JPH0826287B2 - Composition for forming protective film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for forming a protective film suitable for forming a protective film such as a transparent substrate or a color filter in a liquid crystal display device.

(Prior Art) In recent years, many color liquid crystal displays in which a color filter for color separation is combined with a liquid crystal element have been proposed.

When the color filter is used in combination with a liquid crystal element as a color liquid crystal display element, the color filter is arranged in series with respect to the optical path. Therefore, when viewing the display from the front of the color liquid crystal display element, the display is You can see it neatly.

However, for example, when the color filter is arranged outside the liquid crystal element, and when the display pixel is fine due to the thickness of the glass used for the liquid crystal element, the ""Parallaxshift" occurs.

In order to prevent such parallax displacement, a color liquid crystal display element in which a color filter is arranged inside the liquid crystal element has been proposed (for example, “Nikkei Electronics”, # 9).
~ 10, published on September 10, 1984, published by Nikkei McGraw-Hill Inc., No. 1
See pages 211-240).

As described above, the following two methods are known as methods for disposing the color filter inside the liquid crystal element.

Color filter to indium tin oxide (IT
O) or other transparent electrode and a liquid crystal (for example, ITO is first vapor-deposited on a glass substrate, a transparent electrode is formed by photolithography, and then a color filter is provided thereon, and further on this. How to arrange the liquid crystal).

A method of arranging the color filter between the transparent electrode made of ITO or the like and the substrate of the color filter (for example,
First, set the color filter on the glass substrate, and then on this
A method in which ITO is vapor-deposited, a transparent electrode is formed by photolithography, and then a liquid crystal is further arranged thereon.

In the above-mentioned method, after the transparent electrode is formed on the glass substrate, the color filter can be further formed thereon, so that the chemical resistance and heat resistance required for the color filter are not so severe. However, since the driving voltage of the liquid crystal increases as the color filter becomes thicker, it is necessary to make the color filter thinner.

However, if the color filter is made thin, a problem that sufficient color density cannot be exhibited occurs. Also,
In this method, since the color filter is located between the transparent electrode and the liquid crystal, there is also a problem that the components in the color filter seep into the liquid crystal and the performance of the liquid crystal deteriorates.

On the other hand, in the above method, after forming the color filter on the glass substrate, ITO is vapor-deposited on the color filter and the transparent electrode is formed by photolithography, so that the color filter has sufficient heat resistance and chemical resistance. Therefore, it is necessary to form a protective film on the color filter before depositing ITO.

On the other hand, as a substrate for a liquid crystal display element, a glass substrate containing inorganic ions such as sodium is generally used in many cases, and when a normal liquid crystal display element is formed using this glass substrate, the inorganic ions in the glass substrate become liquid crystal. It is known that since it dissolves in the liquid, it adversely affects the liquid crystal display device ["Liquid crystal display technology" (1983) published by Kogyo Kenkyukai,
Page 141].

As a protective film of such a color filter or a glass substrate, an inorganic thin protective film such as silicon dioxide is provided, so-called undercoat treatment is proposed, but this undercoat treatment has a treatment temperature of 400 to 500.
Since the temperature is as high as ℃, there is a problem that the color filter or the glass substrate is deteriorated due to the oxidation of the transparent electrode such as ITO, and further the contamination of the inner surface of the direct coupling processing apparatus is caused by the oxide.

(Problems to be Solved by the Invention) The present invention has been made against the background of the above-mentioned conventional technical problems, and when used as a color filter or a protective film of a transparent substrate, it is uniform and dense, and has heat resistance and heat resistance. It has excellent cracking properties and prevents the components in the color filter or the transparent substrate from seeping out into the liquid crystal, and it is possible to arrange a fine transparent electrode on the color filter. And, it is an object of the present invention to provide a composition for forming a protective film, which has excellent adhesiveness and adhesiveness and can form a protective film capable of solving parallax shift of a color liquid crystal display element. To do.

(Means for Solving Problems) That is, the present invention provides a composition for forming a protective film (hereinafter, simply abbreviated as “composition”) obtained by mixing the following (a) to (e). Is.

(A) an organoalkoxysilane represented by the general formula RSi (OR ¹ ) ₃ (wherein R and R ¹ represent an organic group) (hereinafter, simply referred to as “organoalkoxysilane”), a hydrolyzate of an organoalkoxysilane And / or partial condensate (b) A silyl group-containing vinyl polymer having at least one silyl group having a silicon atom bonded to a hydrolyzable group at the terminal or side chain in one molecule of the polymer (hereinafter, simply (Abbreviated as "silyl group-containing vinyl polymer") (c) Hydrophilic organic solvent (d) Nonionic surfactant (e) Water Next, the composition of the present invention will be described in detail according to constituent requirements.

(A) Organoalkoxysilane, hydrolyzate of organoalkoxysilane and / or partial condensate The organoalkoxysilane, hydrolyzate and / or partial condensate of organoalkoxysilane used in the present invention is the presence of water. When it becomes a coating film, it is cured by heating or standing at room temperature for dehydration condensation reaction.

R in the organoalkoxysilane is preferably an organic group having 1 to 8 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or an r-chloropropyl group, Vinyl group, 3,3,3
-Trifluoropropyl group, r-glycidoxypropyl group, r-methacryloxypropyl group, r-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group, r-aminopropyl group and the like.

Further, R ¹ in the organoalkoxysilane is preferably an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, for example, ethyl group, n-propyl group, i-
Examples thereof include a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an acetyl group, a propionyl group and a butyryl group.

Specific examples of these organoalkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane, r-chloropropyltriethoxysilane, vinyltriethoxysilane, and 3, 3,3-Trifluoropropyltriethoxysilane, r-glycidoxypropyltriethoxysilane, r-methacryloxypropyltriethoxysilane, r-mercaptopropyltriethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyl Examples thereof include triethoxysilane, methyltri-n-propoxysilane, methyltryptoxysilane, and methyltri-i-propoxysilane.

On the other hand, the hydrolyzate and partial condensate of the organoalkoxysilane are soluble in a hydrophilic organic solvent obtained by hydrolyzing or further polycondensing the organoalkoxysilane.

That is, the organoalkoxysilane liberates an alcohol by hydrolysis to produce a hydrolyzate, and further polycondensates to produce a partial condensate, that is, an organopolysiloxane.

Of these components (a), methyltrimethoxysilane, methyltriethoxysilane and phenyltriethoxysilane, and their hydrolyzates or partial condensates are particularly preferred.

These (a) components can be used alone or in combination of two or more.

(B) Silyl Group-Containing Vinyl Polymer The silyl group-containing vinyl polymer used in the present invention is a silicon atom whose main chain is composed of a vinyl polymer and whose end or side chain is bonded to a hydrolyzable group. The polymer contains at least one, preferably at least two silyl groups in one molecule, and most of the silyl groups are represented by the following general formula: (In the formula, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
Hydrolyzable group such as amino group, R ² is hydrogen atom, carbon number 1
To an alkyl group having 10 to 10 or an aralkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3).

Such a silyl group-containing vinyl polymer may be produced by reacting (a) a hydrosilane compound with a vinyl polymer having a carbon-carbon double bond, and (b) the following general formula: (Provided that X, R ² and n are the same as described above, and R ³ is an organic group having a polymerizable double bond),
It may be produced by polymerizing various vinyl compounds, and the production method is not limited.

Here, examples of the hydrosilane compound used in the production method shown in (a) above include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldiethoxysilane, methyldimethoxysilane, Alkoxysilanes such as phenyldimethoxysilane, trimethoxysilane, triethoxysilane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane; Methyldiaminoxysilane, triaminoxysilane, dimethylaminoxy Examples include aminosilanes such as silane and triaminosilane.

The vinyl-based polymer used in the production method shown in (a) is not particularly limited except for the vinyl-based polymer containing a carbon-carbon double bond, for example, methyl (meth) acrylate, Ethyl (meth) acrylate, (meth)
Butyl acrylate, (meth) acrylic acid esters such as 2-ethylhexyl (meth) acrylate; carboxylic acids such as (meth) acrylic acid, itaconic acid, fumaric acid and acid anhydrides such as maleic anhydride; glycidyl (meth) Epoxy compounds such as acrylates; amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; (meth) acrylamides, itaconic acid diamides, α-ethyl acrylamides, crotonamides, fumaric acid diamides, maleic acid diamides, N-butoxymethyl Amide compounds such as (meth) acrylamide Vinyl compounds selected from acrylonitrile, iminol methacrylate, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, etc., and butadiene, iso A vinyl-based polymer having a carbon-carbon double bond obtained by copolymerizing a conjugated diene compound such as prene and chloroprene and / or an acrylic acid derivative having a carbon-carbon double bond that does not participate in the polymerization such as allyl (meth) acrylate. Coalescence is preferred.

On the other hand, examples of the silane compound used in the production method shown in (b) include And the like.

As the vinyl compound used in the production method represented by (b), it is possible to use the vinyl compound used in the production of the vinyl polymer in the production method of (a), In addition to the method described in the production method (a), vinyl compounds having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, and N-methylolacrylamide are used. You can also list them.

Specific examples of the silyl group-containing vinyl polymer used in the present invention as described above include Kanefuchi Chemical Co., Ltd., Zemlac, Cyril; Toshiba Silicone Co., Ltd., and silicone acrylic varnish. .

These (b) components can be used alone or in combination of two or more.

The amount of the silyl group-containing vinyl polymer used is the amount of the component (a).
3 to 1000 parts by weight, preferably 10 per 100 parts by weight
To 200 parts by weight, particularly preferably 15 to 50 parts by weight, 3
If it is less than part by weight, crack resistance tends to be low, while
If it exceeds 1000 parts by weight, heat resistance tends to deteriorate and hardness tends to decrease.

(C) Hydrophilic organic solvent The hydrophilic organic solvent mainly mixes the components (a) to (d) uniformly, and is a concentration adjusting agent for the components (a) and (b), and also the component (a). And for adjusting the hydrolysis rate of the component (b) during curing.

As the hydrophilic organic solvent, alcohols, esters, ethers, ketones, amides and the like can be used. Here, examples of alcohols include monohydric or polyhydric alcohols, specifically, methanol,
Ethanol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin,
Examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, butyl cellosolve, ethyl cellosolve and carbitol.

Examples of the esters include ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, γ-butyrolactone, carbitol acetate. , Ethyl acetate cellosolve, butyl acetate cellosolve and the like.

Examples of ethers include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether.

As the ketones, acetone, methyl ethyl ketone,
Examples include diisopropyl ketone and cyclohexanone.

Examples of the amides include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

Of these hydrophilic solvents, alcohols, esters and ketones are preferable.

These (c) components can be used alone or in combination of two or more. A hydrophobic solvent can be mixed with these hydrophilic solvents as long as the stability of the protective film-forming composition is not impaired. Examples of the hydrophobic solvent include hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as cycloethane and chloroform.

The amount of component (c) used is usually 2 to 100 parts by weight per 100 parts by weight of component (a).

(D) Nonionic Surfactant The nonionic surfactant shortens the aging time of the composition after mixing the component (a), improves the wettability of the object, and improves the leveling property of the composition. However, it prevents the generation of foreign matters and the appearance of orange peel in the protective film, facilitates overcoating, improves dispersibility, and helps stabilize the composition.

Examples of such nonionic surfactants include fluorine-based surfactants having a fluorinated alkyl group or perfluoroalkyl group, polyether alkyl-based surfactants having a polyether alkyl group, and the like.

Among them, the fluorine-based surfactants include C ₉ F ₁₉ CONHC ₁₂ H ₂₅ , C ₈ F ₁₇ SO ₂ NH- (C ₂ H ₄ O) ₆ H, C ₉ F ₁₇ O (Pluronic L-35) C ₉ F ₁₇ , C ₉ F ₁₇ O (Pluronic P-84) C ₉ F ₁₇ , C ₉ F ₇ O (Tetronic-704) (C ₉ F ₁₇ ) ₂ , (where Pluronic L-35: Asahi Denka Kogyo Polyoxypropylene (50 wt%)-polyoxyethylene (50 wt%) block copolymer, average molecular weight 1,900; Pluronic P-84: Asahi Denka Kogyo KK, polyoxypropylene (50) Wt%)-Polyoxyethylene (40 wt%)
・ Block copolymer, average molecular weight 4,200; Tetronic-
704: Asahi Denka Kogyo Co., Ltd., N, N, N ', N'-tetrakis (polyoxypropylene-polyoxyethylene block copolymer, polyoxyethylene content in the molecule 40% by weight, average molecular weight 5,000 C _n F _{2n + 1} XR ¹ (where n is an integer of 4 to 25; X is --CONH--, --SO ₂ NH--, --SO ₂
NR ² -, - O-(pluronic) -, or - (Tetronic) R ² -; R ¹ and R ² _{ClH 2f + 1, C k F} 2k + 1 ,, or - (CH _{2j + 1} O) _n H; l and k are integers of 4 to 25; j is an integer of 2 to 4 and m is an integer of 2 to 20).

Specific examples of these fluorine-based surfactants include Ftop EF301, EF303, and EF352 (Shin-Akita Kasei Co., Ltd.).
Made), Megafac F171, same F173 (manufactured by Dainippon Ink Co., Ltd.), Asahi Guard AG710 (manufactured by Asahi Glass Co., Ltd.),
Fluorine-based surfactants exemplified in JP-A-57-178242, Florard FC-170C, FC-430, FC-431 (Sumitomo 3M Limited), Surflon S-382, SC101, SC101 SC
102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, 1100 (manufactured by BM-Chemie), Sch
sego FIuor (made by Schwegmann) etc. can be mentioned.

Further, as the polyether alkyl-based surfactant,
Polyoxyethylene alkyl ether, polyoxyethylene allyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester,
Examples thereof include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and oxyethyleneoxypropylene block polymer. Specific examples of these polyether alkyl-based surfactants include:
Emulgen 105, 430, 810, 920, Leodoll SP-4
0S, TW-L120, Emanol 4110, Exel P-40S (all manufactured by Kao Corporation), Nonipol 55 (Sanyo Chemical Co., Ltd.)
Made), bridge 30, bridge 52, bridge 72, bridge
92, Arassel 20, Emazole 320, Tween 20, Tween 60, Emanone 3199, Marge 45 (all manufactured by Kao Corporation) and the like.

These nonionic surfactants may be used alone or in combination of two or more.

The amount of these nonionic surfactants used is (a) +
The amount is preferably 0.005 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight, relative to 100 parts by weight of the component (b). If it is less than 0.005 part by weight, the aging time for forming a uniform coating film is too long. In addition, overcoating may be difficult, while if it exceeds 1 part by weight, the resulting composition tends to foam,
Also, heat may cause discoloration.

(E) Water Next, water is an essential component for hydrolysis of the components (a) and (b).

As such water, general tap water, distilled water, ion-exchanged water or the like can be used. In particular, when the composition is to be highly pure, distilled water or ion-exchanged water is preferable, and ion-exchanged water having an electric conductivity of 2 μS / cm or less is particularly preferable.

The amount of water used is preferably 10 to 70 parts by weight, particularly preferably 25 to 50 parts by weight, relative to 100 parts by weight of component (a), and if less than 10 parts by weight, hydrolysis or curing of component (a) is performed. However, if the amount exceeds 70 parts by weight, the stability of the composition deteriorates.

As described above, the composition of the present invention has the above (a) to
The component (e) is mixed, and the total solid content concentration is preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight. If it is less than 10% by weight, the solid content concentration is too low. The protective film may not exhibit various properties such as heat resistance, water resistance, chemical resistance, and weather resistance, and pinholes may be formed in the formed protective film. On the other hand, if it exceeds 50% by weight, the solid content concentration may be too high and storage stability of the composition may be deteriorated, or it may be difficult to form a uniform protective film.

In the composition of the present invention, water and / or
Alternatively, colloidal silica dispersed in a hydrophilic organic solvent can be added.

Such colloidal silica is used for increasing the solid content of the composition of the present invention, and the thickness of the coating film obtained can be controlled by the amount of the component used.

Further, in the composition of the present invention, various acids can be further added to the composition in order to accelerate the curing of the protective film after coating.

Such acids include, for example, inorganic acids such as nitric acid and hydrochloric acid,
Or acetic acid, formic acid, propionic acid, maleic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, glutaric acid, glycolic acid, malonic acid, toluenesulfonic acid,
Organic acids such as oxalic acid can be mentioned, but acetic acid is particularly preferable.

Further, the composition of the present invention includes a composition for preventing gelation,
Metal oxides such as colloidal alumina, aluminum oxide, zirconium oxide, and titanium oxide are further added for the purpose of thickening and improving the heat resistance, chemical resistance, hardness and adhesion of the resulting protective film, and preventing static electricity. It is also possible to mix them appropriately.

In preparing the composition of the present invention, for example, (a)
~ (E) component may be mixed at once, (b) ~
The mixture of the component (e) and the component (a) may be mixed, and the preparation method is not particularly limited.

The composition of the present invention is used by forming a coating film on the surface of a substrate and curing it, and examples of the substrate include a transparent substrate in a liquid crystal display device and a color filter. As the transparent substrate herein, a transparent substrate made of float glass, soda glass or visible polyester terephthalate, polyester film such as polybutylene terephthalate, further polyether sulfone, polycarbonate, other plastic film and the transparent substrate. Those having a transparent electrode such as tin oxide (NESA) or indium tin oxide (ITO) on the top can be mentioned.

Further, as the color filter, there can be exemplified one in which a colored layer composed of three primary colors of red, green and blue is provided on the transparent substrate by a photographic method, a printing method, an electrodeposition method or the like.

Here, the color filter by the photographic method is one manufactured by the method described in JP-A-60-216307, and a specific example of the color filter by the printing method is JP-A-60-2.
Examples manufactured by the method described in JP-A-63123 and color filters by the electrodeposition method are disclosed in JP-A-60-238.
Examples thereof include those produced by the method described in Japanese Patent Publication No. 03, etc.

The composition of the present invention can be applied to a substrate by a coating method such as a dipping method, a spray method, a roll coating method, a curtain coating method, a spin coating method, or a printing method such as screen printing or offset printing. it can. Further, the substrate to be coated may be surface-treated with ultraviolet rays and / or ozone in advance. The composition of the present invention is applied so that the film thickness after drying is preferably about 0.01 to 50 μm, particularly preferably about 0.1 to 10 μm, and this is applied using a heating means such as a hot plate or a gear oven.
At a temperature of about 50 to 300 ° C, preferably about 100 to 200 ° C,
For example, by heating for 10 to 120 minutes, or 1
It can be cured by drying at room temperature for about 7 days to form a protective film.

The protective film obtained by curing the composition of the present invention can be subjected to a surface treatment with ultraviolet rays and / or ozone or the like, whereby the adhesiveness with the sealant can be improved.

(Examples) Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the examples, parts and% are parts by weight and% by weight, unless otherwise specified.

Reference example (Production of color filter) 20 parts of gelatin and 2 parts of ammonium dichromate are added to ultrapure water.
It was dissolved in 80 parts and filtered through a membrane filter having a pore size of 0.2 μm to prepare a photosensitive composition for forming a layer to be dyed. Next, the photosensitive composition was spin coated on an optically polished glass substrate and dried in a nitrogen atmosphere. When the film thickness of the coating film after drying was measured by a stylus type film thickness meter "Alphastep" (manufactured by Tencor Co.), it was 1 μm. The obtained coating film was irradiated with ultraviolet rays through a photomask and then developed with ultrapure water to obtain a relief image of the gelatin layer. The relief image thus obtained was immersed in the following red dyeing bath and dried in a nitrogen atmosphere to obtain a red relief image.

Red dyeing bath Red-14P (manufactured by Nippon Kayaku Co., Ltd.) 1g Acetic acid 1g Ultrapure water 98g Next, a solution containing glycidyl methacrylate polymer as a main component is spin-coated on a glass substrate having a red relief image and dried. Then, a dye-proof protective film was formed. A relief image of gelatin was formed on the dye-protective protective film in the same manner as above, and treated in the following green bath to obtain a green relief image.

Green dyeing bath Green-1P (manufactured by Nippon Kayaku Co., Ltd.) 1g Acetic acid 1g Ultrapure water 98g Next, a dye-proof protective film was formed by the same operation as described above, and then a relief image of gelatin was formed. A blue relief image was formed by treatment with a blue bath.

Blue dyeing bath Blue-5C (manufactured by Nippon Kayaku Co., Ltd.) 1 g Acetic acid 1 g Ultrapure water 99 g A color filter substrate consisting of three primary colors of red, green and blue was obtained. Then, a solution containing the glycidyl methacrylate polymer as a main component was further spin-coated and dried to form a surface protective film to obtain a color filter.

Example 1 100 g of methyltrimethoxysilane was charged into a round bottom flask equipped with a condenser for cooling, a dropping funnel and a stirrer, and 40 g of ion-exchanged water was slowly dropped from the dropping funnel at room temperature, followed by stirring at 60 ° C. for 2 hours. 50 g of methyl ethyl ketone, 50 g of isopropyl alcohol, 12.5 g of an acrylic resin containing an alkoxysilyl group (Zemlac: manufactured by Kanebuchi Chemical Industry Co., Ltd.) and a fluorine-based surfactant (BM1000: (BM-Chemie Co.) were added to the reaction mixture thus obtained. Made)
0.6 g was added to make a uniform solution, which was filtered through a membrane filter having a pore size of 0.2 μm to obtain the composition of the present invention. The composition thus obtained was spin coated on the color filter manufactured in Reference Example at a rotation speed of 1000 rpm and heat-treated at 170 ° C. for 1 hour to form a protective film having a thickness of 3 μm.

Next, the color filter with the protective film was used with a photo cleaner (manufactured by E-HTC)
It was irradiated with ultraviolet light in the presence of oxygen for 10 minutes at room temperature. Indium tin oxide (ITO) was vapor-deposited on the thus-prepared color filter with a protective film according to a conventional method, and a positive resist (PF, manufactured by Japan Synthetic Rubber Co., Ltd., PF
R-3003) after forming the desired pattern, the ITO of the exposed part
Was removed by immersing it in a concentrated hydrochloric acid-ferric chloride aqueous solution at room temperature for 5 minutes, and after washing with water, the positive resist layer was peeled off. The color filter having the ITO pattern thus obtained was observed in detail with an optical microscope, but no cracks or wrinkles were observed in the color filter and the protective film, and the dye did not seep out from the dyed layer of the color filter. The adhesiveness and adhesion between the color filter and the protective film were also good.

Example 2 Using a flask similar to that of Example 1, 100 g of phenyltriethoxysilane and ion-exchanged water 15 were used in the same manner as in Example 1.
After mixing g and stirring at 60 ° C. for 4 hours, 25 g of butyl cellosolve, 75 g of carbitol acetate, 30 g of a silyl group-containing vinyl polymer (silicone acrylic varnish: manufactured by Toshiba Silicone Co., Ltd.) and a fluorochemical surfactant (BM1000 : (B.
(M-Chemie) 0.6g to make a uniform solution,
The composition of the present invention was obtained by filtration through a 0.2 μm membrane filter. The composition thus obtained was spin coated at 2000 rpm on the color filter produced in Reference Example,
A heat treatment was carried out at 00 ° C. for 2 hours to form a protective film having a film thickness of 1.5 μm.

Then, after the ITO pattern was formed by the same operation as in Example 1, the color filter was observed in the same manner as in Example 1, but no cracks or wrinkles were observed in the color filter and the protective film. The dye did not seep out from the dyed layer, and the adhesiveness and adhesion between the color filter and the protective film were good.

Example 3 The composition of the present invention used in Example 1 was coated on a soda glass (manufactured by Nippon Sheet Glass Co., Ltd.) substrate by the dipping method and then heat-treated at 200 ° C. for 1 hour to form a film having a thickness of 1 μm. A protective film was formed. At this time, the adhesion and adhesiveness between the substrate and the protective film were good. The substrate having the protective film thus obtained is immersed in ultrapure water and heat-treated at 120 ° C. for 12 hours,
The elution amount of sodium ions is quantified by atomic absorption spectrometry,
This value was divided by the area where the protective film came into contact with water, and the sodium ion concentration per unit area was evaluated to be 0.2 ppm / c
It was m ² .

Comparative Example 1 The sodium ion elution amount of the soda glass plate having no protective film formed in Example 3 was evaluated in the same manner as in Example 3, and the result was 3.0 ppm / cm ² .

Example 4 Using the same flask as in Example 1, 100 g of methyltrimethoxysilane and 40 g of deionized water were used in the same manner as in Example 1.
Were mixed and stirred at 60 ° C. for 2 hours, and then 27 g of methyl ethyl ketone, 25 g of isopropyl alcohol, 50 g of butyl cellosolve acetate, 15 g of carbitol, and an acrylic resin containing an alkoxysilyl group (Zemlac: Kanegafuchi Chemical Industry Co., Ltd.).
20 g and fluorochemical surfactant BM1000: (BM-Chemie
(Manufactured by K.K.) 0.6 g was added to make a uniform solution, and this was 0.2 μm
The composition of the present invention was obtained by filtering with a membrane filter of The composition thus obtained was spin coated on the color filter manufactured in Reference Example at a rotation speed of 1500 rpm, and the coating was carried out at 200 ° C. for 1 hour.
A heat treatment was performed for an hour to form a protective film having a film thickness of 2.5 μm. Then, after forming an ITO pattern by the same operation as in Example 1, the color filter was observed in the same manner as in Example 1, but no cracks or wrinkles were observed in the color filter and the protective film, and The dye did not seep out from the dyed layer, and the adhesiveness and adhesion between the color filter and the protective film were good.

Comparative Example 2 A detailed observation of the substrate on which the ITO pattern was formed on the color filter manufactured in Reference Example in the same manner as in Example 1 revealed that the dyed layer of the color filter was decolorized and further fine cracks were generated. It was

(Effect of the invention) The composition for forming a protective film of the present invention can form a protective film that is uniform and dense and has excellent heat resistance and crack resistance. This protective film can be used in a color filter or a transparent substrate. It prevents the components from seeping out into the liquid crystal, and also allows fine transparent electrodes to be placed on the color filter, and has excellent adhesiveness and adhesion to both the color filter and the transparent substrate, and It is also possible to solve the parallax shift of the color liquid crystal display element.

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Claims (1)

[Claims] 1. A composition for forming a protective film, which is obtained by mixing the following (a) to (e). (A) an organoalkoxysilane represented by the general formula RSi (OR ¹ ) ₃ (wherein R and R ¹ represent an organic group), a hydrolyzate and / or a partial condensate of the organoalkoxysilane (b) a terminal Alternatively, a silyl group-containing vinyl polymer having at least one silyl group having a silicon atom bonded to a hydrolyzable group in its side chain in one molecule of the polymer (c) hydrophilic organic solvent (d) nonionic surfactant Agent (e) Water