JPS637883A - Method for modifying film - Google Patents

Abstract

PURPOSE:To enhance the adhesiveness of an adhesive or paint, by irradiating a vitreous film obtained by applying a specific composition with ultraviolet rays in the presence of ozone. CONSTITUTION:A composition obtained by mixing components (a)-(d) is applied in order to form the protective film of a color filter to make it possible to form a thin vitreous film. That is, organosilane represented by a generals formula RSi(OR')3 (wherein R and R' are a same or different org. group) and/or a partial condensate thereof (a), fine particulate silica (b), a hydrophilic org. solvent (c) being alcohols and an alcohol derivative and water (d) are mixed to prepare the composition which is, in turn, applied and further irradiated with ultraviolet rays in the presence of ozone. Whereupon, the org. substance present on the surface of the film is removed to modify the film so as to enhance the adhesiveness thereof with a sealant.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for modifying a coating film, and more specifically, it is applicable to applications such as a protective film formed on a substrate used in a liquid crystal display element, etc. The present invention relates to a method for modifying a coating film.

[Conventional technology]

In recent years, many color liquid crystal display elements have been proposed, each of which is a combination of a liquid crystal element and a color filter for color separation.

When a 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 the optical path, so when viewing the display from the front of the color liquid crystal display element, the display must be You can see it clearly. However, for example, if a color filter is placed outside the liquid crystal element, due to the thickness of the glass used for the liquid crystal element, if the display pixels are minute, the thickness of the glass may cause problems when viewed from an oblique direction. This causes "parallax shift" in the display. In order to prevent such parallax shift, 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 to 1).
0, September 10, 1984, published by Nikkei McGraw-Hill, pp. 211-240).

The following two methods are known for arranging a color filter inside a liquid crystal element in this way.

■The color filter is made of indium tin oxide (ITO).
), etc., between the transparent electrode and the liquid crystal (
For example, a method in which ITO is first vapor-deposited on a glass substrate, a transparent electrode is formed by photolithography, a color filter is provided on this, and a liquid crystal is further placed on this). ■A method of placing Color 7 Ilter between a transparent electrode made of ITO or the like and a color filter substrate (for example, first a color filter is provided on a glass substrate, ITO is vapor-deposited on this, and a transparent electrode is formed by photolithography. After forming the liquid crystal, how to place the liquid crystal on top of it).

In method (2) above, after forming a transparent electrode on a glass substrate, a color filter can be further formed on this, so the chemical resistance, heat resistance, etc. required for a 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 thinner, a problem arises in that sufficient color density cannot be achieved. Further, in this method, since the color filter is located between the transparent electrode and the liquid crystal, there is also a problem that components in the color filter leak into the liquid crystal, degrading the performance of the liquid crystal.

On the other hand, in the method (2) above, after a color filter is formed on a glass substrate, ITO is vapor-deposited on the color filter and a light electrode is formed by photolithography, so the color filter has sufficient heat resistance and resistance. Chemical properties are required, and it is necessary to form a protective film on the color filter before vapor depositing To.

Recently, a color liquid crystal display device has been proposed in which a glass plate of about 500 μm is placed on the color filter as a protective film for such a color filter, and a transparent electrode is formed on the glass plate (Television Society Technical Report , published on February 25, 1982). However, when a glass plate is used as a protective film for a color filter, the liquid crystal and color filter are separated, so it is not possible to sufficiently prevent the parallax shift described above, especially when the display pixels are minute. However, there is a problem that a vivid image cannot be obtained due to parallax shift.

On the other hand, glass containing inorganic ions such as sodium is generally used as a substrate for liquid crystal display elements.
When a normal liquid crystal display element is formed using this glass,
It is known that inorganic ions in the glass elute into the liquid crystal, which has a negative effect on liquid crystal elements ["Latest Technology in Liquid Crystals" (1983-) Published by Kogyo Kenkyukai, p. 141]
.

As a protective film for such color filters or glass substrates, a so-called undercoat treatment has been proposed in which a thin inorganic protective film such as silicon dioxide is provided.
The temperature is as high as 0° C., and it cannot be used with a substrate having a color filter because it causes thermal decomposition, and it is necessary to conduct the process under an inert atmosphere in order to prevent oxidation of transparent electrodes such as ITO.

In order to solve these technical problems, we can prevent the components in the color filter from seeping into the liquid crystal by using a glassy film obtained by applying a specific composition as a protective film for the color filter. A color filter has been proposed in which a protective film is formed, which allows fine transparent electrodes to be disposed on the color filter, and which can also solve the parallax shift of color liquid crystal display elements. However, the coating film formed by applying this particular composition may not have sufficient adhesion with the sealant.
A substrate for a liquid crystal display element using this as a protective film has a problem in that its adhesion to the sealant may still be insufficient.

[Problem that the invention seeks to solve]

The present invention was made against the background of the above-mentioned conventional technical problems, and it is possible to apply adhesives, paints, etc. by irradiating ultraviolet rays in the presence of ozone to a glassy film obtained by applying a specific composition. The purpose is to significantly improve adhesion.

[Means for solving problems]

That is, the present invention provides the following T on part or all of the substrate.
a) ~! The present invention provides a method for modifying a coating film, which comprises applying a composition obtained by mixing d) and irradiating the resulting coating film with ultraviolet rays in the presence of ozone.

(al General formula RSi (OR')3 (wherein,
R and R' represent the same or different organic groups. ) and/or a partial condensate of the organosilane, (bl particle silica, (c) hydrophilic organic solvent, (d) water.

Generally speaking, the following two methods are widely known as methods for manufacturing color filters.

(b) A patterned resist layer is provided on the layer to be dyed on a transparent substrate such as glass, the exposed part of the layer to be dyed is dyed to form a dyed area, and then the resist layer is peeled off, and then the same process is performed. method to form the next dyed area (method of dyeing a single layer to be dyed into multiple dyed areas) After forming a patterned layer to be dyed by exposure and development, dyeing to form a dyed layer, then covering with a transparent resisting film, and then forming the next dyed layer on top of it in the same way. Method (method of laminating layers to be dyed and resisting layers alternately). The method for modifying a coating film of the present invention is a protective film of a color filter obtained by the method of (a) dividing a single dyed layer into a plurality of dyed parts, It is also applicable to a protective film of a color filter obtained by a method of laminating dyed layers alternately, or a protective film of a glass substrate or a substrate made of other materials.

Examples of the substrate made of other materials include plastics such as polyethylene terephthalate, polyphenylene, and polycarbonate, other metals, and ceramics.

The material forming the dyed layer used in the production of color filters is not particularly limited, and may include natural proteins such as gelatin, casein, glue, albumin, etc.
Examples include synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide.

In addition, examples of photocrosslinking agents that impart photosensitivity to these materials include dichromates such as ammonium dichromate and potassium dichromate, as well as bisazide compounds. Specific examples of such bisazide compounds include 4,4'-diazidostilbene-2,2'-disulfonic acid and 4,4'-diazidobenzal as described in Japanese Patent Publication No. 51-48946. In addition to water-soluble bisazide compounds of acetophenone-2-sulfonic acid, 4,4'-diazidostilbene-α-monocarboxylic acid, and their alkali metal, ammonium, etc. salts, p-
Phenylene bisazide, 4,4'-diazidobenzophenone, 4,4'-diazidostilbene, 4,4'-diazidophenylmethane, 4,4'-diazidobenzalacetophenone, 2.6 -di(4'-azidobenzal)cyclohexanone, 2,6-di(4'-azidobenzal)-4-methylcyclohexanone, and the like.

Further, dyes used to form the color filter include acidic or basic water-soluble dyes, such as Kayanol Milling Turquoise Blue 8G, Kayanol Milling Yellow ○, Kayanol Cyanine G1 Kayanol Milling Resodo RS125, Kayaku Acid Orange II (manufactured by Nippon Kayaku), Mitsui Nylon Fast Yellow 5G, Mitsui Brilliant Milling Green B1 Mitsui Acid Milling Sky Blue PSE (manufactured by Mitsui Toatsu Chemical), Suminol Milling Brilliant Green 5G, Acid Brilliant Milling Green B1 Suminol Milling Red P
C (manufactured by Sumitomo Chemical Corporation), Diacid Fast Rubinol 3G200, Diacid Fast Orange NP200 (manufactured by Mitsubishi Chemical Corporation), Guinea Green (manufactured by Tokyo Kasei Corporation), and the like.

In addition, when manufacturing color filters by the method described above, the material for forming the resist dye layer is not particularly limited as long as it is a transparent material that has resist dye properties, but (meth)acrylic Examples include thermosetting compositions containing a polymer such as glycidyl acid and a polyhydric carboxylic acid such as phthalic anhydride, itaconic anhydride, succinic anhydride, or anhydride thereof.

In addition, when manufacturing a color filter using the method (a) above, a cross-linked product of polyvinyl alcohol is formed as a protective layer on the layer to be dyed before dyeing the layer to be dyed. A color filter with a color pattern can be obtained.

Now, in the coating film modification method of the present invention, by first applying a composition obtained by mixing the components (al to (d)) above on a substrate, a thin layer of vitreous material that will become a protective film is formed. It forms a film.

Components (a) to (d) of this composition will be explained in detail below by component.

(a) An organosilane represented by the general formula RSi (OR')3 and/or a partial condensate of the organosilane The organosilane used in the present invention undergoes hydrolysis and polycondensation reactions due to the presence of water. It is a compound that increases in molecular weight and acts as a binder in the composition used in the present invention.

R in such an organosilane is an organic group, preferably an organic group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Others T-chloroprobyl group, vinyl group, 3,3.3-
}Reflopropyl group, γ-glycidoxypropyl group,
Examples include a γ-methacryloxypyl group, a γ-mercaptopropyl group, a phenyl group, a 3,4-epoxyhexylethyl group, and a γ-aminopropyl group.

Furthermore, R' in the organosilane is an organic group, preferably an organic group having 1 to 5 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group. , ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, acetyl group, propanoyl group, i-propanoyl group, n-butanoyl group, i-butanoyl group, etc. can be mentioned.

Specific examples of these organosilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-
Propyltriethoxysilane, γ-chloropropylltrimethoxysilane, T-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3.3.3-}lifluoropylltrimethoxysilane, 3. 3.3-trifluoropyrtriethoxysilane, γ-glycidoxypiltrimethoxysilane,
γ-glycidoxypyltriethoxysilane, γ-methacryloxypyltrimethoxysilane, T-methacryloxypyltriethoxysilane, γ-mercaptopyltrimethoxysilane, T-mercaptopyltriethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3.4-epoxyhexylethyltrimethoxysilane, 3.4-epoxyhexylethyltriethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane , T-glycidoxyprobyltriacetoxysilane, methyltriprobanoyloxysilane, ethyltriisobutanoyloxysilane, methyltriisobutanoyloxysilane, n-propyltriprovanoyloxysilane, i-propyltrin -Butanoyloxysilane and the like can be mentioned.

Further, the partial condensate of organosilane is a polysiloxane obtained by hydrolyzing organosilane and soluble in a hydrophilic organic solvent.

These organosilanes or partial condensates of organosilanes can be used alone or in combination of two or more. Among these honoreganosilane or partial condensates of 8-honoreganosilane, methyltrimethoxysilane or a partial condensate of methyltrimethoxysilane is particularly preferred.

The proportion of the organosilane or the partial condensate of the organosilane in the composition is preferably 10 to 40 parts by weight, particularly preferably 20 to 30 parts by weight, and if it is less than 10 parts by weight, the composition itself may not be preserved. Although the stability is good, the adhesion of the obtained protective film is weak and the hardness is insufficient.On the other hand, if it exceeds 40 parts by weight, the storage stability of the composition deteriorates, and the amount of fine particle silica described later There is a tendency for the target function to decrease as the number of targets decreases relatively.

(b) Particulate silica Particulate silica is used to increase the solid content of the resulting protective film while maintaining its transparency, and the thickness of the resulting protective film is determined by the amount of this component. It is.

Such fine particle silica is high purity silicic anhydride, and usually has an average particle diameter of 5 to 50 mμ, preferably 10 to 20 mμ.
μ, and is generally available as an aqueous dispersion with a solid content concentration of about 18 to 30% by weight. The pH of this aqueous dispersion of particulate silica is preferably in the range of 2 to 5, particularly 2 to 4. Such an aqueous dispersion of particulate silica generally has a low sodium content and is suitable for acidic regions. Therefore, it is suitable for curing the composition after applying it. This aqueous dispersion of fine particle silica with a pH of 2 to 5 is as follows:
For example, manufactured by Nissan Chemical Industries ■, Snowtefx 0: manufactured by DuPont, USA, Ludox; manufactured by Monsanto, USA, Syn
ton; manufactured by Nalco Chemical Company, USA, Nalcoag
etc. can be mentioned. Also, instead of the aqueous dispersion of fine particle silica as described above, Si (OR')4
Uses fine particle silica made of a hydrolyzate obtained by hydrolyzing a silane compound represented by (wherein R' is the same as above) or a polycondensate thereof (hereinafter simply referred to as "hydrolyzate"). It is also possible to do so. Here, examples of the silane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-proboxysilane, tetra-i-propoxysilane, and tetra-n-propoxysilane.
-butoxysilane, tetrasec-butoxysilane,
Examples include tetra-tert-butoxysilane, and these silane compounds may be used alone or in combination of two
A mixture of two or more species can be used.

When using particulate silica made of such a hydrolyzate, it is usually prepared as an aqueous dispersion, preferably with a pH of 2 to 5.
It is used when the solid content concentration is 10 to 30% by weight. The proportion of fine particle silica in the composition is preferably 3 to 3.
0 parts by weight, particularly preferably 5 to 20 parts by weight, and 3
If it is less than 30 parts by weight, the resulting protective film may be too thin, while if it exceeds 30 parts by weight, the protective film may become too thick or cracks may occur.

(c) Hydrophilic organic solvent The hydrophilic organic solvent is a decomposition medium for fine particle silica, and is used to homogeneously mix (al organosilane or a partial condensate of the organosilane). This is to prevent the partial condensate of silane from gelling when it is hydrolyzed by water due to the synergistic effect with the fine particle silica.

Examples of such hydrophilic organic solvents include alcohols and alcohol derivatives, including monohydric alcohols,
Examples include ethylene glycol or its derivatives, which are dihydric alcohols, and glycerin, diglycerin, pentaerythritol, and derivatives thereof, which are trihydric or higher alcohols. Among these, the monohydric alcohol is preferably an aliphatic alcohol having 1 to 8 carbon atoms, and specifically, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, sec-butyl alcohol, tart-butyl alcohol, i -Butyl alcohol, n-amyl alcohol, i-amyl alcohol, sec-amyl alcohol, n-hexyl alcohol, 4-methyl-2-pentyl alcohol, etc., and alcohol derivatives include:
Examples include ethylene glycol monobutyl ether and acetic acid ethylene glycol monoethyl ether. Further, examples of trivalent or higher alcohol derivatives include glycerin heptamethyl ether, glycerin monoethyl ether, glycerin dimethyl ether, glycerin diethyl ether, diglycerin monomethyl ether, diglycerin monoethyl ether, diglycerin dimethyl ether, diglycerin diethyl ether, Examples include diglycerol trimethyl ether, diglycerol triethyl ether, pentaerythritol dimethyl ether, and pentaerythritol trimethyl ether.

These hydrophilic organic solvents are particularly preferably i-
proyl alcohol, sec-7′ methyl alcohol,
Ethylene glycol monobutyl ether and acetic acid ethylene glycol monoethyl ether.

These hydrophilic organic solvents can be used alone or in combination of two or more.

The proportion of hydrophilic organic solvent in the composition is preferably 10
-60 parts by weight, particularly preferably 20 to 40 parts by weight; if it is less than 10 parts by weight, (a) polycondensation of the organosilane or the partial condensate of the organosilane will proceed too much and gelation will easily occur; Also, particulate silica tends to be insufficiently separated, and on the other hand, if it exceeds 60 parts by weight, the amount of other components becomes relatively small, and the resulting protective film may have weak adhesion or be too thin.

The hydrophilic organic solvent may contain acetone,
It is also possible to use a mixture of polar solvents such as tetrahydrofuran and dimethylformamide. fd) Water Water is an essential component for the hydrolysis of organosilane or a partial condensate of the organosilane, and also serves as a dispersion medium for particulate silica.

Such water is preferably distilled water or ion-exchanged water, but when fine particle silica is used as an aqueous dispersion, the water in the dispersion can be used as is.

The proportion of water in the composition is preferably 10 to 70 parts by weight, particularly preferably 25 to 50 parts by weight, and if it is less than 10 parts by weight, hydrolysis of the organosilane or a partial condensate of the organosilane may occur. sufficiently difficult to occur, while 70
If the amount exceeds 1 part by weight, the composition tends to gel.

The proportions of each component (a) to Td) in the composition are based on a total of 100 parts by weight. In the composition obtained by mixing the components (al to (d)), in order to promote the hydrolysis of the organosilane or a partial condensate of the organosilane and to promote the curing of the protective film, the entire composition is added. An acid can be further added to the range of pH 3 to 6.

Examples of such acids include inorganic acids such as nitric acid and hydrochloric acid, acetic acid, formic acid, probionic acid, maleic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, curtaric acid, glycolic acid, malonic acid, toluenesulfonic acid, The composition used in the present invention, which can include organic acids such as oxalic acid, is formed by mixing the components (a) to (d) above, and is effective in preventing gelation of the composition, thickening it, and obtaining a protective film. Metal oxides such as colloidal alumina, aluminum oxide, zirconium oxide, and titanium oxide can be added as appropriate to improve heat resistance, chemical resistance, hardness, and adhesion, as well as to prevent static electricity. be. (In this case, the coating film becomes opaque.

) The composition used in the present invention also includes a surfactant,
Additives such as coupling agents can also be added. When preparing the composition used in the present invention, for example, components (a) to (d) may be mixed at once, or (
(Al component may be added to the mixed solution of components b) to (d), and (Td) component may be further added to the mixed solution of (al to tc+components), and the solid content concentration is usually 1O to 50 weight%
It is prepared in

This composition can be made into a uniform dispersion by methods such as high-speed stirring.

The composition used in the present invention can be applied to the surface of a color filter opposite to the transparent substrate side such as glass by a coating method such as a spray method, a roll coating method, a curtain coating method, a spin coating method, or a dispersion method. In addition, by coating methods such as screen printing and offset printing, the film thickness after drying is preferably about 0.01 to 50 μm,
Particularly preferably, it is applied to a thickness of about 0.1 to 10 μm. This is usually heated to about 50-300°C, preferably 100-300°C using a heating means such as a hot plate or gear open.
It is cured by heating at a temperature of about 200° C. for, for example, about 10 to 120 minutes or by drying at room temperature for about 1 to 7 days to form a protective film having heat resistance, chemical resistance, etc.

The composition used in the present invention usually forms a hard coating film of 2H or more when the pencil hardness is measured on a glass substrate according to the JIS K5400 pencil scratch test.

Then, in the present invention, the above fal~(d
) is applied, and then irradiated with ultraviolet rays in the presence of ozone.

Generally, when a low-pressure mercury lamp is lit in air, the wavelength is 16
Ultraviolet rays of 0 to 400 nm are emitted to the outside, and a small amount of other wavelengths are also emitted.

In this way, oxygen in the air is converted into ozone and decomposed by ultraviolet light with a wavelength of 160 to 400 nm, and the reaction activity produces oxygen atoms, which decomposes the organic components in the paint film. , is known to be dispersed in a gaseous state. Therefore, in the present invention, it is practical to irradiate ultraviolet rays as described above and simultaneously generate ozone using the ultraviolet rays, and as a lamp that generates ultraviolet rays,
Low-pressure mercury lamps, xenon lamps, metal halide lamps,
A lamp that generates ultraviolet light having a wavelength of 160 to 400 nm, such as a carbon arc lamp, is preferably used.

In particular, in the present invention, a lamp that generates ultraviolet rays of two wavelengths, 165 to 205 nm and 235 to 275 nm, is preferable.

The amount of ultraviolet rays emitted from these lamps is
The ozone concentration during ultraviolet irradiation is preferably 0.01 J/aJ or more, and the ozone concentration at the time of ultraviolet irradiation is preferably 0.001 volume % or more. If the ultraviolet irradiation amount and ozone concentration are low, it will be difficult to fully exhibit the effects of the present invention. be. The amount of ultraviolet irradiation can be measured using an ultraviolet intensity measuring device, and the ozone concentration can be measured using a detection tube method. Although the details of the reason why the coating film is modified by the present invention are unknown, it is presumed that the organic substances present on the coating film surface are removed by ozone and ultraviolet rays.

The time for irradiating ultraviolet rays in the presence of ozone is usually 1
-120 minutes, preferably 3-60 minutes, and the temperature at that time is usually 15-100°C, preferably 20-50°C.
That's about it.

When using a color filter or a glass substrate having a protective film, which is a thin layer of glassy film, obtained in this way as a color liquid crystal display element or a normal liquid crystal display element, for example, on the color filter or on the glass substrate, On the protective film formed above, ITO is vapor-deposited and a transparent electrode is formed by photolithography, and a liquid crystal alignment film made of polyimide or the like is further placed on the ITO, and a liquid crystal alignment film is placed inside this. After placing the glass substrates facing each other and gluing the periphery with a sealant, a liquid crystal is sealed between them to form a color liquid crystal display element.
Alternatively, it is used as a liquid crystal display element. In addition, at this time, the sealant (or adhesive) for the color liquid crystal display element or the substrate for the liquid crystal display element is not particularly limited, but for example, a material based on epoxy resin can be used. , Structbond XN-10 (manufactured by Mitsui Toatsu Chemicals), Araldite (manufactured by Ciba Geigy), and SR Ipond B-70 (manufactured by Sunrise Myojo).

Furthermore, the method of curing these sealants is not particularly limited, and may be a method using heat, a method using light, or the like. [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

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

In addition, the peel strength was determined by the following adhesion test. That is, in the adhesion test, as shown in FIG.
By overlapping each end face of the sheets and gluing them using sealant 2 (adhesive), an adhesive piece is produced, and this is placed on the balance 3.
Place it on jig A set above, and evaluate the adhesive strength by the force applied to point B. Example 1 To 200 g of an aqueous dispersion of fine particle silica having an average particle diameter of about 15 mμ, containing 20% in terms of solid content and having a pH of 3 (manufactured by Nissan Chemical Industries, Ltd., Snotefx 0), 100 g of isopropyl alcohol and methyl After adding 110 g of trimethoxysilane, mixing and adjusting the pH to 5 with acetic acid, the mixture was left to stand for about 1 hour to prepare a composition.

Next, soda glass (made by Japanese sheet glass) was used as the substrate.
The composition was applied to the substrate using a rotation speed of 2.00 Orp.
Spin coating was performed at 150°C, followed by heat treatment at 150°C for 30 minutes until the film thickness after drying was 0. A protective film of 9 μm was formed.

The thus prepared substrate with a protective film was irradiated with ultraviolet rays mainly having wavelengths of 185 nm and 254 nm for 10 minutes at room temperature using a low-pressure mercury lamp. The amount of UV irradiation at this time was 5J/c! The lI1 ozone concentration was 2% by volume.

ITO was deposited on the thus obtained substrate according to a conventional method, and a positive resist (manufactured by Nippon Synthetic Rubber Co., Ltd.,
After applying PFR-3003) and forming the desired pattern, the exposed ITO was soaked in concentrated hydrochloric acid at room temperature for 55 minutes.
Etching was performed by dipping for a minute, and after washing with water, the positive resist was peeled off. A polyimide-based liquid crystal alignment film (manufactured by Japan Synthetic Rubber Co., Ltd., J
IB) was applied, dried, and then bonded using a sealant containing 1% spacer made of alumina with a particle size of 8 μm (Structvold XN-10, manufactured by Mitsui Toatsu Kagaku@). It was extremely good. In addition, when an adhesion test was conducted on a glass substrate, point B was found to be 5. OOO
The glass broke when a force of g was applied.

Example 2 Copolymer of vinylpyrrolidone (68 parts), 2-methacryloyloxyethyltrimethylammonium chloride (14 parts), and methyl methacrylate (18 parts) (limited in 0.1% aqueous sodium chloride solution) Viscosity: 1.1d!/g
)1Og was dissolved in 90g of methyl cellosolve.

4.4′-Diazidostilbene-2.2 was added to the resulting solution.
After adding 0.4 g of sodium '-disulfonate and stirring to mix uniformly, this solution was filtered through a filter with a pore size of 0.2 μm to prepare a photolactic composition for forming a layer to be dyed.

Next, a solution containing a glycidyl methacrylate polymer as a main component (weight-average molecular size calculated by gel permeation chromatography as calculated by weight average molecular weight of polystyrene: 65,000) was applied onto the glass substrate, and then the photosensitive composition was rotated. Spin coating was performed at several 3.00 rpm. The thickness of the coated film after drying was 0.9 μm.The entire surface of the thus obtained warm coated film was irradiated with ultraviolet rays to crosslink the coated film forming the layer to be dyed.

Next, a solution of 10 g of polyvinyl alcohol (degree of polymerization: 500, saponification rate, 100%) and 0.5 g of ammonium dichromate dissolved in 90 g of water was placed on the layer to be dyed, and the pore size was
．． The composition prepared by filtration through a 2 μm filter was spin coated at a rotational speed of 3.00 rpm. This is 11
After drying at 0°C for 10 minutes, the entire surface of the coating was irradiated with ultraviolet rays to photocure, forming a 0.5 μm thick protective layer for the layer to be dyed. - On the thus obtained laminate consisting of two layers, the layer to be dyed and its protective layer, a positive resist rPFR-300 is applied.
3J (manufactured by Japan Synthetic Rubber) at rotation speed 3, OOOrp
Spin coated with m.

Thereafter, the resist was patterned by drying it at 80°C for 10 minutes, irradiating it with ultraviolet rays through a photomask with the desired pattern, and developing it with a developer rPD524J (manufactured by Japan Synthetic Rubber ■). A resist pattern layer was formed and a dyeing substrate was prepared. The obtained dyeing substrate was dyed with Kayanol Milling Red R.
The layer to be dyed was dyed by immersing it in a ° dyeing bath consisting of S125 (1 g), acetic acid (Ig), and water (98 g) at 25 °C for 5 minutes. Thereafter, the entire substrate was irradiated with ultraviolet rays, the resist pattern layer was removed with the developer, washed with water, and dried to form a first color pattern on the layer to be dyed.

Next, the operations of forming a resist pattern layer, dyeing, and removing the resist pattern layer are repeated in the same manner as the above procedure to form a second dyed part and a third dyed part,
A dyed layer was formed.

Furthermore, a glycidyl methacrylate polymer (weight average molecular weight in terms of boristyrene; 65.0
00) was applied as the main component and dried to a film thickness of 2 μm.
A color filter was obtained by forming a surface protective film of m. On the color filter substrate prepared in this way,
Example 1 The prepared composition was applied as in Example 1,
After curing, the substrate was irradiated with ultraviolet rays in the same manner as in Example 1 to form a color liquid crystal display element, and an adhesion test was conducted. When a force of s,ooog was applied to point B, the substrate broke. Example 3 Instead of the sealant (manufactured by Mitsui Toatsu Chemical Co., Ltd., Structbond
g, bisphenol A diacrylate (manufactured by Osaka Organic Chemical Co., Ltd., Viscoat #700) 5 g, benzoin ethyl ether 0.15 g, silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., KBM503) 0.1 g, and talc (
Using a sealant consisting of 4g of a mixture of Nippon Talc (Micro Ace), apply and press, then irradiate with a high pressure mercury lamp.
A substrate for a liquid crystal display element was prepared in the same manner as in Example 1, except that the sealant was not effective. When an adhesion test was conducted, the substrate broke when a force of 5,000 g was applied to point B.

Comparative Example 1 A substrate for a liquid crystal display element was prepared in the same manner as in Example 1 except that no ultraviolet irradiation was performed, and an adhesion test was conducted.
When a force of 800 g was applied to point B, the board was peeled off at the adhesive portion without breaking.

〔Effect of the invention〕

As described above, the present invention is characterized in that the adhesion of adhesives, paints, etc. is significantly improved by irradiating a glassy film obtained by applying a specific composition with ultraviolet rays in the presence of ozone. This method is extremely useful as a method for modifying the protective film of a liquid crystal display element.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of an apparatus for carrying out an adhesion test. In Figure 1, 1.1' is the substrate to be adhered to, 2 is the adhesive, and 3 is the adhesive.
is a balance and A is a jig.

Claims (3)

[Claims] (1) Apply a composition obtained by mixing the following (a) to (d) on part or all of the substrate, and on the resulting coating film,
A method for modifying a coating film characterized by irradiating ultraviolet rays in the presence of ozone. (a) General formula RSi(OR')_3 (where R and R
′ represents the same or different organic group. ) and/or a partial condensate of the organosilane; (b) fine particle silica; (c) a hydrophilic organic solvent; (d) water. (2) The method for modifying a coating film according to claim 1, wherein the ozone concentration is 0.001% by volume or more. (3) The method for modifying a coating film according to claim 1 or 2, wherein the amount of ultraviolet irradiation is 0.01 J/cm^2 or more.