Coloration of glasses with organic colorants by the sol-gel colored coating method

Hiroyuki Nakazumi,*l Shinya Amano,1 and Kazuo Sakai2

1 Department of Applied Material Science, College of Engineering, University of Osaka Prefecture,
Gakuen-cho 1-1, Sakai, Osaka 593, Japan
2 Fuji Pigment Co. Ltd., 2-23-2 Obana, Kawanishi, Hyogo 666, Japan

ABSTRACT
A transparent colored thin gel layer (100-300 nm thick) was formed on a glass surface by the dipping-withdrawing
coating (1-3 mm s-i) method. The colored coating layer was dried at ambient atmosphere, and then heated at 100 C for 15
mm. Cationic dyes, such as triphenylmethane, phenoxazinium, phenazinium, and phenothiazinium dyes, can be soluble

uniformly under the silica sol processing conditions where hydrolysis and condensation of tetraethoxysilane or
methyltriethoxysilane in the presence of water and acid occur. Superfine particles of some organic pigments also are dispersed

uniformly in such sol in high concentration, and they are coated on the glass by similar method. The effects of nickel
complexes and matrix gels on the photofading of the colored thin gel film using organic cationic dyes by the irradiation of
ifitered visible light (>390 nm) using 500W-Xe lamp have been studied. Anthraquinone, phenazinium, and phenoxazinium
dyes with terminal triethoxysilyl group to connect them directly with silica matrix of the gels were prepared, as reactive
dyes, and reactivity of the reactive dyes under conditions of sol-gel processing has been investigated.
Keywords: Sol-gel method, Organic dyes, Organic pigments, Coloration of glass, Lightfastness, Nickel complex, Particle
size, Reactive dye

1. INTRODUCTION
The so-called sol-gel process has attracted a great deal of attention in the preparation of advanced glass and ceramic
materials'2 and is particularly important in thin coatings on glass substrates. Even though colored silica bulk gels have
been prepared using organic dyes, such as quinizarine, acridine and Rhodamine B, for photochemical hole burning applied to

high density optical data storage systems,34 little is known about thin gel films colored by organic dyes. In the colored
bulk gels, low concentration of dye required, and the colored concentration of ca. 10 mol 1-1 was generally used in sol.

However, for coloration of glass by the gel film, much concentrated solution of organic colorants needs in sol, and thus

higher solubiity of organic colorants in sol is required. This coating technology is also interesting for the preparation of
colored glasses using organic colorants and is presently being applied to the surfaces of CRTs for improving color TV image
resolution.5 In this study, the basic sol-gel colored coating method for the coloration of glass plates and features of organic
colorants required for this coloration will be described.

2. SOL-GEL COLORED COATING

First, the colored sol was prepared by mixing tetraethoxysilane (JEOS) or methyltriethoxysilane (MTES), alcohol,
water, acid, and dye at room temperature for 1-5 h. The amount of dye added was 0.2-0.8 wt% of TEOS or MTES for
coloration of glass by the sol-gel colored coating method. The colored gel film on glass plates was formed by the dippingwithdrawing method (rate of drawing: 1-3 mm i) using the colored sol.68 The coloring concentration of the gel film is
dependent on the dip coating rate. The faster coating rate leads to higher coloring concentration due to the formation of a
thick film. Drying this colored glass at ambient atmosphere and then heating it at 100-200C promotes gelation to form a
hard transparent colored gel film, in which the organic dyes are dispersed in the 5i02 network. Therefore, they are not effused
to the organic solvent. The sol-gel colored coating offers the following practical advantages.

356 ISPIE Vol. 2288 So/-Gel Optics II! (1994)

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

0819416126/94/$6.OO

1 . Transparent coloring in various hues by organic dyes

2. Easy formation of a thin colored film (thickness: 100-300 nm)
3. Formation of a hard transparent film by heating
4. Easy coloring in various shapes of glasses

Two methods are used to make colored gel films: method 1 (disperse coloration) is a dispersion of dyes in the
2 network
(Fig.1) and method 2 (coloration with organic reactive dyes) involves the direct connection of reactive dyes7 with a network

of Si02 matrix gels. In method 2, the dyes with a terminal triethoxysilyl group are available to connect with a network
under the silica sol processing conditions, as Scheme 1.

t.

-0Si 0 Si 0 Si 0 SiOSiOSiOSi

OSiOSiOSiOSiOSi 0Si 0Si

I

c?

? ?

? ?

0Si0Si0SI 0Si 0Si0Si 0Si

?
: Organic Colorants

Figure 1. Schematic representation of the colored gel film prepared by disperse coloration

II

i H3O

n j-Si(oH)a

Sch

iI
6

c
Si(OEt)4

[jSi(OEt)3

j H3O
+

m51(OH)4

LF

O0SiOSiO

eme 1. Sch ematic representation of the colored gel film prep ared by reactive dyes

3.

ORGANIC COLORANTS FOR SOL-GEL COLORATION

3.1. Organic dyes for sol-gel coloration

For use in a colored gel film, the organic dyes need to have an intense absorption band in the visible region. The values
for molar absorptivity (e) need to be large (>10 4), for the dyes to show higher coloring ability. Another necessary property

SPIE Vol. 2288 Sol-Cel Optics Ill (1994)! 357

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

of the organic dyes for this application is that they should have good solubility in an alcohol-water solution, because the sol
is formed in such a solvent (ca 1.0-10 wt%). In addition, they need a high melting or decomposition point, because a colored
gel film has to be heated for more gelation to occur. The most useful dyes for the dispersed coloration method are basic dyes
1-5 which are commercially available, because they have higher c and good solubiity.9

1-

Me2N
X

Me2N

O7NMe2

NMe

2: X=S
3: X=O
4: X=NR

When other dyes containing some sulfonic residues were used, they were not adsorbed sufficiently into the gel matrix,
because the sulfonic residues interacted strongly with the matrix gel. Solvent dyes, such as C. I. Solvent Red 1306
available for this coloration. The absorption band is broad in the silica gel film relative to the band observed in similar
concentrations. The spectrum of the dye in the matrix gel changes slightly after coating the substrate. (Fig.2)

Generally, basic dyes such as 1-5, have poor lightfastness, and cause decoloration by photooxidation. Some nickel
complexes are known to be effective in inhibiting the photofading of these dyes, and to be most effective quencher of singlet

oxygen causing photodegradation of dyes. The effects of nickel complexes on the photofading of colored thin gel by
irradiation of the ifitered visible light (>390 nm) using 500 W-Xe lamp have been studied.

Wavelength I nm

Figure 2. Absorption spectra of Methylene Blue 2 (R=H) in the gel films prepared from TEOS (a), and from MTES (b),
and in EtOH (c)

The addition of nickel complexes, bis(O,O-diethylphosphorodithiolato)nickel (DPD), bis(N,N-dibutyldithiocarbamato)nickel (NBC), and bis(dithiobenzil)nickel (DTB), as typical stabilizers, results in an improvement of the light-fastness of dye

358 /SPIE Vol. 2288 Sol-Ce/ Optics III (1994)

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

2 in a gel film prepared from MTES, as shown in Fig. 3. Nickel complex DPD is the most effective for improvement of
lightfastness of the colored gel film. However, effects of nickel complexes are very little in a gel film from TEOS which
formed smaller pores (Fig.3 (b)).

40

4(

U)

U)

C)

C)

0
U

C.)

2
Irradiation time / h

Irradiation time / h

Figure 3. (a) Photofading of dye 2 (R=H) in gel film prepared from MTES. The dotted curve represents photofading
observed in CH 2C12 of 2. (b) Photofading of dye 1 (R=R=H, R"=4'-NH2) )in gel film prepared from TEOS
and MTES in the presence of DPD.

3.2. Organic pigments for sol-gel coloration

20

0
.0

10

(13

a)

N
Cl)

12

16

20

25

Diameter of particles / mi

Figure 4. Size distribution of organic pigment particles (Magenta pigment) in isopropanol

SPIE Vol. 2288 So/-Ge/ Optics III (1994)! 359

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

Organic pigments for sol-gel coloration also need to have same absorption properties to that of organic dyes. Organic
pigments in a suitable crystalline form are insoluble in water-alcohol solution and have optimum particle size (50-2000 nm).

In application to the sol-gel color processing of organic pigments, the size reduction of the pigment is of the most
importance. To get transparent colored gel film, the particle size should be below 300 nm, and should be uniformly
dispersed in a sol. The shorter particle size leads to poor lightfastness such a cationic dye. A possible size range of
pigment particles for sol-gel coloration was 10-25 nm, as shown in Fig. 4. Copper phthalocyanine, as typical organic
pigments, was used for this coloration. One of the advantages of sol-gel coloration by using organic pigments is that high
colored concentration of organic pigments could be made up in a sol and thin gel film. For example, a colored ifiter was
made up by the dipping-coating method overlapped 4 times (thickness: ca. 800 nm), as shown in Fig. 5. Transparent yellow
to blue coating layer on slide glass was easily formed by using various organic pigments.

2.0
C)

1.0

Wavelength /

nm

Figure. 5. Absorption spectra of slide glass colored by the dipping-coating method overlapped ((a) 1; (b) 2; (c) 3; (d) 4
times) using copper phthalocyanine (C.I. Pigment Blue 15)

3.3. Reactive organic dyes for sol-gel coloration

NH2 0

111I1T'1IILNHR

0 NH2 0

R= (CH2)3Si(OEt)3

We have prepared some phenoxazinium, phenazinium, and quinone dyes, 6-8, with a terminal triethoxysilyl group

connected directly with a network of Si-O matrix gels in the sol-gel processing. For example, preparation of dye .6 is shown

in Scheme 2. Reaction of the corresponding phenoxazinium, phenazinium, or anthraquinone derivatives with

360 ISPIE Vol. 2288 So/-Gel Optics III (1994)

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

aminopropyltriethoxysilane in refluxing EtOH gave dyes 6-8 with a terminal triethoxysilyl group in 20-30% yield [6,
Xmax 628 nm(logc= 4.63); 7, Xmax 573 nm(logc=4.30) in EtOH; 8, Xmax 616 nm(logc=4.15) in acetone].

NH2(CH2)3Si(OEt)3

NHR
CI

Scheme 2. Preparation of dye 6 having a terminal triethoxysilyl group

We have succeeded in coating glass surfaces with these reactive dyes by the above described sol-gel colored coating

method using dyes 6

and 7 .

A transparent blue or violet coating layer on a slide glass was formed by the dipping-

withdrawing method. The absorption band is broad in the silica thin layer and shifted to shorter wavelength, compared with a

similar concentration of dye in water, as shown in Fig.6. However, the colored coating by anthraquinone dye 8 was not
successful, since it has poor solubiity in alcohol-water.

0.2

I)

0.12

400

500

600

700

A I rim

Figure 6. Absorption spectra of dye 6

(a)

in gel film (thickness 200 nm) prepared from TEOS and (b) in water

Hydrolysis of dye 6 was performed under the silica sol processing conditions to examine the reactivity of the terminal
triethoxysilyl group. The hydrolysis product resembled a gel powder, and was insoluble in organic solvents. The JR spectra
of the hydrolyzed and unhydrolyzed dye differ noticeably. In the hydrolysis product of 6, the peak intensity at 2900 cm1
assigned to CH3 and CH2 stretching mode decreased, and the peak intensity around 3500 cm for OH group increased, as
shown in Fig. 7. Also, the peaks at 950 and 1070 cm1 assigned to Si-OEt bond stretching and deformation disappeared.

An endothermic peak at 120 C, which is assigned to the polycondensation of the Si-OH group, was observed in the
DTA-TGA (differential thermal analysis-thermal gravimetric analysis) of the hydrolysis product of 6, as shown in Fig. 8.
Such an endothermic peak is generally observed in silica gels produced by the sol-gel process. The IR spectra and thermal
analyses of the hydrolysis product of 7 were similar.

SPIE Vol. 2288 So/-Gel Optics III (1994) /361

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

Thus, the reactive dyes 6 and 7 with a terminal triethoxysilyl group are easily hydrolyzed and directly polycondened with

hydrosilane generated during the gelation of the alkylsilane. These reactive dyes can be directly connected with an Si-O
network in the silica-coating layer, and are easily coated on glass by this new method.

0
0
0

Waveriumber I

cm

Figure 7. JR spectra of dye 6 in KBr (a) after hydrolysis and (b) before

dO
U,

0
C

16
30

90

150

210

270

Temperature / C

Figure 8. DTA and TG curves for the hydrolysis product of 6 (10 C/min under nitrogen)

362 ISPIE Vol. 2288 Sol-Cel Optics Ill (1994)

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms

4. EXPERIMENTAL
4.1. Preparation of the colored gel film
A colored transparent gel film on a slide glass was formed by the dipping-withdrawing method (rate of drawing: 1-3 mm

s1) using a coating solution which consisted of TEOS (12.5 g), ethanol (25 ml), water (12 ml), dilute HCI (0.15 ml), and
organic dyes (50-75 mg). Heating this coating layer for 15 mm at 100 C formed a hard colored gel film. The thickness of
the coating gel film is 100-300 nm. Addition of nickel complex to organic dyes was 1:1 molar ratio. In the use of organic
pigment, 3.0 wt% super-fine dispersed solution( 16 ml) of organic pigment in isopropanol was added to the mixture (36 ml)
of TEOS-(EtOH-BUOH)-H20-HCI (or FINO3) (1:2:1:0.6).

4.2. Photofading of the colored gel film on glass plate

The colored gel film on glass plate was irradiated with a ifitered visible light (>390 nm) using 500W-Xe lamp. The
relative changes in the absorbance of dye on the glass plate at its absorption maximum were determined spectrophotometrically.

4.3. Synthesis of organic reactive dyes

Reaction of the corresponding phenoxazinium, phenazinium derivatives, as shown in Scheme 2 , and some quinone dyes
with aminopropyltriethoxysilane in refluxing EtOH for 15-30 h gave 6-8 . The products were reprecipitated with ethanolether or recrystallized from EtOH, and identified from 1H-NMR spectra.

5. REFERENCES
1. L.L. Hench and J. K. West, Chem. Rev., 90, 33, 1990.
2. J. D. Mackenzie, 'Ultrastructure Processing of Ceramics, Glasses, and Composites', ed., L.L.Hench and D.R.
Ulrich, pp 15, Wiley, New York, 1984.
3. T. Tani H. Namikawa, K. Arai, and A. Makishima, J. Appl. Phys., 58, 9, 1985.
4. D. Avnir, D. Levy and R. Reisfeld, J. Phys. Chem., 88, 5956, 1984.
5. T. Itoh, S. Matsuda and K. Shimizu, Toshiba Rev., 45, 831, 1990.
6. H. Nakazumi, S. Amano and T. Kitao, Chem. Express, 6, 607, 1991.
7. H. Nakazumi and S. Amano, J. Chem. Soc. Chem. Commun., 1992, 1079.
8. H. Nakazumi, S. Amano and E. Minatoya, J. Jpn. Soc. Color. Mater., 66, 517, 1993.
9. H. Nakazumi, S. Amano and E. Minatoya, J. Jpn. Soc. Color. Mater., in press 1994.

SPIE Vol. 2288 So/-Gel Optics 111 (1994)! 363

Downloaded From: http://proceedings.spiedigitallibrary.org/ on 06/13/2013 Terms of Use: http://spiedl.org/terms