JPH1077448A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating compsn. which is prepd. at a low cost and has high reliability, smoothness, and adhesiveness by incorporating at least one kind of compd. selected from among four specific kinds of compds. into a compsn. essentially comprising a polymer and a solvent. SOLUTION: This compsn. contains a polymer (A) which is soluble or at least swellable in an aq. alkali soln., is a reaction product of polymerizable unsatd. compds., has segments repersented by formula I or II, and is a copolymer at least of (meth)acrylic acid with a monomer such as one represented by fomrula III [wherein R is a 1-15C alkyl, a cycloalkyl, an arom. hydrocarbon group, hydroxyl, or a 1-15C alkyl or hydroxylated arom. hydrocarbon group having a group represented by formula IV (wherein m is 1-10; and n is 1-5)] and a solvent (B) as the essential ingredients. The compsn. further contains at least one kind of compd. (C) selected from among alkoxysilane compds., alkoxytitanium compds., alkoxyaluminum compds., etc., and a thermal cross- linking agent (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition for obtaining a smooth and transparent surface useful for forming a protective film, and more particularly to a coating composition for a protective film of a color filter formed on glass or a transparent material.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices have been actively applied to electronic devices such as AV devices and personal computers. In particular, demand for a color display is rapidly increasing due to good visibility and abundant information. Generally, in order to obtain a color display, for example, a mosaic or stripe color filter is dyed on a substrate such as a transparent glass,
It is formed by a printing method, a pigment dispersion method, an electrodeposition method, or the like. A color filter is usually manufactured to about 1 micron, but has a submicron step on the surface. In the color STN, this step affects the display quality (color unevenness and the like), and the surface flatness must be 0.1 to prevent display unevenness.
It is necessary to keep it below a micron. Normally, to obtain a smooth surface, a thermosetting acrylic resin was applied to the surface of the color filter to flatten the surface. Also, not only the liquid crystal display device, but also the surface of the color filter in the solid-state imaging device, is processed in a post-manufacturing process,
For example, it is necessary to provide a protective film for protecting the color filter from severe conditions such as immersion treatment with a solvent, an acid, or an alkali solution, or high temperature generated when the electrode layer is formed by sputtering.

The protective film is required to be smooth and tough, to have excellent transparency, and to have excellent heat resistance and chemical resistance which do not cause discoloration or deterioration over a long period of time. A thermosetting resin containing an epoxy copolymer has been used to satisfy such requirements.
However, this protective film needs to be a film having excellent adhesion on glass and color filters, and various adhesion improving agents have been used. However, this kind of adhesion improver may significantly deteriorate the storage stability of the solution, and a highly reliable material having good adhesion and good storage stability has been desired.

On the other hand, for a master substrate such as an MD (mini-disc) and a CD (compact disc), an excellent protective film for protecting the surface is required for the transport operation during the manufacturing process. The protective film material can be easily applied,
It is necessary that the surface of the master substrate be mechanically and chemically protected (waterproof, oxygen-blocked) and easily peeled off.

[0005]

The above-mentioned problems of the conventional protective film, for example, the variation in the developing process due to insufficient tolerance of the developing time after the irradiation of the photosensitive protective film with active rays. In addition, the conventional protective films have not been able to obtain satisfactory characteristics with respect to flatness and adhesion to a substrate or a color filter, which are characteristics that are particularly important for the protective film. An object of the present invention is to solve such a problem, and to provide a material which is inexpensive and has high reliability, flatness, and adhesion.

[0006]

In order to solve these problems, the present invention uses a mixture having the following composition to provide heat resistance, chemical resistance, transparency, flatness, and the like.
A protective film having excellent adhesion and the like could be provided. That is, according to the present invention, the coating composition comprising (a) a polymer and (b) a solvent as essential components contains at least one compound selected from an alkoxysilane compound, an alkoxytitanium compound, an alkoxyaluminum compound and an alkoxyzirconium compound. A coating composition is provided.

[0007] Also provided is a thermosetting coating composition, wherein the coating composition further comprises (c) a thermal crosslinking agent. Also provided is a photosensitive coating composition wherein (a) the polymer is a polymer that is soluble or at least swells in an aqueous alkali solution, and further comprises (d) an actinic ray irradiation polymerization initiator. The photosensitive coating composition preferably further contains (e) a compound having a polymerizable unsaturated bond.

The alkoxysilane compound, alkoxytitanium compound, alkoxyzirconium compound and alkoxyaluminum compound used in the present invention include, for example, acetoalkoxyaluminum diisopropylate, aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-aluminate. Butyrate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), aluminum mono-acetylacetonate bis (ethyl acetoacetate), aluminum di-sec-
Butoxide monoethyl acetoacetate, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ- Aminopropylmethyldimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Methacryloxypropylmethyldimethoxysilane, γ
-Ureidopropyl triethoxysilane, isopropyl triisostearoyl titanate, isopropyl tridecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, tris (dioctyl pyrophosphate)
Ethyl titanate, zirconium-n-propylate,
Zirconium-n-butyrate, tetra-n-butoxyzirconium and the like can be mentioned.

The following general formulas (1) to (8)

[0010]

Embedded image

[0011]

Embedded image

(Wherein R ^{1 to} R ⁴ are the same or different and each have 1 carbon atom which may be substituted by a vinyl group, an amino group, an aminoalkyl group, a keto group or a mercapto group)
To 30 linear or branched alkyl groups, acyl groups or aminoalkyl groups). Particularly preferably, the above general formulas (1) to (1)
In (8), R ^{1 to} R ⁴ are the same or different and are a linear or branched alkyl group having 1 to 30 carbon atoms which may be substituted by an amino group, an aminoalkyl group or a mercapto group. , An acyl group or an aminoalkyl group.

[0013] Alkoxysilane compounds are particularly preferred in terms of adhesion. The addition amount of the selected compound is 0.1 to 20% by weight, preferably 0.2 to 10% by weight, based on the non-solvent component. Examples of the polymer (a) include a novolak resin, polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, a carboxyl group-containing (meth) acrylic resin, (meth) acrylic acid and (meth) acrylic resin. Copolymers of acrylates, such as those having a polymerizable unsaturated bond introduced into these polymers, such as polymers soluble or at least swelling in aqueous alkali solutions, epoxy resins, phenolic resins, polyimides, polyurethanes, melamine resins And unsaturated polyester resins. Particularly, as the epoxy resin, a bisphenol A type epoxy resin such as a bisphenol A type epichlorohydrin resin, an epoxy novolak resin, and a brominated bisphenol A type epoxy resin can be mentioned.

The polymer component (a) has at least the following general formula (I) or (II) because it has good compatibility with the adhesion improver of the present invention and improves adhesion.

[0015]

Embedded image

It is preferred that the polymer contains a segment represented by the following formula: In particular, the polymer component (a) is composed of at least acrylic acid and / or methacrylic acid and the following general formula (III)

[0017]

Embedded image

(Wherein R represents 1 to 15, preferably 1
Alkyl group having 10 to 10 carbon atoms, cycloalkyl group, aromatic hydrocarbon group, hydroxyl group or the following general formula

[0019]

Embedded image

Wherein m is an integer of 1 to 10 and n is an integer of 1 to 5
, Preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having a hydroxyl group), the following general formula (IV)

[0021]

Embedded image

(Wherein R represents the same group as described above), a compound represented by the following general formula (V)

[0023]

Embedded image

And the following general formula (VI)

[0025]

Embedded image

Wherein R ′ is 1 to 15, preferably 1
Alkyl group having 10 to 10 carbon atoms, aromatic hydrocarbon group, 1 to 15 having hydroxyl group, preferably 1 to 10
Represents an alkyl group having two carbon atoms or an aromatic hydrocarbon group having a hydroxyl group).

In particular, the polymer component (a) is preferably a reaction product with a compound having a polymerizable unsaturated bond in the molecular structure. Further, more preferably, for example, (meth) acrylic acid- (meth) acrylic acid ester copolymer, for example, poly (methacrylic acid-co-methyl methacrylate), poly (methacrylic acid-co-methyl acrylate), poly ( Methacrylic acid-co-butyl acrylate), poly (acrylic acid-co-methyl methacrylate), poly (acrylic acid-co-methyl acrylate),
Poly (methacrylic acid-co-benzyl methacrylate), poly (methacrylic acid-co-hydroxymethyl methacrylate), etc. (meth) acrylic acid-lactone-modified hydroxyethyl (meth) acrylate copolymer, for example, the following general formula

[0028]

Embedded image

(Wherein, R ⁵ represents a hydrogen atom or a methyl group, p and q each represent a degree of polymerization, and n represents an integer of 1 to 5), and (meth) acrylic acid-styrene Polymers. (B) As the solvent, ethyl cellosolve, propylene glycol methyl ether acetate (PGMEA), ethyl lactate, polyethylene glycol, polypropylene glycol, cyclohexanone, propylene glycol methyl ether, or the like is used. Good.
Incidentally, a stabilizer, a plasticizer, an antioxidant and the like can be further added to the mixture of the present invention.

The thermal crosslinking agent (c) may be a blocked isocyanate or a compound having at least two same or different residues such as alkoxy and acyloxy, for example, a bis-, tris- or tetra- (hydroxymethyl) -substituted compound. Aromatic or heterocyclic aromatic compounds, bis-, tris- or tetra- (acetoxymethyl) -substituted aromatic or heterocyclic aromatic compounds, N-
Melamine having a hydroxymethyl group, melamine having an N-alkoxymethyl group or melamine having an N-acyloxymethyl group, novolak type epoxy resin, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, alicyclic epoxy A compound containing an epoxy group such as a resin, and an acetal resin such as polyvinyl butyral are used. These may be used alone or in combination of two or more.

As blocked isocyanates, for example, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, etc. are blocked with various blocking agents, for example, ethanol, butanol, dimethyl malonate, imidazole, ε-caprolactam, methylcellosolve, ethylene glycol and the like. Is used. In addition, instead of blocked hexamethylene diisocyanate, peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, acetyl peroxide and lauroyl peroxide are also used.

As the actinic ray irradiation polymerization initiator (d),
Various compounds such as azide compounds, halomethyloxazole compounds, halomethyl-s-triazine compounds, onium salts, benzoin ethers, benzophenones, xanthones, and acetophenone derivatives can be used. The following are specific examples of the azide compound.

4,4'-diazidostilbene, 4,4'-diazidostilbene-2,2'-disulfonic acid-N, N-diethyleneoxyethylamide, 4,4'-diazidostilbene-2,2 '-Disulfonic acid-N-propylhydroxyamide, 4,4'-diazidostilbene-2,2'-disulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid-N, N-diethylamide , 4,4 '
-Azidostilbenes such as diazidostilbene-2,2'-disulfonic acid sodium salt and derivatives thereof; 2,6-di- (p-
(Azidobenzal) -cyclohexanone, 2,6-di- (p-azidobenzal) -4-methylcyclohexanone, 2,6-di- (p-azidobenzal) -4-tert-amylcyclohexanone, 2,6-di
Azidobenzalcyclohexanones and derivatives thereof, such as-(p-azidocinnamylidene) -4-tert-aminocyclohexanone; azidocinnamylidenecyclohexanones and derivatives thereof; p-azidobenzalacetophenone, p-azidobenzalacetone , 4,4'-diazidochalcone, 2,6-
Bis (4'-azidobenzal) acetone, 2,6-bis (4'-azidobenzal) acetone-2'-sulfonic acid-N, N-diethyleneoxyethylamide, 2,6-bis (4'-azidobenzal) -acetone Azidobenzal ketones such as -2,2'-disulfonic acid-N, N-diethyleneoxyethylamide and derivatives thereof.

Further, a polymer in which an azide group is introduced into a polymer chain can also be used. Halomethyl oxazole compounds include 2-trichloromethyl-5-styryl-1,3,4
-Oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxa Diazole and the like.

As the halomethyl-s-triazine compound, in particular, a trihalomethyl-s-triazine compound such as 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (Trichloromethyl) -6- (1
-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (p-phenylstyryl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2,4-bis (trichloromethyl) -6-phenyl-s-triazine, 2 (2 '(5'-methylfuryl) ethylidene) -4,6-bis (trichloromethyl) -
s-triazine, 2 (2'-furylethylidene) -4,6- (trichloromethyl) -s-triazine, 5,7-bis (tribromomethyl) -s-triazolo [1,5-a] pyrimidine, etc. No.

These may be used alone or in combination of two or more. Examples of benzoin ethers include benzoin methyl ether and benzoin isobutyl ether. As benzophenones, for example, acetophenone, 2,2-dimethoxy-2
-Phenylacetophenone, 1,1-dichloroacetophenone, Michler's ketone, o-benzoylmethylbenzoate and the like. Xanthones include, for example, xanthone, thioxanthone, 2-chlorothioxanthone, 2-
Examples thereof include alkylthioxanthone and 2,4-dialkylthioxanthone.

Examples of the acetophenone derivative include acetophenone, trichloroacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenylacetophenone. Examples of the onium salt include various sulfonium salts, iodonium salts, and diazonium salts. Specific examples include triphenylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and α-naphthylmethyl-4-. Hydroxyphenylmethylsulfonium hexafluorophosphate (or hexafluoroantimonate), diphenyl-t-butylphenylsulfonium trifluoromethanesulfonate, diphenylmethoxyphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, di-t-butylphenyliodonium Trifluoromethanesulfonate (or hexafluoroantimonate, or tetrafluoroborate) Over g), methoxyphenyl phenyl iodonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, aminophenyl tetrafluoroborate include pyrene diazonium tetrafluoroborate.

These may be used alone or in combination. Further, a sensitizer may be used in combination for improving the sensitivity. Examples of the sensitizer include 2-nitrofluorene, 2,4,7-trinitrofluorenone, benzuanthrone, picramide, 1,2-benzanthraquinone, 11-chloro-6-hydroxybenzanthrone, phenanthranquinone, and 4 -(4-butoxyphenyl) -2,6-diphenylthiopyrylium perchlorate and the like.

Examples of the compound (e) having a polymerizable unsaturated bond include various vinyl monomers and vinyl oligomers. Specifically, acrylate monomers,
Examples include methacrylate monomers, and include esters of polyhydric alcohols such as ethylene glycol and trimethylolpropanol with acrylic acid and methacrylic acid, and the above esters of polymers and oligomers having an alcoholic hydroxyl group such as polyvinyl alcohol. Also, acrylate melamine, methacrylate melamine,
Urethane methacrylate, urethane acrylate and the like are also included in the present invention. More specifically, examples thereof include 2-hydroxyethyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, diethylene glycol dimethacrylate, polyethylene glycol methacrylate, trimethylolethanetetramethacrylate, and tetramethylolmethanetetraacrylate.

These may be used alone or in combination of two or more. It is preferable to add a leveling agent to the coating composition of the present invention, particularly to the coating composition for a color filter protective film. By adding a leveling agent, better surface flatness can be obtained. As this leveling agent, for example, polyether-modified dimethylpolysiloxane-based BYK300, BYK301, BYK306, B
YK307, BYK335, BYK330, BYK33
1, BYK341, BYK344, BYK346, BY
K302, BYK164 and the like, polyether-modified dimethylalkylpolysiloxane-based BYK320 and BYK32
5, BYK077, polyester-modified dimethylalkylpolysiloxane-based BYK370, polyester-modified methylalkylpolysiloxane-based BYK322, BYK
075 (All BK Chemie (B
YK Chemie).

Examples of the fluorine-based leveling agent include fluoroalkylcarboxylic acid, disodium N-perfluorooctanesulfonylglutamate, sodium 3- [ω-fluoroalkyloxy] -1-alkylsulfonate, perfluorocarboxylic acid, and perfluorocarboxylic acid. Examples thereof include fluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonamidopropyltrimethylammonium salt, and monoperfluoroalkylethyl phosphate.

The coating composition of the present invention is used for MD, CD
When used for a protective film for a master substrate such as described above, a thermal crosslinking agent, a polymerization initiator and the like may not be contained. The composition is spin-coated on a master substrate, by an appropriate method such as spray coating,
It is applied to a thickness of 0.5-20 μm, and
After drying for a minute, a protective film is formed. After work
To remove the protective film, for example, NMP, γ-butyrolactone, acetone, isopropylamine (IPA), ethyl alcohol, butyl alcohol, methyl alcohol,
Performed using a wide range of organic solvents such as dimethylacetone,
In order to promote the removal, means such as an ultrasonic bath may be further used. This protective film has heat resistance of about 200 ° C. and also has mechanical strength. Also, it can be easily applied and peeled off.

The thermosetting coating composition and the photosensitive coating composition of the present invention are mainly used as a color filter protective film. As a method of applying the composition of the present invention to a substrate, for example, on a glass substrate on which a color filter is formed, spray, flow coating, roll coating, spin coating, dip coating, for example, 0.5 to 10
It can be applied to a thickness of μm. Next, the solvent is removed by evaporation, and the pattern forming material is left on the substrate.
Removal of the solvent can be accelerated by heating or reducing pressure as desired. It is important that the heating temperature does not cause deterioration of the forming material and the base material.
It can be heated to 0 ° C. In the case of a photosensitive resin, the layer is then irradiated with actinic radiation so as to project a pattern.
Next, the layer is treated with a developing solution, the irradiated portion is insolubilized, and the unirradiated portion is dissolved to reveal a protective film pattern. Further, development may be performed after irradiation and heating. By this heating, for example, the sensitivity can be further improved. The heating temperature is preferably such that the pattern shape, the substrate, and the like do not deteriorate. For example, the heating temperature can be 200 ° C. or less. As a light source used for the irradiation, for example, 190 to 450 nm, preferably 200 to 400 nm
UV irradiation of the region is mentioned, and electron beam or X-ray irradiation is also used. In order to make the inclination of the pattern edge gentle, irradiation with actinic radiation may be performed at a distance between the layer surface and the mask during UV irradiation of usually several micrometers. The distance between the layer surface and the mask varies depending on the desired shape, but is generally from 0.2 to 200 μm. Further, it is also possible to adjust the image forming position of the pattern up and down by using an actinic ray irradiation device such as a stepper or a mirror projection to make the inclination of the pattern end portion gentle.

It is preferable that the pattern obtained by the development is further cured by heating or irradiation with actinic radiation to improve crack resistance, solvent resistance and the like. In the above, for example, a silicate, metasilicate, hydroxide, hydrogen phosphate, ammonia, or the like of an alkali metal and / or an alkaline earth metal, particularly, an ammonium ion is used as the developer. In addition, as a developer not containing metal ions,
For example, US Pat. No. 4,729,941, EP-A62,7
Known materials described in the specification of No. 33 and the like can be used. Further, a surfactant, a detergent, an organic solvent, and the like may be added to the developer. Examples of those added to the developer for the above purpose include nonionic activators, ionic activators, alcohols, carboxylic acids, amines and derivatives thereof, and specifically, polyalkylene glycols and esters thereof, Oxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, alkylphenol alkylenoxide adduct, sulfonate, sulfonate, carboxylate, carboxylate, alkylamide alkylene oxide adduct, alkylamine And the like. These may be added alone or in combination of two or more. In this case, the amount of addition is preferably 0.1 to 0.3% by weight based on the developer.

In the case of a thermosetting resin, after coating, unnecessary portions of the protective film pattern are removed by a wiping method. As a wiping method, there is a method of wiping an unnecessary portion of the coating layer with a cloth or a brush using a commercially available machine. 10
After drying the solvent at about 0 ° C., heat treatment is performed on a hot plate at 190 ° C. to 250 ° C. for 10 to 20 minutes to obtain a protective film having excellent heat resistance and chemical resistance. In the case of a photosensitive resin, a protective film having excellent heat resistance and chemical resistance can be obtained by performing a heat treatment on a hot plate at 190 to 250 ° C. for 10 to 20 minutes after development.

By adding an alkoxide compound according to the present invention, the photosensitive resin protective film or the thermosetting resin protective film has a wider allowable range of development time and improved adhesion. It is thought that the explanation can be given by the adhesion to the film. That is, the reason why the allowable range of the development time is narrow is presumed to be that the adhesion to the substrate is weak and the developing solution enters between the substrate and the protective film or between the color filter and the protective film during the development and causes peeling. It is thought that the addition of the compound according to the present invention improves the adhesion at the interface with the substrate or the color filter, and improves the allowable range of development time and the adhesion.

[0047]

The present invention will be described more specifically with reference to the following examples.

[0048]

[Table 1]

Example 1 The following materials were prepared as photosensitive coating compositions: Polymer I (glycidyl methacrylate adduct of methacrylic acid-methyl methacrylate copolymer: acid value 80, molecular weight 20,000, double bond equivalent 500) ): 91 g 2,4-bis (trichloromethyl) -6-styryl-s-triazine: 5 g Blocked hexamethylene diisocyanate (Coronate 2507 (manufactured by Nippon Polyurethane Co.)): 3 g Compound I: 1 g Based on the above composition Propylene glycol methyl ether acetate was added as a solvent, and the non-solvent component was 20%.
A composition containing% by weight was prepared.

Each of the above compositions was spin-coated to a thickness of 1.5 μm on a substrate on which a 1.2 μm color filter was formed, and then dried on a hot plate at 100 ° C. for 1 minute. The photosensitive coating layer was exposed to a PROXIMITY exposure of about 100 μm with a high-pressure mercury lamp through a predetermined mask. Next, the photosensitive coating layer irradiated with the pattern actinic radiation was developed with 0.05 N potassium hydroxide to obtain a pattern. Then, place on a hot plate at 230 ° C for 10 minutes.
Heat cured for minutes. As a result, a pattern having a gentle edge with good transparency, in visible light of 400 μm or more, excellent in adhesion, abrasion resistance, stain resistance, and chemical resistance was obtained. FIG. 1 shows a transmittance curve of the protective film according to the present embodiment. Example 2 In the composition of Example 1, compound I was substituted for compound I
A photosensitive coating composition was prepared in the same manner as in Example 1 except that II was used, and subjected to PROXIMITY exposure and development. Excellent adhesion, abrasion resistance, stain resistance, chemical resistance,
A transparent pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Example 3 In the composition of Example 1, instead of compound I, compound
A photosensitive coating composition was prepared and subjected to PROXIMITY exposure and development in the same manner as in Example 1 except that III was used. Excellent adhesion, abrasion resistance, stain resistance, chemical resistance,
A transparent pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Example 4 In the composition of Example 1, compound I was substituted for compound I
A photosensitive coating composition was prepared in the same manner as in Example 1 except that IV was used, and subjected to PROXIMITY exposure and development. Excellent adhesion, abrasion resistance, stain resistance, chemical resistance,
A transparent pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Example 5 A photosensitive coating composition was prepared and subjected to PROXIMITY exposure and development in the same manner as in Example 1 except that Compound V was used instead of Compound I in the composition of Example 1. Excellent adhesion, abrasion resistance, stain resistance, chemical resistance,
A transparent pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Example 6 In the composition of Example 1, compound I was substituted for compound I
A photosensitive coating composition was prepared in the same manner as in Example 1 except that VI was used, and subjected to PROXIMITY exposure and development. Excellent adhesion, abrasion resistance, stain resistance, chemical resistance,
A transparent pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Example 7 In the composition of Example 1, compound I was used instead of compound I.
A photosensitive coating composition was prepared in the same manner as in Example 1 except that VII was used, and subjected to PROXIMITY exposure and development. Excellent adhesion, abrasion resistance, stain resistance, chemical resistance,
A transparent pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Example 8 The following materials were prepared as a thermosetting coating composition: Polymer I: 92 g Bisphenol A type epichlorohydrin: 5 g Blocked hexamethylene diisocyanate (Coronate 2507 (manufactured by Nippon Polyurethane Co., Ltd.)): 2 g Compound I 1 g of propylene glycol methyl ether acetate was added as a solvent to the composition, and the non-solvent component was 20 g.
A composition containing% by weight was prepared.

Each of the above compositions was spin-coated to a thickness of 1.5 μm on a substrate on which a 1.2 μm color filter was formed, and a coating layer of a protective film pattern was formed by a wiping method. Then on a hot plate at 100 ° C for 1
Dried for minutes. Then, it was cured on a hot plate at 230 ° C. for 15 minutes. This allows adhesion, wear resistance,
A protective film excellent in stain resistance and chemical resistance and having good transparency in visible light of 400 μm or more was obtained. Example 9 The following materials were prepared as a thermosetting coating composition: Polymer I: 92 g Bisphenol A type epichlorohydrin: 5 g Blocked hexamethylene diisocyanate (Coronate 2507 (manufactured by Nippon Polyurethane Co., Ltd.)): 2 g Compound II : 1 g In the same manner as in Example 8, a protective film having excellent adhesion, abrasion resistance, stain resistance, and chemical resistance and a pattern having a gentle edge with good transparency in visible light of 400 μm or more was obtained. Was done. Example 10 In the photosensitive coating composition shown in Example 1,
Mix 0.25 g of BYK164 (leveling agent)
A composition was prepared.

The above composition was prepared in the same manner as in Example 1 and the PR
OXIMITY Exposure and development were performed. Surface flatness is ± 0.1
The pattern was improved from μm to ± 0.05 μm, and a gentle edge pattern having excellent adhesion, abrasion resistance, stain resistance, and chemical resistance was obtained. Example 11 0.25 g in the thermosetting coating composition of Example 8
Was added to prepare a composition. The above composition was formed into a film in the same manner as in Example 11. As a result, the surface flatness ranges from ± 0.1 μm to ± 0.1 μm.
The pattern was improved to 05 μm, and a gentle edge pattern having excellent adhesion, abrasion resistance, stain resistance, and chemical resistance was obtained. Example 12 A photosensitive coating composition was prepared in the same manner as in Example 1 except that the following polymers were used in place of the polymer I in the composition of Example 1, and PROXIMITY exposure and development were performed. A pattern having good adhesion, abrasion resistance, stain resistance, and chemical resistance, good transparency in visible light of 400 μm or more, and a gentle edge was obtained. Polymer 1. 1. poly (methacrylic acid) _0.25- co- (benzyl methacrylate) _0.75 molecular weight: about 30,000 2. poly (methacrylic acid) _0.3 -co- (methyl methacrylate) _0.7 molecular weight: about 25,000 Poly (styrene) _0.8- co- (methacrylic acid)
_0.2 molecular weight: about 15,000 Poly (methacrylic acid) _0.2 -co- (butyl methacrylate) _0.8 Molecular weight: about 45,000 Example 13 In the composition of Example 8, the following polymers were used in place of the polymer I, respectively. Similarly, a thermosetting coating composition was prepared to obtain a protective film. Excellent adhesion, stain resistance and chemical resistance
A pattern with good transparency and a gentle edge was obtained when placed in visible light of 00 μm or more. 1. 1. poly (methacrylic acid) _0.25- co- (benzyl methacrylate) _0.75 molecular weight: about 30,000 2. poly (methacrylic acid) _0.3 -co- (methyl methacrylate) _0.7 molecular weight: about 25,000 Poly (styrene) _0.8- co- (methacrylic acid)
_0.2 molecular weight: about 15,000 Poly (methacrylic acid) _0.2- co- (butyl methacrylate) _0.8 Molecular weight: about 45,000 Example 14 Polymer I: 99 g Compound IV: 1 g of propylene glycol methyl ether acetate was added as a solvent to a composition comprising A composition containing 20% by weight of a solvent component was prepared. The composition is
It was applied to a thickness of about 10 μm on an MD master substrate by a spray method and dried at 60 ° C. to form a protective film. Thereafter, the surface of the MD master substrate with a protective film was exposed to a transport environment. The film was immersed in acetone and the film was removed in about 15 minutes. When the film was immersed in acetone in an ultrasonic bath to promote the removal of the film, the film could be removed in about 1 minute. The protective film showed sufficient strength against mechanical damage, had high adhesiveness, and could be easily removed with an organic solvent such as acetone, and was suitable for work.

The photosensitive coating composition of the present invention and the layer forming step thereof are formed in the above-described configuration, thereby providing protection having excellent adhesion, abrasion resistance, stain resistance, chemical resistance, heat resistance, and smoothness. It can be used as a membrane, and its industrial value is extremely high. In addition, a gentle edge at the end, which was conventionally considered difficult, could be realized, and no problem such as disconnection of the conductive film occurred.

[Brief description of the drawings]

FIG. 1 is a transmittance curve of the photosensitive coating composition of the present invention.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 6, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 7

[Correction method] Change

[Correction contents]

Embedded image (Wherein, R represents an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group, a hydroxyl group, or a compound represented by the following general formula:

Embedded image (Wherein m is an integer of 1 to 10 and n is an integer of 1 to 5) having an alkyl group having 1 to 15 carbon atoms or an aromatic hydrocarbon group having a hydroxyl group. The following general formula (IV)

Embedded image (Wherein, R represents the same group as described above),
(V)

Embedded image And the following general formula (VI)

Embedded image (Wherein R ′ represents an alkyl group having 1 to 15 carbon atoms, an aromatic hydrocarbon group, an alkyl group having 1 to 15 carbon atoms having a hydroxyl group, or an aromatic hydrocarbon group having a hydroxyl group. The coating composition according to claim 6, which is a copolymer with at least one monomer represented by the following formula:

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 8

[Correction method] Change

[Correction contents]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C09D 201/02 C09D 201/02 201/08 PDF 201/08 PDF // C08F 290/06 MRS C08F 290 / 06 MRS (72) Inventor Hidemasa Yamaguchi 1-3-2 Minamidai, Kawagoe-shi, Saitama Hextoin Industry Co., Ltd. Advanced Materials Technology Laboratory (72) Inventor Yuko Nozaki 1-3-2 Minamidai, Kawagoe-shi, Saitama Street Co., Ltd. Advanced Materials Technology Research Laboratory

Claims (8)

[Claims] 1. A coating composition comprising (a) a polymer and (b) a solvent as essential components, comprising at least one compound selected from an alkoxysilane compound, an alkoxytitanium compound, an alkoxyaluminum compound and an alkoxyzirconium compound. A coating composition comprising: 2. The coating composition according to claim 1, further comprising (c) a thermal crosslinking agent. 3. The polymer component (a) is a polymer that is soluble or at least swells in an aqueous alkaline solution,
The coating composition according to claim 1, further comprising (d) an actinic ray irradiation polymerization initiator. 4. The coating composition according to claim 3, further comprising (e) a compound having a polymerizable unsaturated bond. 5. The weight ratio of at least one compound selected from the group consisting of the alkoxysilane compound, alkoxytitanium compound, alkoxyaluminum compound and alkoxyzirconium compound, based on the content of the non-solvent component of the coating composition, The coating composition according to any one of claims 1 to 4, which is 0.1 to 20% by weight. 6. The polymer component (a) has at least the following general formula (I) or (II): A polymer containing a segment represented by the formula:
The coating composition according to any one of the above. 7. The polymer component (a) comprises at least acrylic acid and / or methacrylic acid and a compound represented by the following general formula (II)
I) (Wherein R is an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group, a hydroxyl group, or a compound represented by the following general formula: (Wherein m is an integer of 1 to 10 and n is an integer of 1 to 5) having an alkyl group having 1 to 15 carbon atoms or an aromatic hydrocarbon group having a hydroxyl group. The following general formula (IV): (Wherein, R represents the same group as described above),
(V) And the following general formula (VI): (Wherein R ′ represents an alkyl group having 1 to 15 carbon atoms, an aromatic hydrocarbon group, an alkyl group having 1 to 15 carbon atoms having a hydroxyl group, or an aromatic hydrocarbon group having a hydroxyl group. The coating crude product according to claim 6, which is a copolymer with at least one monomer represented by the following formula: 8. The coating crude product according to claim 6, wherein the polymer component (a) is a reaction product with a compound having a polymerizable unsaturated bond in a molecular structure.