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Esnek poliretan kpn imalat iin yntem

WO 2010023885 A1
ZET

Mkemmel su direncine ve alkaliye direncine sahip, ok iyi basn dayanma gerginliine sahip esnek
bir poliretan kpk. Bir poliretan kp, bir poliol bileeni (A) ve bir difenilmetan diizosiyanat esasl
poliizosiyanatn (B) bir katalizr (C), kpk giderici madde (D), kprme maddesi (E) ve apraz
balayc madde varlnda tepkimeye girmesiyle elde edilir. (A), bitki kaynakl bir balang malzemesi
olan hintyana dayanan bir poliol (a1) poliol bileenine (A) gre% 10 ila 50 ktle ierdii polimer
balama maddesi (F) ierir.

HAK TALEPLERI (5) u dilden evrildi: Japonca

1. The polyol component (A) and diphenylmethane diisocyanate-based polyisocyanate (B),


catalyst (C), foam stabilizer (D), is obtained by reacting in the presence of a blowing agent
(E) and the crosslinking agent (F) soft In polyurethane foam, characterized by containing
10 to 50 mass% with respect to castor oil-based polyol as a raw material of plant origin
(a1) is a polyol component (A), and a process for producing a flexible polyurethane foam.

2. The polyol component according to claim 1 (A) is castor oil-based polyol (a1),
characterized in that comprising a polyether polyol (a2) and the polymer polyol
(a3), process for producing a flexible polyurethane foam.

3. Oxyethylene group content of the polyol component (A) is characterized in that


not more than ~ 13% 6% or more, the method for producing a flexible
polyurethane foam according to claim 1 or 2.

4. Average functionality of the diphenylmethane diisocyanate-based


polyisocyanate (B) is characterized in that in the range of 2.1-2.5, the method
for producing a flexible polyurethane foam according to any one of claims 1 to 3.

5. Wherein the foam density is 70 ~ 120kg / m 3, 25% ILD is 250 ~ 950N /


314cm 2, and method for producing a flexible polyurethane foam according to
any one of claims 1 to 4.

AIKLAMA u dilden evrildi: Japonca

Process for producing a flexible polyurethane foam

The present invention relates to a process for producing a flexible polyurethane foam. More
particularly, by using a castor oil is a polyol derived from a vegetable, water resistance, excellent alkali
resistance, and compressive residual strain is a method for producing a very good flexible
polyurethane foam.

Conventionally, flexible polyurethane foams since it has flexibility and excellent impact-absorbing
properties, are widely used as cushioning materials and cushioning materials such as sofa. However,
many of the polyurethane foam to be those lightweight using the toluene diisocyanate-based
polyisocyanate, foam physical properties can not be said sufficient with respect to aging
durability. Further, toluene diisocyanate-based polyisocyanate has a high volatility, the health effects of
isocyanates of workers in production locations are concerned. Furthermore Conventional polyurethane
foams, since the alkali resistance performance against water resistance or alkali detergent is
insufficient, swollen by washing or has a problem occurs strength lowers degradation. As a method for
producing excellent flexible polyurethane foam in the water resistance, the specific example the polyol
component comprises a polyoxyalkylene polyol, wherein the polyoxyalkylene polyols when taken as
100 wt%, the content of oxyethylene units is 18 wt. % or less and a method for has been proposed
(see Patent Document 1), description of the durability is not made.
JP-A-09-071627 Publication Patent Publication No. 2006-104404

An object of the present invention is excellent in water resistance and alkali resistance. Moreover,
compressive residual strain is to provide a very good flexible polyurethane foam. Furthermore, the
working environment without using a toluene diisocyanate-based polyisocyanates for improvement,
and it is to use more raw materials less plant origin of the viewpoint from the environmental impact of
recent environmental protection.

The present inventors, with the aim of solving the above problems, water resistance, alkali resistance,
and to provide a good foam physical properties such as compression residual strain, Ya organic
diisocyanate is a major raw material for the flexible polyurethane foam For polyols, also the blowing
agent and the foam stabilizer and other auxiliaries or the polymerization conditions and the
polymerization catalyst for such further to obtain a flexible polyurethane foam having a proper density
and hardness range, the overall thinking turned and is subjected to various studies, it was repeated
experimental trials and multifaceted considerations.

In those processes, as a result of accumulation of experimental examination with attempts to solve the
above problems, by using a castor oil-based polyol derived from plants in the polyol component, and
the resolution of the problem of the present invention Can be a, the water resistance, alkali resistance,
relates to providing an excellent flexible polyurethane foam physical properties such as compression
residual strain, and found to be very effective, which resulted in the creation of the present invention.

In the present invention, the addition amount of the castor oil based polyol (a1) to be used, relative to
the polyol component (A), it is particularly effective when it is in the range of 10 to 50% by weight.

Basic and main components in the present invention, the polyol component (A), diphenylmethane
diisocyanate-based polyisocyanate (B), catalyst (C), foam stabilizer (D), the foaming agent (E),
crosslinking agent (F) a process for preparing a flexible polyurethane foam by composition for molding
composed of other auxiliaries, characterized in that the addition of 10-50% by weight castor oil based
polyol (a1) relative to the polyol component (A) and a process for producing a flexible polyurethane
foam.
Furthermore, in the present invention, specific identifying such polyol component and
diphenylmethane diisocyanate-based polyisocyanate or foaming agent, more excellent improvement
results.
In the present invention, the flexible polyurethane foam, water resistance, alkali resistance, and, it is
possible to obtain physical properties such as excellent compressive residual strain. Therefore, in the
flexible polyurethane foam obtained by the present invention, can be utilized as a buffer around a
mainly washable cushioning material or a washing machine, it is very useful.

In addition it will be described in detail the contents of the present invention.


First, the polyol component used in the production of polyurethane foams in the present invention (A)
is intended to form the polyurethane by diisocyanate and polyaddition, castor oil-based polyol (a1), a
polyether polyol (a2) and polymer polyol (a3), consisting of capital.

Castor oil-based polyol (a1) as a purified castor oil, semi-refined castor oil, may be any unrefined
castor oil, hydrogenated castor oil was added hydrogen, castor oil fatty acid and a polyol (the low-
molecular polyol and / or linear or branched polyester obtained by reaction of polyether polyols), for
example, castor oil fatty acid diglyceride, monoglyceride, mono and castor oil fatty acid and trimethylol
alkanes, di- or triester, and castor oil fatty acid mono with polypropylene glycol, like di- or tri-ester,
etc.. From the point of view of petroleum reduction and environmental protection of chemical raw
material Among this, it is preferred to use the castor oil of unmodified. Here, the main component of
the "castor oil" is a triglyceride of ricinoleic acid include hydrogenated castor oil is the "castor oil".
Moreover, the main component of the "castor oil fatty acid" is a ricinoleic acid, in the "castor oil fatty
acid" includes hydrogenated castor oil fatty acid. Also, the "trimethylol alkane", for example trimethylol
methane, trimethylol ethane, trimethylol propane, trimethylol butane, trimethylol pentane, trimethylol
hexane, trimethylol heptane, trimethylol octane, trimethylol nonane and trimethylol decane It can be
mentioned. The number-average molecular weight of castor oil or castor oil-modified polyol is
preferably from 500 to 6,000, more preferably is 900 to 2,000. By number average molecular weight is
to use 900 to 2,000 castor oil based polyol (a1), it is possible to obtain a flexible polyurethane foam
having a density and hardness range suitable for applications such as cushioning materials and
cushioning materials . The URIC specifically manufactured by Ito Seiyu Ltd.
And the like H-24 and URIC H-30, but is not limited thereto. Castor oil-based polyol (a1) for the polyol
component (A), it is preferred to use 10 to 50% by weight. It is not possible to express water, alkali
resistance performance sufficiently below this range. Further, the moldability is deteriorated if it
exceeds this range.

Polyether polyol (a2) is, in the present invention, the number-average molecular weight of 1,000 to
10,000, a nominal functionality of 2 or more are preferred. Is less than the number average molecular
weight is lower, the flexibility of the resulting foam is insufficient, whereas if it exceeds the upper limit,
tends to decrease the hardness of the foam. In addition, when it is less than 2 nominal functionality, is
a problem that the compressive residual strain becomes worse occur. Incidentally, the nominal
functionality and will refer to functional groups of the initiator used in obtaining the polyol.

The (a2), such as polypropylene ethylene polyol (PPG) and polytetramethylene ether glycol (PTG) is
used as polyester polyols, adipic acid ethylene glycol polyester polyol of a polycondensation polyester
polyols and lactone-based polyester polyol such as polycaprolactone polyol is used.
Polymer polyol (a3), a method of polymerizing ethylenically unsaturated monomers in polyether
polyols, additional method of mixing the produced polymer particles in the polyether polyol, the
macromonomer and an ethylenically unsaturated having an ethylenically unsaturated group It is
produced by a method of polymerizing monomers in a polyether polyol.
The ethylenically unsaturated monomers such as styrene, acrylonitrile and the like. Of these, preferred
are those obtained by polymerizing ethylenically unsaturated monomers in a polyether polyol, more
preferably one obtained by polymerizing ethylenically unsaturated monomers in the polyoxypropylene
triol. The content of the polymer fine particles is 50% by weight relative to total polyol or less,
particularly preferably not more than 30 mass%. When the content of the polymer fine particles
exceeds 50 mass%, the viscosity of the polymer polyol, the workability in molding deteriorates.

As the polyol component (A), in addition to the above-mentioned (a1) ~ (a3), a polyester polyol,
polycarbonate polyol, polybutadiene polyol, it is possible to also use the lactone-based polyols and the
like.

The polyisocyanate component used in the production of polyurethane foams in the present invention
is a diphenylmethane diisocyanate based polyisocyanate (B).
As the diphenylmethane diisocyanate-based polyisocyanate (B), specifically, for example, 4,4'-
diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate
and diphenylmethane diisocyanate comprising a mixture thereof (Pure MDI), polymethylene
polyphenylene polyisocyanates (p-MDI), these urethane-modified products, urea-modified products,
allophanate-modified compounds, various modified products such as biuret modified products it may
also be used. Note, in particular, pure described above MDI, when using a mixture of MDI and p-MDI,
it is possible to obtain a better quality of flexible polyurethane foams. The average functionality of the
diphenylmethane diisocyanate-based polyisocyanate (B) is preferably in the range 2.1 to 2.5. Average
shaping stability of the foam obtained when the functionality of less than 2.1 is insufficient, it is difficult
to obtain foams having good durability. If it exceeds 2.5, the elongation percentage of the foam tends
to decrease.

As the catalyst (C), the various urethane catalysts are well known and can be used in the art.
By illustration, triethylamine, tripropylamine, tributylamine, N- methyl Mori holin, N- ethyl Mori holin,
dimethylbenzylamine, N, N, N', N'- tetramethyl hexamethylenediamine, N, N, N', N', N''-
pentamethyldiethylenetriamine, bis - (2-dimethylaminoethyl) ether, triethylenediamine, 1,8-diaza -
bicyclo (5,4,0) undecene -7,1,2- dimethyl imidazole, dimethyl ethanolamine, N, N- dimethyl--N-
hexanolamine, further these organic acid salts, stannous octoate, organic metal compounds such as
zinc naphthenate may be mentioned. Furthermore, N, N- dimethylethanolamine, N, an amine catalyst
having active hydrogen, such as N- diethylethanolamine preferred.
The addition amount of the catalyst (C), relative to the polyol component (A), is preferably 0.01 to 10
wt%. In the range less than is likely to be insufficient curing moldability and above this range may
deteriorate.

Foam stabilizer (D) is typically the surfactant is used, an organic silicon-based surfactants can be
suitably used. For example, such as Goldschmidt Co., Ltd. B-4113LF and Nippon Unicar Co., Ltd. L-
5309 and the like. These may be used singly, or two or more kinds.
The addition amount of the foam stabilizer (D) is, in order to form a uniform cell, relative to the polyol
component (A), is preferably 0.01 to 10 wt%.

As the foaming agent (E), mainly we use water. Water generates carbon dioxide by reaction with
isocyanate groups, so that the thereby foamed. It is also possible to use water and additionally any of
the blowing agents. For example, it may be used in combination with low boiling organic compounds,
such as small amounts of cyclopentane and isopentane, it can also be foamed to be mixed into
dissolved air or nitrogen gas or liquefied carbon dioxide into the stock solution using a gas loading
device.
The addition amount of the foaming agent by setting the density of the resulting products. Normally,
0.5 to 15% by weight relative to the polyol component (A), when considered as a cushion material or
buffer material applications, it is preferably 0.8 to 1.5% by weight. May exceed the upper limit of foam
does not easily stabilized, it is less than the lower limit might foaming is not made effective.

As the crosslinking agent (F), and preferably low molecular alcohols used in the synthesis of the
aforementioned polyester polyol, a low molecular amines, such as low molecular aminoalcohols, and
be given a low molecular active hydrogen compound having a molecular weight of less than 500 I
can.
It can be mixed with any alone or two or more kinds. Among these, from the reaction of isocyanate
groups gentle point, low molecular aminoalcohols, more preferably diethanolamine.

And, in the production of flexible polyurethane foams of the present invention, anti-aging agents such
as antioxidants and ultraviolet absorbers, fillers such as calcium carbonate or barium sulphate, flame
retardants, plasticizers, coloring agents, antifungal agents various known additives etc., can be used if
necessary to aid.

Next will be described specifically on the basis of the present invention examples and comparative
examples, unless the present invention is that it does not exceed the gist thereof, is not limited to
these examples. Unless otherwise specified, "%" in the sentence it is assumed to be mass.

Examples 1-8, Comparative Examples 1-6


Among the raw materials shown in Table 1, 2 and 3, a mixture of all materials other than the
polyisocyanate compound to liquid temperature (polyol system) was adjusted to 25 1 ,
adjusting the polyisocyanate compound to the liquid temperature of 25 1 It was. In addition a
predetermined amount of the polyisocyanate compound to the polyol system, after foamed mixer
injected polyurethane foam (min 7000 rotation) in the mixing and mold 7 seconds, taken out crushing
process from the mold (urethane foam is foamed The molded product after the inside of the gas that
is, through that) to escape by breaking the cells, the physical properties of the obtained flexible
polyurethane foam were measured. Incidentally, isocyanate index (NCO Index) of Table 1, 2 and 3 are
equivalent ratio of NCO groups to NCO-reactive groups present in the formulation (NCO / NCO-
reactive groups).
[Foaming conditions]
Mold temperature: 55 ~ 60
Mold shape: 100 300 300mm
Mold material: aluminum curing conditions: 55 ~ 60 6 minutes crushing conditions: five-stage
crushing roller

Use raw materials]


(Polyol component)
Polyol 1: PO / EO EO end content obtained by adding a = 14%, average functionality = 3.0, hydroxyl
value = 24 polyoxyethylene polyoxypropylene polyol (mgKOH / g), Asahi Glass Urethane Co., Ltd. Ltd.
EL-851B
Polyol 2: glycerin and then addition polymerization of PO / EO, further polymeric polyols,
manufactured by Asahi Glass Urethane Co., Ltd. EL of the average number of functional groups = 3.0,
which is obtained by polymerizing acrylonitrile monomer, hydroxyl value = 28 (mgKOH / g) -910
Polyol 3: Average number of functional groups = 2.7, hydroxyl value = 160 (mgKOH / g) crude castor
oil, Ito Oil Co., Ltd. URIC H-24
Polyol 4: a commercially available two kinds of polyoxyethylene polyoxypropylene polyols are blended
with the polyol component (A) manufactured by Nippon Polyurethane Industry Co., Ltd. EO content
was adjusted to 14.1% in NE-697
Polyol 5: a commercial two kinds of polyoxyethylene polyoxypropylene polyols are blended with the
polyol component (A) manufactured by Nippon Polyurethane Industry Co., Ltd. EO content was
adjusted to 12.6% in NE-698
Polyol 6: Commercially available two polyoxyethylene polyoxypropylene polyols are blended with the
polyol component (A) manufactured by Nippon Polyurethane Industry Co., Ltd. EO content was
adjusted to 11.9% in NE-699
Polyol 7: Commercially available two polyoxyethylene polyoxypropylene polyols are blended with the
polyol component (A) the adjusted Nippon Polyurethane Industry Co., Ltd. NE-700 as EO content is
11.2% in
Polyol 8: Commercially available two polyoxyethylene polyoxypropylene polyols are blended with the
polyol component (A) manufactured by Nippon Polyurethane Industry Co., Ltd. EO content was
adjusted to be 6.7% in NE-701
Polyol 9: Commercial two kinds of polyoxyethylene polyoxypropylene polyols are blended with the
polyol component (A) manufactured by Nippon Polyurethane Industry Co., Ltd. EO content was
adjusted to be 5.3% in NE-702

(Poly isocyanate component)


Polyisocyanate 1: nominal average functionality = 2.27, NCO content = 28.8%, viscosity = 100mPa s
MDI polyisocyanate (trade name "CEF-300", manufactured by Nippon Polyurethane Industry Co.,
Ltd.)
Polyisocyanate 2: toluene diisocyanate-based polyisocyanate

(Catalyst)
Catalyst 1: 33% dipropylene glycol solution of triethylenediamine, manufactured by Tosoh Corporation
TEDA-L33
Catalyst 2: bis 70% dipropylene glycol solution of (2-dimethylaminoethyl) ether, manufactured by
Tosoh Corporation TOYOCAT ET
(Foam stabilizer)
Foam stabilizer: silicone-based foam stabilizer, gold shoe mid Co., Ltd. B-4113LF

[Method for measuring the physical properties of the polyurethane foam]


It was performed according to the method of JIS K6401.
The 25% ILD, with a force which is obtained a foam sample when compressed by 25%, it becomes the
indicator of the hardness.
Evaluation of alkali resistance, 5 days of 25 conditions, was immersed a form in an alkaline
aqueous solution of pH = 13, swelling ratio of the foam after immersion and (%), tensile strength,
elongation, and the retention of tear strength It was carried out by measuring the rate (%).

The swelling ratio (%)


= {- / Immersion length of the front of the specimen (the length of the specimen after the immersion
length of the specimen before immersion)} 100

Water resistance evaluation, five days in 25 condition, is immersed forms in tap water, the swelling
ratio of the foam after immersion and (%), tensile strength, elongation, and the retention ratio of tear
strength (%) It was carried out by measuring the.
As shown in Comparative Examples 1-2 in Table 1, curing property is lowered to contain 10% toluene
diisocyanate based polyisocyanate in the polyisocyanate component, the molding property is
deteriorated. Further, even when the content of toluene diisocyanate-based polyisocyanate was less
than 10%, due to the high volatility of toluene diisocyanate-based polyisocyanates it is likely to be
affected the health of workers in production locations.
As shown in Comparative Example 3 in Table 2, in the case of unused castor oil-based polyol stability
is degraded filling property of the foam is deteriorated. Moreover, the water resistance test and alkali
resistance test, the swelling ratio is increased, retention of mechanical properties is reduced. On the
other hand, as shown in Comparative Example 4, when the amount of the castor oil-based polyol
exceeds 50 mass%, the strong German foaming of the foam, cracking occurs in the crushing stroke
after demolding.
Table 3 shows the castor oil-based polyol is fixed to 20 wt%, by respectively adjusting the EO content
by changing the mixing ratio of the polyol component (A), a physical property measurement results but
to produce a flexible polyurethane foam. As shown in Comparative Example 5, when the EO content is
too high, it deteriorates stability is deteriorated filling of the foam. Moreover, the water resistance test
and alkali resistance test, the swelling ratio is increased, retention of mechanical properties is
reduced. On the other hand, as shown in Comparative Example 6, when the EO content is too small,
becomes strong German foaming of the foam, cracking occurs in the crushing stroke after demolding.

By comparing the Examples and Comparative Examples described above, in the present invention,
uses a diphenylmethane diisocyanate-based polyisocyanate (B), a castor oil based polyol (a1) is
blended 10-50 wt%, and the polyol component EO content of (A) is more than 6% - 13%
If it was less, excellent working environment, water resistance, alkali resistance and durability
(compression residual strain) that obtain good polyurethane foams it is clear and pronounced the
significance of the configuration of the present invention excellence it can understand.

PATENT ATIFLARI