
may be obtained in some cases.
A coating solution with which such an increase
of film strength of the over coat layer can be
seen preferably has a composition wherein the
concentration of metal oxide, as calculated from
the amount of organometallic compound or
hydrolysate thereof, is 0.00001 weight % or
more and 0.3 weight % or less, the acid
concentration is 0.0001 moles/L or more and 1.0
mole/L or less, and the water content is 0.001
weight % or more and 10 weight % or less. More
preferably, the coating solution has a
composition wherein the abovementioned
concentration of metal oxide is 0.001 weight %
or more and 0.1 weight % or less, the
abovementioned acid concentration is 0.01
moles/L or more and 0.3 moles/L or less, and
the abovementioned water content is 0.001
weight % or more and 3 weight % or less.
Nitric acid or hydrochloric acid is preferable as
the acid to be used in this case, and the use of
an acid with a concentration of 0.3 times or more
the water content is preferable. That is, when an
acid in the form of aqueous solution is to be
used, the acid is preferably a high-concentration
acid with a concentration of 23.1% or more.
When the acid is to be used in the form of an
ethanol solution, if for example the ethanol
solution has a water content of 0.5 weight %, the
concentration of acid in the ethanol solution is
preferably 0.15 weight % or more.
When an abovementioned chlorosilyl-group-
containing compound is to be used, the water
and acid do not have to be added necessarily.
Even when no additional water or acid is added
at all, the hydrolysis will progress due to the
water contained in the solvent or the water
contained in the atmosphere. The hydrochloric
acid in the solution will dissociate in
accompaniment with this hydrolysis, and this will
cause the hydrolysis to progress further.
However, there is no problem in adding
additional water or acid.
It is not preferable for the content of the
abovementioned silica microparticles in the film
to be too low since the effect of adding the metal
oxide microparticles, that is, the antifogging and
anti-soiling performance and the retention of
anti-soiling and anti-fogging properties that are
obtained will be inadequate. On the other hand,
when the content of the silica microparticles is
too high, the metal oxide matrix phase,
originating from the organometallic compound or
chlorosilyl-group-containing compound,
becomes discontinuous, and there will be a
strong tendency for the film to be brittle and the
strength of the film to be low. In addition, the
anti-fogging and anti-soiling performance and
the retention of anti-soiling and anti-fogging
properties will be saturated and practically be
unimproved.
The content of the silica microparticles in the film
is thus preferably 5 weight % or more and 80
weight % or less, more preferably 10 weight %
or more and 70 weight % or less, and even more
preferably, 20 weight % or more and 60 weight
% or less.
The abovementioned organometallic compound
or chlorosilyl-group-containing compound is
dissolved in the solvent, the catalyst and water
are added, and hydrolysis is carried out for 5
minutes to 2 days at a fixed temperature
between 10 C. and the boiling point of the
solution. If silica microparticles are to be added,
the silica microparticles and, if it is necessary,
the dispersing agent are added, and the reaction
is continued, if necessary, at a fixed temperature
between 10 C. and the boiling point of the
solution for 5 minutes to 2 days to obtain the
coating solution for forming the overcoat layer.
In the case where a chlorosilyl-group-containing
compound is to be used, the catalyst and water
do not have to be added in particular. Also, the
metal oxide microparticles may be added prior to
the hydrolysis process. Also in order to omit the
process of hydrolysis of the organometallic
compound, an abovementioned commercially-
available organometallic compound hydrolysate
solution may be used. The coating solution that
is thus obtained may thereafter be diluted with a
suitable solvent in accordance with the coating
method.
The above-described coating solution for
forming the overcoat layer is coated onto the
substrate on which the photocatalyst film has
already been formed. Drying and, where
necessary, heat treatment are then carried out to
form a metal oxide overcoat layer on the
substrate.
A known technique may be used as the method
of coating, and though not restricted in
particular, examples include methods using a
spin coater, roll coater, spray coater, curtain
coater or other device, methods, such as the
dipping and drawing method (dip coating
method), the flow application method (flow
coating method), and various printing methods,
such as screen printing, gravure printing, and
curved surface printing.
After coating, the substrate is preferably dried at
a temperature between room temperature and
150 C. for 1 minute to 2 hours and thereafter
heat treated if necessary at a temperature
between 350 C. and the heat resistance
temperature of the substrate for 5 minutes to 2
hours. The heat resistance temperature of the
substrate refers to the upper limit temperature at
which the characteristics of the substrate can be
retained for practical purposes, and refers, for
example, to the softening point or devitrification
point normally, 600 to 700 C. in the case of a
glass substrate or, for example, to the glass
transition point, crystallization temperature, or
decomposition point in the case of a plastic
substrate.
The above-described overcoat layer preferably
has an average thickness of 0.1 to 50 nm. If this
average thickness is less than 0.1 nm, the anti-
fogging and anti-soiling performance
improvement effect will not be significant, and an
average thickness that is greater than 50 nm is
not preferable since improvement of the
hydrophilicity and anti-fogging property by
illumination of light tend not to be exhibited.
The above-described overcoat is preferably a
porous body. Here, a porous body refers to a
thin film having numerous pores, a thin film
having numerous gaps between particles, a thin
film that is attached in insular form, etc., and
preferably, a rate of porosity is 1 to 50%.
A porous overcoat layer and especially a porous
overcoat layer with a rate of porosity of 1 to 50%
is preferable since the ability to retain water on
the surface will be great and the anti-fogging
and anti-soiling performance will be improved
further. Since the antifogging property recovery
performance and hydrophilicity recovery
performance upon illumination of light will also
be improved further, the anti-fogging and anti-
soiling performance will be high.
A porous overcoat layer can be obtained by
adding at least one type of organic polymer,
selected from the group comprised of
polyethylene glycols, polypropylene glycols, and
polyvinyl alcohols, to the above-described
overcoat forming coating solution, coating the
solution, obtained by dissolving the above
components, onto a substrate on which the
abovementioned photocatalyst film has been
formed, drying this coated solution, and then
heating at 350 to 650 C. for 5 minutes to 2
hours to decompose the added organic polymer
compound.
The added amount of the abovementioned
organic polymer compound is 1 weight % or
more and 30 weight % or less, with respect to
the total solids as oxide of the abovementioned
overcoat forming coating solution. An added
amount of less than 1 weight % is not preferable
since the formation of pores will be inadequate
and the pore forming operation will not
contribute to the improvement of the anti-fogging
and anti-soiling performance. An added amount
of more than 30 weight % is not preferable since
the porous film that is obtained will be too brittle.
[Organic Substance Adhesion Prevention Layer]
An organic substance attachment prevention
layer, such as that described below, is preferably
formed on top of the above-described
photocatalyst film and overcoat layer.
Immediately after illumination by ultraviolet rays,
a titanium oxide film or other photocatalyst film
with a high activity will have a small contact
angle of 5 degrees or less and will exhibit
considerably good initial anti-fogging
performance. However, since the surface of
such a film tends to readily absorb organic
substance, the anti-fogging performance tends
to degrade with time as the amount of adsorbed
organic substance increases. With the present
invention, a monomolecular-equivalent layer of
SiOX (whereis 1 or 2) is preferably formed on
the photocatalyst film surface. The adsorption of
organic substance can thereby be restrained
effectively and the degradation of anti-fogging
property can be prevented while retaining high
photocatalytic activity. A monomolecular-
equivalent layer of SiOX, which is an organic
substance adhesion prevention layer, may be
formed favorably by chemical adsorption of a
vapor of a silicon compound, such as 1,3,5,7-
tetramethylcyclotetrasiloxane, onto the
photocatalytic surface or by applying a solution
containing an organosilicon compound, such as
tetraalkoxysilane, onto the photocatalyst film
surface and then illuminating ultraviolet light in
an oxygen atmosphere or heating to decompose
the organosilicon compound. A monomolecular-
equivalent layer of SiOX may also be formed
directly by a vacuum vapor deposition method,
LB method, a liquid phase precipitation method,
etc. The anti-soiling performance will also be
improved significantly by coating the surface of
the photocatalyst film with an organometallic
compound containing at least one type of
functional group, selected from the group
comprised of polyalkylene oxide groups, alkyl
groups, alkenyl groups, and aryl groups, in the
molecule or a hydrolysate of such an
organometallic compound in place of the
SiOX monomolecular-equivalent layer. Such
organometallic compounds are decomposed
gradually by illumination of ultraviolet light,
temperature rise, and other external factors, and
in the final stage, a monomolecular-equivalent
layer of SiOXor other metal oxide will be formed
to maintain the anti-soiling performance. Here, a
monomolecular-equivalent layer refers to a
molecular layer that is practically a
monomolecular layer and in which 0.5 to 5
molecules are aligned on average in the
thickness direction.
A polyethylene oxide group, polypropylene oxide
group, etc., is mainly used as the polyalkylene
oxide group to be contained in the molecule of
the abovementioned organometallic compound.
A chain alkyl group with 1 to 10 carbon atoms,
such as the methyl group, ethyl group, propyl
group, butyl group, pentyl group, hexyl group,
octyl group, nonyl group, decyl group, etc., or an
cyclic alkyl group with 3 to 10 carbon atoms,
such as the cyclopentyl group, cyclohexyl group,
etc., is mainly used as the abovementioned alkyl
group. A group with 1 to 10 carbon atoms, such
as the vinyl group, aryl group, butenyl group,
propenyl group, hexenyl group, octenyl group,
cyclohexenyl group, etc., is mainly used as the
abovementioned alkenyl group. The phenyl
group, tolyl group, xylyl group, etc. is mainly
used as the abovementioned aryl group.
Examples of organometallic compounds
containing such a functional group, for example,
a polyethylene oxide group, in the molecule
include organosilanes, such as
[alkoxy(polyethyleneoxy)alkyl] trialkoxysilane,
[alkoxy(polyethyleneoxy)alkyl] trichlorosilane,
etc., and organic titanium compounds, such as
[alkoxy(polyethyleneoxy)alkyl] trialkoxytitanium.
These functional groups are favorable since they
are non-polar or low in polarity and make the dirt
attachment property low, restrain the rising of
the contact angle with respect to water drops,
and thus improve the anti-fogging property
retention and hydrophilicity retention. An above-
described anti-fogging, anti-soiling articles that
has been made using an organosilane that
contains a polyalkylene oxide group is especially
good in anti-fogging characteristics, excellent in
anti-fogging property retention and hydrophilicity
retention (in other words, anti-soiling property),
and is thus especially preferable. As has been
mentioned above, when the hydrophilicity
retention is high, the anti-soiling property is
good.
Since the abovementioned functional groups are
non-reactive or low in reactivity, they do not give
rise to chemical bonding with dirt components,
and since the dirt will not become fixed to the
surface and the dirt that has become attached to
the surface can be removed readily by wiping,
etc., the anti-fogging property can be revived
readily even when the anti-fogging property has
become lost due to dirt.
The abovementioned organosilane that contains
a polyalkylene oxide group is preferably an
alkoxysilane or chlorosilane that contains an
alkoxyl group or a chloro group in the molecule.
Since an alkoxyl group or chloro group will
readily undergo hydrolysis so that the
organosilane can be strongly bonded chemically
to the surface of the photocatalyst film or
overcoat layer, a product of higher anti-fogging
property retention can be obtained. Among the
abovementioned organosilanes, alkoxysilanes
that contain a polyethylene oxide group is
preferable, and an
[alkoxy(polyethyleneoxy)alkyl] trialkoxysilane,
such as [methoxy(polyethyleneoxy)propyl]
trimethoxysilane, is most preferable.
Any method by which an abovementioned
organosilane or hydrolysate thereof can be
contacted with the surface of the above-
described photocatalyst film or overcoat layer
may be used as the method for bonding or
attaching an abovementioned organosilane or
hydrolysate to the surface of the above-
described photocatalyst film or overcoat layer.
Examples include methods of coating a liquid
containing an abovementioned organosilane or
hydrolysate thereof onto the photocatalyst film or
overcoat layer (coating methods), methods of
immersing an article on which the photocatalyst
film has been formed or an article on which the
photocatalyst film with an overcoat has been
formed in a liquid containing an abovementioned
organosilane or hydrolysate thereof (liquid
phase chemical adsorption methods), methods
in which an abovementioned article is placed in
a vapor of an abovementioned organosilane or
hydrolysate thereof to cause the
abovementioned organosilane or hydrolysate to
become adsorbed on the surface (gas phase
chemical adsorption methods), etc.
Of the abovementioned methods, coating
methods are especially preferable since they are
most simple and low in cost. A known technique
may be used as the method of coating, and
though not restricted in particular, examples
include methods using a spin coater, roll coater,
spray coater, curtain coater or other device,
methods, such as the dipping and drawing
method (dip coating method), the flow
application method (flow coating method),
methods in which the uneven photocatalyst film
surface is contacted with a cloth or paper
soaked with a coating solution and then rubbed
by application of a suitable force (rubbing
methods), and various printing methods, such as
screen printing, gravure printing, and curved
surface printing.
Though the solvent for dissolving an
abovementioned organosilane is not restricted in
particular, water, alcohols, and ketones are
preferably used in a solitary or mixed form from
the standpoint of safety, cost, and workability.
Examples of alcohols include methanol, ethanol,
propanol, butanol, etc., and examples of ketones
include acetone, methyl ethyl ketone, diethyl
ketone, etc.
An abovementioned organosilane is used upon
being subjected to hydrolysis if necessary.
Water, and where necessary, an acid catalyst
are added to the organosilane solution,
hydrolysis is carried out for a fixed amount of
time under a fixed temperature, and the resulting
solution is used for coating upon diluting if
necessary.
Though the conditions of hydrolysis are not
restricted in particular, the hydrolysis is
preferably carried out for 3 minutes to 50 hours
under a temperature of 20 to 60 C. If the
temperature is lower than 20 C. or the time is
shorter than 3 minutes, the promotion of
hydrolysis will be inadequate. On the other
hand, a temperature higher than 60 C. or a time
longer than 50 hours is not preferable since the
hydrolysis promotion effect will improve no
further and the life of the coating solution will be
short.
Besides mineral acids, such as hydrochloric
acid, sulfuric acid, and nitric acid, organic acids,
such as acetic acid, formic acid, citric acid, p-
toluenesulfonic acid, etc., are used as the
abovementioned acid catalyst. Though the
amount of acid added is not restricted in
particular, the mole ratio of the added acid to
organosilane is preferably 0.0001 to 5. If the
mole ratio of the added acid is less than 0.0001,
the hydrolysis of organosilane will not be
promoted adequately and a mole ratio of greater
than 5 is not preferable since the hydrolysis
promotion effect will improve no further and the
acidity will be excessive.
Though the amount of water to be added for
hydrolysis is not restricted in particular, the mole
ratio of the water added to the organosilane is
preferably 0.1 or more. A mole ratio of added
water of less than 0.1 is not preferable since the
hydrolysis of organosilane will not be promoted
adequately.
On the other hand, with an
[alkoxy(polyethyleneoxy)alkyl] trichlorosilane or
other polyalkylene-oxide-group-containing
organosilane with a high rate of hydrolysis, the
hydrolysis may proceed adequately with just the
water adsorbed on the surface of the
photocatalyst film or overcoat layer and the
organosilane may become fixed to the surface
by a dehydration condensation reaction in some
cases. In such a case, it is more preferable to
prepare a coating solution using a non-aqueous
solvent from which the dissolved water has been
lessened adequately since weatherability, anti-
fogging and anti-soiling properties, anti-fogging
property retention, and hydrophilicity retention of
the article that will be obtained will then be
excellent. Examples of non-aqueous solvents
include n-hexane, cyclohexane, xylene, toluene,
etc.
Although the concentration of the organosilane
solution used for coating is not restricted in
particular, a concentration of 0.001 to 5 weight
% is preferable. If the concentration is less than
0.001 weight %, adequate improvement of anti-
fogging property retention and hydrophilicity
retention will tend not to be seen in the anti-
fogging, anti-soiling articles obtained, and a
concentration of more than 5 weight % is not
preferable since this will be uneconomical as the
anti-fogging performance and anti-soiling
performance will not be improved further.
After coating of the organosilane solution, the
photocatalyst film or photocatalyst film with
overcoat is preferably dried or heat treated for 3
minutes to 3 hours under a temperature of 20 to
180 C. By this treatment, the bonding of
organosilane onto the surface will become
strong and the durability, anti-fogging property
retention, and hydrophilicity retention of the anti-
fogging, anti-soiling articles will improve. A
temperature lower than 20 C. or a time shorter
than 3 minutes is not preferable since the
abovementioned effects will be inadequate. A
temperature higher than 180 C. is not
preferable since the organosilane may
decompose in some cases. A time longer than 3
hours is not preferable from the point of
productivity since the abovementioned effects
will improve no further.
If an organosilane monomolecular-equivalent
layer is formed on top of the above-described
photocatalyst film or overcoat layer, the anti-
fogging property retention and anti-soiling
property will improve. This organosilane layer
will be decomposed gradually by illumination of
ultraviolet light, temperature rise, and other
external factors, and in the final stage, a
monomolecular-equivalent layer of SiOX will be
formed to maintain the anti-fogging property
retention and anti-soiling property.
PREFERRED EMBODIMENTS OF THE
INVENTION
Though the present invention shall now be
described on the basis of examples, the present
invention is not limited to these examples.
[Example 1 and Comparative Example 1]
Formation of Alkali-Blocking Film (Silica Film)
96.2 weight parts of ethanol and 3.8 weight parts
of a hydrolysis condensation polymerization
solution of ethyl silicate (trade name: HAS-10,
made by Colcoat, K.K., silica content: 10 weight
%) were mixed at room temperature and stirred
for 1 hour to obtain a coating solution for forming
an alkali-blocking silica film.
A soda lime silicate glass plate (1501503
mm), which had been surface polished and
washed with a cerium oxide polishing agent,
subject to ultrasonic washing in pure water, and
then dried, was suspended vertically in an
environment of 20 C. and 30% RH, and the
abovementioned coating solution for forming an
alkali-blocking silica film was made to flow from
the upper end of the glass plate to coat a film
onto the surface of one side of the glass plate
(flow coating method). This glass plate was dried
at 100 C. for 30 minutes, dried further at 250
C. for 30 minutes, and then heat treated for 1
hour inside a 500 C. oven to obtain a glass
substrate on which an alkali-blocking silica film
of approximately 30 nm thickness was formed.
Example 1 Formation of a Silica Film with
Magnesium Oxide Added and Titanium Oxide
Microparticles Dispersed
24 g of ethanol were added to 1 g of magnesium
chloride hexahydrate to dissolve the magnesium
chloride hexahydrate and thereby prepare a
magnesium addition solution. 463 g of ethanol, 6
g of a hydrolysis condensation polymerization
solution of ethyl silicate (trade name: HAS-10,
made by Colcoat, K.K., silica content 10 weight
%), 10 g of a titania microparticle dispersion
(trade name: ST-K01, made by Ishihara Sangyo,
Co., Ltd., titanium oxide content: 8 weight %,
average diameter of titania microparticles: 35
nm, inorganic binder content: 2 weight %), and
25 g of the abovementioned magnesium
addition solution were mixed and stirred at room
temperature for approximately 1 hour to obtain a
photocatalyst film forming coating solution.
The above-described soda lime silicate glass
substrate with alkali-blocking silica film was
suspended vertically in an environment of 20 C.
and 30% RH, and the abovementioned
photocatalyst film forming coating solution was
made to flow from the upper end of the glass
plate to coat a film on top of the alkali-blocking
silica film of the glass substrate (flow coating
method). Thereafter, the glass plate was heat
treated for 1 hour at 500 C. to form a
photocatalyst thin film comprised of silica with
magnesium oxide added and titanium oxide
microparticles dispersed. The sample obtained
in this manner shall be referred to as sample A
(glass substrate/silica film/silica thin film with
magnesium oxide added and titanium oxide
microparticles dispersed).
The silica thin film with magnesium oxide added
and titanium oxide microparticles dispersed had
a thickness of approximately 60 nm, a
composition of 44.4 weight % silicon oxide, 44.4
weight % titanium oxide, and 11.1 weight %
magnesium oxide and the Mg/Ti (atomic ratio)
was 0.49.
Comparative Example 1 Formation of Silica Film
with Titanium Oxide Microparticles Dispersed
463 g of ethanol, 6 g of a hydrolysis
condensation polymerization solution of ethyl
silicate (trade name: HAS-10, made by Colcoat,
K.K., silica content: 10 weight %), and 10 g of a
titania microparticle dispersion (trade name: ST-
K01, made by Ishihara Sangyo, Co., Ltd.,
titanium oxide content: 8 weight %, inorganic
binder content: 2 weight %) were mixed and
stirred at room temperature for approximately 1
hour to obtain a photocatalyst film forming
coating solution.
The above photocatalyst film forming solution
was coated onto the above-described soda lime
silicate glass substrate with alkali-blocking silica
film by the flow coating method in the same
conditions as those of the first example. Heat
treatment of the same conditions as those of the
first example was then carried out to obtain a
glass substrate having formed thereon at an
approximately 70 nm-thick silica thin film with
titanium oxide microparticles dispersed. The
sample obtained in this manner shall be referred
to as sample B (glass substrate/silica film/silica
thin film with titanium oxide microparticles
dispersed).
Evaluation of Anti-fogging Property
The above-described samples A and B were left
inside a room, which was not exposed to direct
sunlight but was bright with indirect sunlight and
into and from which people constantly entered
and exited, and the degree to which the surface
became soiled and the anti-fogging property
dropped was evaluated by the degree of fogging
that occurred upon exhalation onto the sample
(exhalation test). That is, whereas with a sample
immediately after the cleaning of the surface,
fogging will not occur even upon exhalation onto
the sample, when the sample is left inside the
room, the dirt components in the atmosphere will
become attached to the sample surface so that
the sample will become fogged by the exhalation
test. The time from which the leaving of the
sample in the room was started to the time at
which fogging began to occur (anti-fogging
retention time) was used as an index of the anti-
fogging retention. The greater this value, the
higher the anti-fogging retention. The anti-
fogging retention of the above samples were
evaluated in accordance with Table 1 below.
Furthermore, onto a sample for which the anti-
fogging property had been lowered upon leaving
inside a room (i.e. a sample for which fogging
had occurred in the above-described exhalation
test), light from a xenon lamp (intensity of
ultraviolet rays when no ultraviolet ray cutting
filters were used: 2 mW/cm2; measured by the
ultraviolet ray photometer UVR-2/UD-36 made
by Topcon K.K.) was illuminated via the
ultraviolet ray cutting filter L-42 (made by
Toshiba Glass Co., Ltd., transmittance at
wavelengths of 390 nm or less: 0%,
transmittance at a 400 nm wavelength: 5%,
transmittance at a 420 nm wavelength:
approximately 50%, transmittance at a 450 nm
wavelength: approximately 80%, transmittance
of visible light of 520 nm wavelengths or more:
approximately 90%) for 2 hours continuously,
and the magnitude of lowering of the water drop
contact angle (water drop contact angle reviving
amount) was used as an index of the anti-
fogging property recovery. This anti-fogging
property recovery also indicates the catalytic
activity of the photocatalyst film. An ultraviolet
ray (340 to 395 nm) illumination intensity of
2mW/cm2 corresponds to approximately 80% of
the ultraviolet ray intensity in direct sunlight from
outdoor solar light at a location of lat. 35 N on a
sunny day in winter. If the water drop contact
angle is lowered by this light (visible light and
weak ultraviolet light) from which ultraviolet rays
have been cut, the sample can be said to have
an extremely good anti-fogging property
recovery. Using a contact angle gauge (CA-DT,
made by Kyowa Kaimen Chemical Co., Ltd.), the
contact angle with respect to a water drop of 0.4
mg was measured before and after 2 hours of
light illumination, the amount by which the
contact angle dropped due to illumination was
determined as a water drop contact angle
reviving index defined as (contact angle after 2
hours of light illumination)/(contact angle before
light illumination), and the antifogging property
recovery was evaluated in accordance with
Table 2 shown below. It can be said that the
smaller this index, the stronger the tendency for
the hydrophilicity to be improved by visible light
and weak ultraviolet light.
TABLE 1
Evaluation of
anti-
fogging
property
Anti-fogging property
retention
retention period
Does not fog or the condition
in which only a slight
non-uniformity is seen
continues for 9 days or more.
6 days or more but less than
9 days
3 days or more but less than
6 days
X less than 3 days
TABLE 2 TABLE 3

Water drop contact angle Evaluation of

recovery amount (water anti-
Evaluation of drop contact angle after 2 soiling
Soiling conditions
anti- hours of light property
fogging illumination)/(water drop
property contact angle before streaks of dirt can be seen.
recovery light illumination) Soiled and streaks of dirt are

conspicuous.
less than 50% Considerably soiled and
X
50% or more and less than streaks of dirt are quite

70% conspicuous.
70% or more and less than

90%
X 90% or more
Evaluation of Anti-soiling Property
The anti-soiling property was evaluated by the
following outdoor exposure test. That is, sample
plates were set vertically at an outdoor location
in Itami City, Hyogo Prefecture, and an exposure
test was performed for six months from February
to July under an environment simulating a
vertical surface under the eaves on which
rainwater would flow down along the sample
plate surface. The conditions of soiling of the
sample plates after the test were evaluated
visually in accordance with the standards of
TABLE 3
The various evaluation results for the
abovementioned sample A and sample B are
shown in Table 4. It is clear that sample A
(Example 1) is considerably improved in anti-
fogging property retention, anti-fogging property
recovery, and anti-soiling property over sample
B (Comparative example 1).
Example 2 Formation of Silica Thin Film with
Scandium Compound Added and Titanium
Oxide Microparticles Dispersed
A scandium addition solution was prepared by
dissolving 2 g of scandium trichloride
hexahydrate in 48 g of commercially available
alcohol (trade name: AP-7, made by Nihon
Kaseihin, K.K., 85.5% ethanol, 9.6% 1-propanol,
4.9% 2-propanol).

Evaluation of 1.7 g of tetrachlorosilane, 10.0 g of titania

anti-
microparticle dispersion (trade name: ST-K01,
soiling
Soiling conditions made by Ishihara Sangyo, Co., Ltd.), and 32.5 g
property
of the abovementioned scandium addition

Soiling can hardly be solution were added to 120 g of alcohol (trade

name: AP-7, made by Nihon Kaseihin, K.K.) and
noticed.
Slightly soiled and thin
mixing was performed for approximately 1 hour
at room temperature to obtain a coating solution.
Without forming an alkali-blocking silica film, the
abovementioned coating solution was coated by
the flow coating method of the same conditions
as Example 1 onto the surface of a soda lime
silicate glass plate (1501503 mm), which had
been surface polished, washed, and dried in the
same manner as in Example 1. This glass plate
was dried at 100 C. for 30 minutes to obtain a
glass substrate having formed thereon at an
approximately 120 nm-thick silica film with
scandium compound added and titanium oxide
microparticles dispersed (41 weight % silica, 18
weight % scandium oxide (as Sc2O3), 41 weight
% titanium oxide, Sc/Ti=0.50 (atomic ratio)). The
sample obtained thus shall be referred to as
sample C (glass substrate/silica thin film with
scandium compound added and titanium oxide
microparticles dispersed). The various
antifogging and anti-soiling performance
evaluation results of sample C are shown in
Table 4. These clearly show that sample C
exhibits excellent anti-fogging and anti-soiling
performance over sample B (Comparative
example 1).
Example 3 Formation of Alkali Blocking Film
(Silica-Zirconia Thin Film)
5 weight parts of zirconium butoxide were added
to 1 weight part of ethyl acetoacetate and stirring
was performed at 30 C. for 2 hours. The
solution thus prepared shall be referred to as
solution A. On the other hand, 1000 weight parts
of 2-propanol, 2.5 weight parts of 1N nitric acid,
and 50 weight parts of water were added to 50
weight parts of tetraethoxysilane and stirring
was performed at 30 C. for 2 hours. The
solution thus prepared shall be referred to as
solution B. Solution A and solution B were then
mixed and curing while stirring was performed at
50 C. for 3 hours and then at 30 C. for 1 day to
obtain a sol solution for an alkali-blocking film.
A soda lime silicate glass plate (65 mm150
mm3 mm), which had been surface polished
and washed with a cerium oxide polishing agent,
subject to ultrasonic washing in pure water, and
then dried, was immersed in the
abovementioned sol solution for alkali-blocking
film and the glass plate was then drawn out at a
rate of 10 cm/minute. This glass plate was
thereafter dried at room temperature for a few
minutes and heat treated for 3 hours at 500 C.
to obtain a glass plate on which a silica-zirconia
thin film (92 weight % silica, 8 weight % zirconia)
of approximately 30 nm thickness was formed.
Formation of Silica Thin Film with Vanadium
Compound Added and Titanium Microparticle
Dispersed
The method for coating on a silica thin film with
vanadium compound added and titanium
microparticle dispersed by the sol-gel method
shall now be described. 1.00 g of acetylacetone
vanadyl were. dissolved by adding 0.79 g of
35% hydrochloric acid and 8.21 g of alcohol
(trade name: AP-7, made by Nihon Kaseihin,
K.K.) to prepare a vanadium addition solution.
0.34 g of tetrachlorosilane, 2.00 g of titania
microparticle dispersion (trade name: ST-K01,
Ishihara Sangyo, Co., Ltd.), and 2.66 g of the
abovementioned vanadium addition solution
were added to 95.00 g of alcohol (trade name:
AP-7, made by Nihon Kaseihin, K.K.) and mixing
was performed at room temperature for
approximately 2 hours to obtain a coating
solution. Using this coating solution, a film was
formed by the flow coating method of Example 1
on the above-described soda lime silicate glass
substrate with silica-zirconia film. Drying was
then performed at room temperature to obtain
sample D (glass substrate/silica-zirconia thin
film/silica thin film with vanadium compound
added and titanium microparticle dispersed).
Also, sample D was heat treated at 500 C. for 1
hour to form a silica thin film with vanadium
oxide added and titanium microparticle
dispersed. This sample shall be referred to as
sample D (glass substrate/silica-zirconia thin
film/silica thin film with vanadium oxide added
and titanium microparticle dispersed).
The silica thin film with vanadium compound
added and titanium microparticle dispersed of
sample D and the silica thin film with vanadium
oxide added and titanium microparticle
dispersed of sample D both had a thickness of
approximately 60 nm, a composition of 39
weight % silicon oxide, 39 weight % titanium
oxide, and 22 weight % vanadium compound (as
V2O5), and the V/Ti (atomic ratio) was 0.5.
The various anti-fogging and anti-soiling
performance evaluation results of sample D and
D are shown in Table 4. These clearly show that
both samples D and D exhibit excellent anti-
fogging and anti-soiling performance.
Example 4 Formation of Silica Thin Film with
Chromium Oxide Added and Titanium Oxide
Microparticles Dispersed
A chromium addition solution was prepared by
dissolving 1.00 g of chromium trichloride
hexahydrate in 9.00 g of alcohol (trade name:
AP-7, made by Nihon Kaseihin, K.K.). 0.34 g of
tetrachlorosilane, 2.00 g of titania microparticle
dispersion (trade name: ST-K01, made by
Ishihara Sangyo, Co., Ltd.), and 2.67 g of the
abovementioned chromium addition solution
were added to 94.99 g of alcohol at room
temperature and mixing was performed for
approximately 1 hour at room temperature to
obtain a coating solution. Using the same
method as that of Example 1, a 70 nm-thick
silica thin film with chromium oxide added and
titanium oxide microparticles dispersed (40
weight % silicon oxide, 40 weight % titanium
oxide, 20 weight % chromium oxide, Cr/Ti=0.50
(atomic ratio)) was formed on a soda lime
silicate glass plate with silica film of the same
type described in Example 1. The sample
obtained thus shall be referred to as sample E
(glass substrate/silica film I silica thin film with
chromium oxide added and titanium oxide
microparticles dispersed). The various anti-
fogging and anti-soiling performance evaluation
results of sample E are shown in Table 4. These
clearly show that sample E exhibits excellent
anti-fogging and anti-soiling performance.
Example 5 Formation of Silica Thin Film with
Manganese Oxide Added and Titanium Oxide
Microparticles Dispersed
A manganese addition solution was prepared by
dissolving 1.00 g of manganese chloride
tetrahydrate in 9.00 g of alcohol (trade name:
AP-7, made by Nihon Kaseihin, K.K.). 0.34 g of
tetrachlorosilane, 2.00 g of titania microparticle
dispersion (trade name: ST-K01, made by
Ishihara Sangyo, Co., Ltd.), and 1.98 g of the
abovementioned manganese addition solution
were added to 95.68 g of alcohol (trade name:
AP-7, made by Nihon Kaseihin, K.K.) and mixing
was performed for approximately 1 hour at room
temperature to obtain a coating solution.
Besides changing the conditions of heat
treatment after coating to 350 C. for 1 hour, the
same method as that of Example 1 was used to
form a silica thin film with manganese oxide
added and titanium oxide microparticles
dispersed (thickness: 80 nm, 41 weight % silicon
oxide, 41 weight % titanium oxide, 18 weight %
manganese oxide, Mn/Ti=0.50 (atomic ratio)) on
a soda lime silicate glass plate with silica film of
the same type described in Example 1. The
sample obtained thus shall be referred to as
sample F (glass substrate/silica film/silica thin
film with manganese oxide added and titanium
oxide microparticles dispersed). The various
anti-fogging and anti-soiling performance
evaluation results of sample F are shown in
Table 4. These clearly show that sample F
exhibits excellent anti-fogging and anti-soiling
performance.
Example 6 Formation of Silica Thin Film with
Yttrium Oxide Added and Titanium Oxide
Microparticles Dispersed
An yttrium addition solution was prepared by
dissolving 1.00 g of yttrium chloride hexahydrate
in 24.00 g of alcohol (trade name: AP-7, made
by Nihon Kaseihin, K.K.). 0.05 g of
tetrachlorosilane, 1.00 g of titania microparticle
dispersion (trade name: ST-K01, made by
Ishihara Sangyo, Co., Ltd.), and 3.80 g of the
abovementioned yttrium addition solution were
added at room temperature to 45.03 g of alcohol
(trade name: AP-7, made by Nihon Kaseihin,
K.K.) and mixing was performed for
approximately 1 hour at room temperature to
obtain a coating solution. Using the same
method as that of Example 1, a silica thin film
with yttrium oxide added and titanium oxide
microparticles dispersed (thickness: 60 nm, 22
weight % silicon oxide, 46 weight % titanium
oxide, 32 weight % yttrium oxide, Y/Ti=0.50
(atomic ratio)) was formed on a soda lime
silicate glass plate with silica film of the same
type described in Example 1. The sample
obtained thus shall be referred to as sample G
(glass substrate/silica film/silica thin film with
yttrium oxide added and titanium oxide
microparticles dispersed). The various anti-
fogging and anti-soiling performance evaluation
results of sample G are shown in Table 4. These
clearly show that sample G is significantly
improved in anti-fogging property recovery over
sample B (Comparative example 1) and exhibits
good anti-fogging property retention as well as
excellent anti-soiling property.
Example 7 Formation of Silica Thin Film with
Niobium Compound Added and Titanium Oxide
Microparticles Dispersed
A niobium addition solution was prepared by
dissolving 1.00 g of niobium pentachloride in
9.00 g of alcohol. 0.3 g of tetrachlorosilane, 0.5
g of colloidal silica (trade name: Snowtex-OUP,
made by Nissan Chemical Industries, K.K.), 2.00
g of titania microparticle dispersion (trade name:
ST-K01, made by Ishihara Sangyo, Co., Ltd.),
and 2.71 g of the abovementioned niobium
addition solution were added to 94.95 g of
alcohol (trade name: AP-7, made by Nihon
Catechin, K.K.) and mixing was performed at
room temperature for approximately 1 hour to
obtain a coating solution. Besides not
performing the heat treatment at 500 C., the
same method as that of Example 1 was used to
form a silica thin film with niobium compound
added and titanium oxide microparticles
dispersed (thickness: 90 nm, 43 weight % silicon
oxide, 31 weight % titanium oxide, 26 weight %
niobium pentachloride (as niobium oxide),
Nb/Ti=0.50 (atomic ratio)) on a soda lime silicate
glass plate with silica film of the same type
described in Example 1. The sample obtained
thus shall be referred to as sample H (glass
substrate/silica film/silica thin film with niobium
compound added and titanium oxide
microparticles dispersed). The various anti-
fogging and anti-soiling performance evaluation
results of sample H are shown in Table 4. These
clearly show that sample H exhibits excellent
anti-fogging and anti-soiling performance.
Example 8 Formation of Silica Thin Film with
Molybdenum Compound Added and Titanium
Oxide Microparticles Dispersed
A molybdenum addition solution was prepared
by dissolving 2.16 g of ammonium molybdate in
22.84 g of 0.1N hydrochloric acid. 0.34 g of
tetrachlorosilane, 2.00 g of titania microparticle
dispersion (trade name: ST-K01, made by
Ishihara Sangyo, Co., Ltd.), and 3.07 g of the
abovementioned molybdenum addition solution
were added at room temperature to 94.59 g of
alcohol (trade name: AP-7, made by Nihon
Catechin, K.K.) and mixing was performed at
room temperature for approximately 1 hour to
obtain a coating solution. Besides not
performing the heat treatment at 500 C., the
same method as that of Example 1 was used to
obtain a glass substrate on which a titanium
oxide thin film with molybdenum compound
added is formed on a soda lime silicate glass
plate with silica film of the same type described
in Example 1. The sample obtained thus shall be
referred to as sample I (glass substrate/silica
film/silica thin film with molybdenum compound
added and titanium oxide microparticles
dispersed). The thickness of the titanium oxide
thin film with molybdenum compound added of
Sample I was approximately 40 nm. The silicon
oxide content was 30 weight %, the titanium
oxide content was 30 weight %, the ammonium
molybdate content (as NO3) was 40 weight %,
and Mo/Ti=0.75 (atomic ratio). The various anti-
fogging and anti-soiling performance evaluation
results of sample I are shown in Table 4. These
clearly show that sample I is significantly
improved in anti-fogging property recovery over
sample B (first comparative example) and
exhibits good anti-fogging property retention as
well as excellent anti-soiling property.
Example 9 Formation of Silica Thin Film with
Tungsten Oxide Added and Titanium Oxide
Microparticles Dispersed
A tungsten addition solution was prepared by
dissolving 0.50 g of tungstic acid in 9.00 g of
alcohol. 0.34 g of tetrachlorosilane, 2.00 g of
titania microparticle dispersion (trade name: ST-
K01, made by Ishihara Sangyo, Co., Ltd.), and
2.50 g of the abovementioned tungsten addition
solution were added at room temperature to
95.16 g of alcohol (trade name: AP-7, made by
Nihon Catechin, K.K.) and mixing was
performed for approximately 1 hour at room
temperature to obtain a coating solution. The
same method as that of Example 1 was
repeated five times to form an approximately
350 nm-thick silica thin film with tungsten oxide
added and titanium oxide microparticles
dispersed (thickness: 350 nm, 36 weight %
silicon oxide, 36 weight % titanium oxide, 28
weight % tungsten oxide, W/Ti=0.26 (atomic
ratio)) on a soda lime silicate glass plate with
silica film of the same type described in Example
1. The sample obtained thus shall be referred to
as sample J (glass substrate/silica film/silica thin
film with tungsten oxide added and titanium
oxide microparticles dispersed). The various
anti-fogging and anti-soiling performance
evaluation results of sample J are shown in
Table 4. These clearly show that sample J has
excellent anti-fogging and anti-soiling properties.
Example 10 Formation of Silica Thin Film with
Tungsten Oxide and Magnesium Oxide Added
and Titanium Oxide Microparticles Dispersed
A magnesium tungstate addition solution was
prepared by dissolving 1.00 g of magnesium
tungstate in 24.00 g of 0.1N hydrochloric acid.
0.34 g of tetrachlorosilane, 2.00 g of titania
microparticle dispersion (trade name: ST-K01,
made by Ishihara Sangyo, Co., Ltd.), and 6.81 g
of the abovementioned magnesium tungstate
addition solution were added at room
temperature to 90.85 g of alcohol (trade name:
AP-7, made by Nihon Catechin, K.K.) and
mixing was performed for approximately 1 hour
at room temperature to obtain a coating solution.
The same method as that of Example 1 was
carried out to form a silica thin film with tungsten
oxide and magnesium oxide added and titanium
oxide microparticles dispersed (thickness: 90
nm, 27 weight % silicon oxide, 27 weight %
titanium oxide, 39 weight % tungsten oxide, 7
weight % magnesium oxide (W+Mg)/Ti=1.00
(atomic ratio)) on a soda lime silicate glass plate
with silica film of the same type described in
Example 1. The sample obtained thus shall be
referred to as sample K (glass substrate/silica
film/silica thin film with tungsten oxide and
magnesium oxide added and titanium oxide
microparticles dispersed). The various anti-
fogging and anti-soiling performance evaluation
results of sample K are shown in Table 4. These
clearly show that sample K has excellent anti-
fogging and anti-soiling properties.
Example 11
An SiOX monomolecular layer film was formed
on the surface of the silica film with magnesium
oxide added and titanium oxide microparticles
dispersed as in sample A. After setting sample A
in a vacuum dessicator that was kept warm at
80 C., 200 L of 1,3,5,7-
tetramethylcyclotetrasiloxane (MCTS) was
injected with a syringe. After maintaining this
condition for 30 minutes, the temperature was
raised to 100 C. and the interior of the
dessicator was heated for 30 minutes while
drawing a vacuum to remove the unreacted
MCTS. By this method, a monomolecular film of
MCTS was formed on the silica film with
magnesium oxide added and titanium oxide
microparticles dispersed. Then using a 500 W
high-voltage mercury lamp, light was illuminated
for 1 hour from a distance of 8 cm to oxidize and
convert the TMCTS film to a monomolecular-
equivalent film of SiOX. Sample L (glass
substrate/silica film with magnesium oxide
added and titanium oxide microparticles
dispersed/SiOXmonomolecular-equivalent film)
was thus obtained. The various anti-fogging and
anti-soiling performance evaluation results of
sample L are shown in Table 4. These clearly
show that sample L has excellent anti-fogging
and anti-soiling properties.
Example 12
A silica overcoat layer was formed by the
following method on sample D. 0.7 g of a
hydrolysis condensation polymerization solution
of ethyl silicate (trade name: HAS-10, made by
Colcoat, K.K.) and 0.2 g of chain-like silica
colloid (average particle diameter: approx. 15
nm, average length: approx. 170 nm, trade
name: Snowtex OUP, made by Nissan Chemical
Industries, K.K., 15 weight % solids) were mixed
with 99.1 g of ethanol and mixing was performed
for approximately 1 hour at room temperature to
obtain a coating solution. The abovementioned
coating solution was coated onto the surface of
sample D by the same method as the flow
coating method indicated for Example 1 and
heat treatment at 500 C. was performed for 1
hour to obtain sample M (glass substrate/silica-
zirconia thin film/silica thin film with vanadium
oxide added and titanium oxide microparticle
dispersed/silica overcoat layer). The thickness of
the silica overcoat layer was approximately 10
nm. The various anti-fogging and anti-soiling
performance evaluation results of sample M are
shown in Table 4. These clearly show that even
better anti-fogging and anti-soiling properties are
provided by the formation of the silica overcoat
layer.
Example 13
An organic substance adhesion prevention layer,
comprised of organosilane, was formed by the
following method on sample J.
1 mL of 0.1 normal acetic acid was added to
1000 mL of commercially available ethanol
(99.5%) and stirring was performed. To 796 g of
this liquid mainly comprised of ethanol, 4 g of
[methoxy(polyethyleneoxy)propyl]
trimethoxysilane (SIM6492.7 made by Chisso
Co., Ltd., content: 90%, molecular weight: 460 to
590, 6 to 9 ethylene oxide units) and stirring was
performed at 30 C. for 1 hour to prepare an
organosilane coating solution.
The sample J prepared in Example 9 was
immersed in the above-described organosilane
coating solution and then drawn out at a rate of
5 cm per minute to coat the solution onto the
surface of sample J. This sample was dried and
heat treated at 120 C. for 30 minutes and then
cooled to room temperature and washed gently
with pure water to form an approximately 8 nm-
thick organosilane layer containing polyethylene
oxide groups in the molecule and thereby obtain
sample N with a film composition of glass
substrate/silica film/silica thin film with tungsten
oxide added and titanium oxide microparticles
dispersed/
[methoxy(polyethyleneoxy)propyl]trimethoxysilan
e layer. The various anti-fogging and anti-soiling
performance evaluation results of sample N are
shown in Table 4. These clearly show that the
anti-soiling performance is especially improved
and that excellent anti-fogging and anti-soiling
properties are provided by the formation of the
organosilane layer.
Example 14
2.16 g of ammonium molybdate were dissolved
in 22.84 g of 0.1N hydrochloric acid to obtain a
molybdenum addition solution. 0.20 g of
acetylacetone, 0.29 g of titanium isopropoxide,
2.00 g of a titania microparticle dispersion (trade
name: STS-02, made by Ishihara Sangyo, Co.,
Ltd., titanium oxide content: approximately 30
weight %), and 4.36 g of the abovementioned
molybdenum addition solution were added at
room temperature to 94.44 g of alcohol (trade
name: AP-7, made by Nihon Kaseihin, K.K.) and
mixing was performed at room temperature for
approximately 1 hour to obtain a coating
solution. Besides not performing the heat
treatment at 500 C., the same method as that
of Example 1 was used to obtain a glass
substrate on which a titanium oxide thin film with
molybdenum compound added is formed on a
soda lime silicate glass substrate with silica film
of the same type described in Example 1.
Besides performing heat treatment at 400 C. for
1 hour instead of heat treatment at 500 C. for 1
hour, the same method as that indicated for
Example 12 was carried out to form a silica
overcoat layer on top of the abovementioned
thin film.
The sample thus obtained shall be referred to as
sample O (glass substrate/silica thin
film/titanium oxide microparticle thin film with
molybdenum oxide added/silica overcoat layer).
The thickness of the titanium oxide thin film with
molybdenum oxide added of sample O was
approximately 100 nm. The composition was 69
weight % titanium oxide and 31 weight %
molybdenum oxide and Mo/Ti=0.25 (atomic
ratio). The various anti-fogging and anti-soiling
performance evaluation results of sample O are
shown in Table 4. These clearly show that
sample O has excellent anti-fogging and anti-
soiling properties.
Example 15
0.27 g of ruthenium trichloride monohydrate,
0.34 g of tetrachlorosilane, and 2.00 g of titania
microparticle dispersion (trade name: ST-K01,
made by Ishihara Sangyo, Co., Ltd.) were added
at room temperature to 94.99 g of alcohol (trade
name: AP-7, made by Nihon Kaseihin, K.K.) and
mixing was performed for approximately 1 hour
at 40 C. to obtain a coating solution. The same
method as that of Example 1 was carried out to
form a 60 nm-thick silica thin film with ruthenium
oxide added and titanium oxide microparticles
dispersed (33.3 weight % silicon oxide, 33.3
weight % titanium oxide, 33.3 weight %
ruthenium oxide, Ru/Ti=0.60 (atomic ratio)) on a
soda lime silicate glass substrate with silica film
of the same type described in Example 1. The
sample obtained thus shall be referred to as
sample P (glass substrate/silica film/silica thin
film with ruthenium oxide added and titanium
oxide microparticles dispersed). The various
anti-fogging and anti-soiling performance
evaluation results of sample P are shown in
Table 4. These clearly show that sample P has
excellent anti-fogging and anti-soiling properties.
Example 16
0.10 g of rhenium trichloride, 0.34 g of
tetrachlorosilane, and 2.00 g of titania
microparticle dispersion (trade name: ST-K01,
made by Ishihara Sangyo, Co., Ltd.) were added
at room temperature to 103.99 g of alcohol
(trade name: AP-7, made by Nihon Kaseihin,
K.K.) and mixing was performed for
approximately 1 hour at room temperature to
obtain a coating solution. The same method as
that of Example 1 was carried out to form a 75
nm-thick silica thin film with rhenium oxide
added and titanium oxide microparticles
dispersed (40 weight % silicon oxide, 40 weight
% titanium oxide, 20 weight % rhenium oxide,
Ru/Ti=0.16 (atomic ratio)) on a soda lime silicate
glass substrate with silica film of the same type
described in Example 1. The sample obtained
thus shall be referred to as sample Q (glass
substrate/silica film/silica thin film with rhenium
oxide added and titanium oxide microparticles
dispersed). The various antifogging and anti-
soiling performance evaluation results of sample
Q are shown in Table 4. These clearly show that
sample Q has excellent anti-fogging and anti-
soiling properties.
Comparative Example 2
A chromium addition solution was prepared by
dissolving 0.10 g of chromium trichloride
hexahydrate in 99.90 g of alcohol (trade name:
AP-7, made by Nihon Kaseihin, K.K.). 0.34 g of
tetrachlorosilane, 2.0 g of titania microparticle
dispersion (trade name: ST-K01, made by
Ishihara Sangyo, Co., Ltd.), and 2.67 g of the
abovementioned chromium addition solution
were added at room temperature to 94.99 g of
alcohol and mixing was performed for
approximately 1 hour to obtain a coating
solution. Using the same method as that of
Example 1, a 70 nm-thick silica thin film with
chromium oxide doped and titanium oxide
microparticles dispersed (49.85 weight % silicon
oxide, 49.85 weight % titanium oxide, 0.30
weight % chromium oxide, Cr/Ti=0.0064 (atomic
ratio)) was formed on a soda lime silicate glass
substrate with silica film of the same type
described in Example 1. The sample obtained
thus shall be referred to as sample R (glass
substrate/silica film/silica thin film with chromium
oxide doped and titanium oxide microparticles
dispersed). The various anti-fogging and anti-
soiling performance evaluation results of sample
R are shown in Table 4. These clearly show that
the antifogging and anti-soiling properties are
not improved by the doping (addition of minute
amounts) of Cr.