JP3211403B2 - UV curable resin composition and color filter protective film using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curing resin composition and a protective film for a color filter using the composition.

[0002]

2. Description of the Related Art Transparency, adhesion, spatter resistance, coating properties, heat resistance, and the like are required as characteristics required for a resin for a protective film of a color filter, and a (meth) acrylic resin (for example, JP-A-60-216307), epoxy resin (for example, JP-A-4-97102), and polyimide-based resin (for example, JP-A-1-2292).
No. 03) has been studied. Of these resins, (meth) acrylic resins have the highest transparency,
It has been widely studied. However, these resins, including (meth) acrylic resins, have some problems in balancing physical properties such as adhesion, spatter resistance and heat resistance. Many proposals have been made to improve these points. For example, JP-A-60-216307 and JP-A-4-97100 disclose a method in which a polycarboxylic acid anhydride is mixed with an epoxy group-containing polymer and a crosslinked and cured film is formed by heating. But,
Mix high molecular weight compound with strong polar low molecular weight compound,
Since the reaction is carried out, unreacted polycarboxylic anhydride remains to form a non-uniform layer, and the physical properties deteriorate, which is not preferable.

[0003] On the other hand, polyimide resins have the drawbacks that they are essentially inferior in transparency and require high-temperature heating when the film is cured. In addition, it is necessary to remove the protective film around the color filter substrate in the process, which is currently performed using a resist. Recently, Japanese Patent Laid-Open No. 4-153
No. 274, Japanese Unexamined Patent Publication No. 4-164970, etc.
A color filter protective film using an ultraviolet ray effect resin composition is disclosed. However, in these cases, the developer is a highly toxic organic solvent, which is not preferable in operation.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to perform pre-baking, irradiating ultraviolet rays through a mask, and performing development using a less toxic developing solution instead of a conventional highly toxic organic solvent. An object of the present invention is to provide an ultraviolet curable resin composition capable of obtaining a possible coating film. Another object of the present invention is to provide a color filter protective film which is not deteriorated in physical properties and is excellent in transparency, heat resistance, chemical resistance, spatter resistance and adhesion.

[0005]

As a result of various studies, the present inventors have found that the use of a specific ultraviolet-curable resin composition satisfies the required characteristics of the above-mentioned color filter protective film, and at the same time, has a low toxicity and a low alkalinity. The inventors have found that etching can be performed with an aqueous solution, and have completed the present invention. That is,

The ultraviolet curable resin composition of the present invention is characterized by containing the following four components (A), (B), (C) and (D). (A) General formula (I)

Embedded image And a structural unit represented by the general formula (II)

Embedded image An epoxy group-containing (meth) having a structural unit represented by the following as a main structural unit, and having an intrinsic viscosity at 30 ° C. of 0.05 to 1 in diethylene glycol dimethyl ether:
Acrylic copolymer, (B) intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether is 0.0
(C) a monomer having a (meth) acrylic group, which is 5-1 and contains at least one of a carboxylic acid group and a polycarboxylic anhydride group;
(D) a photopolymerization initiator. (However, in the general formulas (I) and (II), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and m and n each independently represent an integer of 1 to 4) .)

The color filter protective film of the present invention is obtained by applying a UV-curable resin composition containing the above four components (A), (B), (C) and (D) to a substrate and, if necessary, prebaking. Then, it is obtained by irradiating ultraviolet rays, performing etching if necessary, and performing post-baking as necessary.

In a preferred embodiment of the ultraviolet-curable resin composition of the present invention, the components (A) are glycidyl methacrylate (hereinafter sometimes abbreviated as GMA) and 2-hydroxyl methacrylate (hereinafter abbreviated as HEMA). And a component (B) comprising methyl methacrylate (hereinafter sometimes abbreviated as MMA), methacrylic acid (hereinafter sometimes abbreviated as MA) and maleic anhydride (Hereinafter abbreviated as MAH), M
It is a copolymer containing MA and MA or MMA and MAH as main components.

The components (A) and (B) can be easily synthesized by ordinary radical polymerization. A monomer having both of these components and (C) a meta (acryl) group,
(D) The ultraviolet curable resin composition of the present invention can be produced by mixing a photopolymerization initiator and, if necessary, additives such as a coupling agent, or dissolving it in an organic solvent, if necessary.

The component (A) used in the present invention has the following general formulas (III) and (IV)

Embedded image

Embedded image (However, in the general formulas (III) and (IV), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and m and n are each independently an integer of 1 to 4. )
Can be obtained by copolymerizing the monomer represented by Of these, the combination of glycidyl methacrylate and 2-hydroxyethyl methacrylate is most preferred. It can be easily obtained by polymerizing these monomers in the presence of a radical polymerization initiator. In this case, another (meth) acrylic monomer or a small amount of a vinyl monomer may be added for copolymerization in order to improve properties such as solubility and adhesion of the obtained polymer.

Other (meth) acrylic monomers include methyl acrylate, ethyl acrylate and n-acrylic acid.
Butyl, 2-ethylhexyl acrylate, acrylic acid 2
Acrylates such as -ethoxyethyl, 2-hydroxyethyl acrylate, or methyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Examples thereof include methacrylates such as benzyl and 2-hydroxypropyl methacrylate.
Other vinyl monomers include styrene, p-hydroxystyrene, α-methylstyrene and the like.

The proportion of these monomers in the polymer is 30 to 90% by weight of the monomer represented by the general formula (III), 10 to 70% by weight of the monomer represented by the general formula (IV), and other (meth) acrylic monomers. 0-30% by weight and 0-30% by weight of vinyl monomer. As a part of another (meth) acrylic monomer or vinyl monomer, a monomer having a carboxylic acid group or a polycarboxylic anhydride group described below within 10% by weight can be added. The component (A) can be easily obtained by subjecting the above monomer to a polymerization reaction in a reaction solvent in the presence of a radical polymerization initiator according to a conventional method. The polymerization degree of the obtained copolymer is preferably such that the intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether is in the range of 0.05 to 1. Below this range, the physical properties of the protective film for the color filter deteriorate, and above this range, the solubility in a solvent decreases, and the selection range of the solvent is unfavorably limited.

The reaction solvent used here includes ketones such as metal ethyl ketone, methyl isobutyl ketone, and methylcyclohexanone; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. And esters such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate.

Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, t-butylperoxybenzoate and lauroyl peroxide, and azobisisobutyronitrile.

The component (B) which contains at least one of a carboxylic acid group and a polycarboxylic acid anhydride group (meth)
The acrylic polymer is composed of 10 to 70% by weight of a monomer having a carboxylic acid group or a polycarboxylic anhydride group, 30 to 90% by weight of the other (meth) acrylic monomer described above,
If necessary, it can be obtained by mixing another vinyl-based monomer in an amount of 30% by weight or less and conducting polymerization using the above-mentioned solvent and radical polymerization initiator according to a conventional method.

The epoxy group-containing (meth) acrylic monomer described above can be added as a part of the (meth) acrylic monomer within a range of 10% by weight or less. In addition, as a monomer containing a carboxylic acid group or a polycarboxylic anhydride group used in the synthesis, (meth) acrylic monomers such as acrylic acid and methacrylic acid, maleic anhydride, citraconic anhydride, 2,3 Examples include maleic anhydride derivatives such as -dimethylmaleic acid, 1-cyclohexane-1,2-dicarboxylic acid, ethylmaleic anhydride, 2-methyl-3-ethylmaleic anhydride, and 2,3-diethylmaleic anhydride can do.

The polymerization degree of the polymer of the component (B) is preferably such that the intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether is in the range of 0.05 to 1. Below this range, the physical properties of the color filter protective film decrease, and above this range, the solubility in solvents decreases,
It is not preferable because the selection range of the solvent is limited.

Examples of the monomer having a (meth) acryl group as the component (C) include the following compounds. Butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, benzyl acrylate, carbitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxylethyl acrylate, 2-hydroxyethyl Methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, N-methylol acrylamide, N-diacetone acrylamide, N, N'-methylenebisacrylamide, N-vinylpyrrolidone, ethylene glycol diacrylate, diethylene glycol Diacrylate, triethylene glycol diacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6 -Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Chromatography, tri triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetra (3-mercaptopropionate), pentaerythritol (mercaptoacetate), glycerol acrylate / methacrylate, etc.,

As the photopolymerization initiator of the component (D), the following compounds can be exemplified. Benzophenone, Michler's ketone, 4,4'-diethylaminobenzophenone, xanthone, thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-
2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether,
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, camphorquinone, benzuanthrone, 2-methyl-1- ｛4-
(Methylthio) phenyl} -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl-1- (4-
Morpholinophenyl) -butanone-1,3,3 ',
4,4'-tetra (t-butylperoxycarbonyl)
Benzophenone, N-phenyl-glycine, p-hydroxy-N-phenylglycine, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, p
-Tolyl disulfide, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 3,
3'-carbonyl-bis (7-diethylamino) coumarin, 2,6-bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene)-
-Methylcyclohexanone, 2,6-bis (p-azidobenzylidene) -4-tert-butylcyclohexanone, ethyl-p- (N, N-dimethylamino) besozoate and the like.

When these components (A), (B), (C) and (D) are mixed, any combination of compounds that are mutually soluble can be used as it is as the composition of the present invention. However, in general, in order to improve coating properties, it is preferable to dissolve these compounds in an organic solvent and use them as a coating solution. As the organic solvent, the above reaction solvents can be used in any mixing ratio. (A) (B) The mixing ratio of both components is that the epoxy group in the component (A) and the carboxylic acid group in the component (B) (the carboxylic acid anhydride group is calculated as two carboxylic acids) are close to equivalent. Is preferred, but not so strict. The component (C) is used in an amount of from 20 to 300 based on 100 parts by weight of the total of the components (A) and (B).
Part by weight is preferred, and 50 to 200 parts by weight is particularly preferred. If the amount is less than this, curing by ultraviolet rays is insufficient, and if it is more than this, the physical properties of the cured film deteriorate. The component (D) is used in an amount of 1 to 50 parts by weight,
20 parts by weight are particularly preferred. If the amount is less than this, curing by ultraviolet rays is insufficient, and if it is more than this, the stability over time of the coating solution is undesirably reduced.

In addition to these components, if necessary, a crosslinking aid, a coupling agent and a thermal polymerization inhibitor of not more than 20% by weight of the polymer can be added. As the crosslinking aid, a compound containing a hydroxyl group, a carboxyl group and an amino group is used. Silane, aluminum and titanate compounds are used as a coupling agent for improving the adhesion to the substrate. Specific examples of these include silanes such as 3-aminopropyltriethoxysilane, 3-aminophenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; Examples include aluminum-based materials such as isopropylate, and titanate-based materials such as tetraisopropylbis (dioctylphosphite) titanate. Hydroquinone, p-methoxyphenol and the like are used as the thermal polymerization inhibitor.

Next, a method for forming a color filter protective film using the ultraviolet curable resin composition of the present invention will be described. The ultraviolet curable resin composition of the present invention is spin-coated,
It is applied on a color filter patterned on a glass substrate by a known method such as immersion or spray printing to form a coating film. The coating film is prebaked at a temperature of 30 to 150 ° C. using a heating means such as an electric furnace or a hot plate to remove most of the solvent in the coating film. A negative mask is placed on the coating film and irradiated with actinic radiation.
Examples of the actinic ray include X-rays, electron beams, ultraviolet rays, and visible rays, and ultraviolet rays and visible rays are particularly preferable. Next, a relief pattern is obtained by dissolving and removing an unexposed portion with a developer as necessary.
As the developing solution, a weak alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, or tetraammonium hydroxide can be used. If necessary, rinsing can be performed in a non-solvent. In order to accelerate the curing of the polymer of the relief pattern formed by development, post-baking can be performed at a temperature of 150 to 300 ° C., preferably 180 to 250 ° C. by the above heating means.

Further, the ultraviolet curable resin composition of the present invention can be prepared by a known method such as spin coating, dipping or spray printing, for example, a silicon wafer, a metal plate, a plastic plate, or the like.
A cured film can be formed by applying a pre-baking and post-baking process similar to the formation of the color filter protective film described above to form a coating film by coating on a substrate such as the above. Can be used.

Hereinafter, the present invention will be described specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to these Synthesis Examples and Examples.

Synthesis of epoxy group-containing (meth) acrylic copolymer [component (A)] (Synthesis Example 1) 35 parts by weight of GMA (hereinafter, all parts by weight), 15 parts of HEMA, azobisisobutyro 2 parts of nitrile (hereinafter abbreviated as AIBN) are dissolved in 300 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) and dissolved in 60 parts.
C. for 4 hours, followed by polymerization at 80 ° C. for 12 hours,
The reaction solution was transferred into a large amount of n-heptane to precipitate a polymer, and dried under reduced pressure in a vacuum drier at 50 ° C. which was separated by filtration for 24 hours to obtain a copolymer of component (A) (referred to as AI). Was. The intrinsic viscosity measured at 30 ° C. in a solution of this polymer in diethylene glycol dimethyl ether (hereinafter abbreviated as DIG) was 0.079.

(Synthesis Example 2) 25 parts of GMA, 20 parts of HEMA, 5 parts of MMA, and 2 parts of AIBN were mixed with 30 parts of MEK.
Synthesis was carried out in the same manner as in Synthesis Example 1 except that the polymer was dissolved in 0 parts to obtain a component (A) polymer (A-II) having an intrinsic viscosity of 0.12.

Synthesis of (meth) acrylic polymer [component (B)] containing one or more of carboxylic acid groups and polycarboxylic anhydride groups: (Synthesis Example 3) 30 parts of MA, MMA 70 parts and AI
Synthesis was performed in the same manner as in Synthesis Example 1 except that 1 part of BN was dissolved in 300 parts of DIG, to obtain a polymer (B-I) of the component (B) having an intrinsic viscosity of 0.18.

(Synthesis example 4) 30 parts of MAH, 10 parts of MA
Parts, 50 parts of MMA, 10 parts of styrene, and AIB
Synthesis was performed in the same manner as in Synthesis Example 1 except that 1 part of N was dissolved in 300 parts of MEK, to obtain a polymer (B-II) of the component (B) having an intrinsic viscosity of 0.14.

Example 1 As component (A), 41 parts of copolymer (AI), (B)
59 parts of the polymer (BI) as a component, 100 parts of pentaerythritol triacrylate as a component (C),
Component (D) is 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1
Parts, 2 parts of ethyl-p- (N, N-dimethylamino) benzoate, 2 parts of isopropylthioxanthone, and a silane coupling agent (S510, manufactured by Chisso Corporation) 5
Part of the solvent diethylene glycol dimethyl ether (D
IG) was dissolved in 300 parts to prepare an ultraviolet-curable resin composition.

These resin compositions were applied on a glass plate and prebaked on a hot plate maintained at 70 ° C. for 20 minutes to form a coating film. These coatings were exposed through a mask for 20 seconds with an ultra-high pressure mercury lamp (20 mw / cm ² ). These were developed by immersing them in a developer containing 2% sodium carbonate for 2 minutes, and rinsed with water. Furthermore, when post-baking was performed in an oven at 200 ° C. for 1 hour, there was no residual film in the unexposed area, and a transparent film remained in the exposed area. Separately, after the entire surface was exposed under the same conditions, post-baking was performed without dipping in a developer to form a coating film.

The film thickness obtained by immersion in the post-exposure developer and the film obtained without immersion in the post-exposure developer, ie, the film thickness depending on the presence or absence of development, was measured, and the remaining film ratio was calculated by the following equation. ,
The results are shown in Table 1. Remaining film ratio = [exposed film thickness (with development) / exposed film thickness (without development)] × 100 Next, transparency, adhesion to a substrate, and chemical resistance required for a color filter protective film. , Heat resistance and spatter resistance were measured. In addition, the physical properties of a resin composition obtained by mixing an epoxy group-containing polymer with a low molecular weight acid anhydride are shown as Comparative Example 1. Table 1 shows the results.

The method for measuring the characteristics required for the color filter protective film is described below. (Transparency) The light transmittance was measured with a spectrophotometer UV-210A manufactured by Shimadzu Corporation, and the light transmittance at a wavelength of 400 nm was shown. (Heat resistance) Transparency after heat treatment at 250 ° C. was shown. (Chemical resistance) N-methyl-2-pyrrolidone solution at room temperature
It was fixed vertically for 0 minutes and immersed, and it was determined whether or not the boundary between the part immersed in the liquid and the part immersed in the liquid could be visually identified. When the boundary line was visible, it was evaluated as x, and when it was not, it was evaluated as ○. (Spatter resistance) When an ITO film (indium-tin oxide) having a thickness of 200 Å at 200 ° C. was formed on the cured film by sputtering, the presence or absence of wrinkling of the film was examined. When there were wrinkles, it was evaluated as x, and when it was absent, it was evaluated as ○. (Adhesiveness) A cut was made on the cured film to make 100 1 mm square pieces, and a cellophane tape was attached to the surface of the piece and immediately peeled off. At that time, when there was peeling of the cured film together with the cellophane tape, it was evaluated as x, and when it did not, it was evaluated as ○.

Examples 2 to 4 Except that the components such as the components were prepared as shown in Table 1,
A UV-curable resin composition was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the characteristics of the composition and the characteristics required for the color filter protective film.

Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 except that the components shown in Table 1 were used without using the components (B), (C) and (D) and a crosslinking agent. Table 1 shows the characteristics required for the color filter protective film.

[0035]

[Table 1]

From the results of the properties of the compositions shown in Table 1, it is clear that the coating film obtained from the resin composition of the present invention can be developed with an aqueous alkali solution.

[0037]

The coating film obtained from the resin composition of the present invention can be developed with an aqueous alkali solution, and the cured film has transparency, which is a necessary property of a color filter protective film,
It satisfies all of the heat resistance, chemical resistance, spatter resistance and adhesion, and it is clear that the resin is suitable for this application.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/027 501 G03F 7/027 501 7/038 503 7/038 503 G09F 9/00 330 G09F 9/00 330D (56) Reference Document JP-A-60-216307 (JP, A) JP-A-61-292604 (JP, A) JP-A-3-149271 (JP, A) JP-A-5-78453 (JP, A) JP-A-6-294 75108 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/20-59/38 C08G 59/42 C09D 133/06-133/12 C09D 163/00 G02B 5/20 G03F 7/027 G03F 7/038 G03F 9/00

Claims (3)

(57) [Claims] 1. An ultraviolet curable resin composition comprising the following four components (A), (B), (C) and (D). (A) General formula (I) And a structural unit represented by the general formula (II): An epoxy group-containing (meth) having a structural unit represented by the following as a main structural unit, and having an intrinsic viscosity at 30 ° C. of 0.05 to 1 in diethylene glycol dimethyl ether:
Acrylic copolymer, (B) intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether is 0.0
(C) a monomer having a (meth) acrylic group, which is 5-1 and contains at least one of a carboxylic acid group and a polycarboxylic anhydride group;
(D) a photopolymerization initiator. (However, in the general formulas (I) and (II), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and m and n each independently represent an integer of 1 to 4) .) 2. Component (A) is a copolymer containing glycidyl methacrylate and hydroxyl methacrylate as main components, and component (B) is methyl methacrylate, methacrylic acid and maleic anhydride, methyl methacrylate. The UV-curable resin composition according to claim 1, wherein the resin composition is a copolymer containing methacrylic acid or methyl methacrylate and maleic anhydride as main components. 3. An ultraviolet curing resin composition containing the following four components (A), (B), (C) and (D) is applied to a substrate, prebaked if necessary, and irradiated with ultraviolet light. A color filter protective film obtained by etching and post-baking as necessary. (A) General formula (I) And a structural unit represented by the general formula (II): An epoxy group-containing (meth) having a structural unit represented by the following as a main structural unit, and having an intrinsic viscosity at 30 ° C. of 0.05 to 1 in diethylene glycol dimethyl ether:
Acrylic copolymer, (B) intrinsic viscosity at 30 ° C. in diethylene glycol dimethyl ether is 0.0
(C) a monomer having a (meth) acrylic group, which is 5-1 and contains at least one of a carboxylic acid group and a polycarboxylic anhydride group;
(D) a photopolymerization initiator. (However, in the general formulas (I) and (II), R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and m and n each independently represent an integer of 1 to 4) .)