JPH06100663A - Ultraviolet-curable resin composition and color-filter-protecting film produced therefrom - Google Patents

Abstract

PURPOSE:To obtain the compsn. which gives a coating film etchable with a low-toxicity developing soln. by compounding a specific epoxidized (meth)acrylic copolymer, a (meth)acrylic polymer, a (meth)acrylic monomer, and a photopolymn. initiator. CONSTITUTION:The compsn. comprises an epoxidized (meth)acrylic copolymer having structural units of formulae I and II wherein R<1> and R<2> are each independently H or a 1-5C hydrocarbon group; and m and n are each independently an integer of 1-4 as the main structural units and an intrinsic viscosity (in diethylene glycol dimethyl ether at 30 deg.C) of 0.05-1, a (meth)acrylic polymer having an intrinsic viscosity (in diethylene glycol dimethyl ether at 30 deg.C) of 0.05-1 and at least either carboxyl or polycarboxylic acid anhydride group, a (meth)acrylic monomer, and a photopolymn. initiator.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Transparency, adhesion, spatter resistance, coating property, heat resistance and the like are required as properties required for a resin for a color filter protective film. JP-A-60-216307), epoxy resin (for example, JP 4-97102 A), polyimide resin (for example, JP 1-22292 A).
No. 03) has been studied. Among these resins, (meth) acrylic resin is the most transparent,
It has been widely considered. 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 polyvalent carboxylic acid anhydride is mixed with an epoxy group-containing polymer and the mixture is crosslinked by heating to form a cured film. But,
Mixing a high molecular weight compound with a strong low molecular weight compound,
Since the reaction is carried out, unreacted polycarboxylic acid anhydride remains to form a heterogeneous layer, resulting in deterioration of physical properties, which is not preferable.

On the other hand, the polyimide resin is inherently inferior in transparency and has a drawback that high temperature heating is required for curing the film. In addition, it is necessary to remove the protective film around the color filter substrate in the process, and this is currently done using a resist. Recently, JP-A-4-153
No. 274 and Japanese Patent Laid-Open No. 4-164970,
A color filter protective film using an ultraviolet effect resin composition is disclosed. However, in any of these, the developing solution is an organic solvent having a strong toxicity, which is not preferable in operation.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to carry out pre-baking, and then irradiate it with ultraviolet rays through a mask to perform development by etching with a developing solution having low toxicity instead of an organic solvent having high toxicity. 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 has no deterioration in physical properties and is excellent in transparency, heat resistance, chemical resistance, spatter resistance and adhesion.

[0005]

As a result of various investigations, the present inventors have found that the use of a specific UV-curable resin composition satisfies the necessary characteristics of the color filter protective film and has a low alkalinity with low toxicity. The inventors have found that etching can be performed with an aqueous solution, and completed the present invention. That is,

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

[Chemical 5] And the general formula (II)

[Chemical 6] An epoxy group-containing (meth) that has a structural unit represented by as a main structural unit and has an intrinsic viscosity of 0.05 to 1 at 30 ° C. in diethylene glycol dimethyl ether.
The intrinsic viscosity at 30 ° C. in an acrylic copolymer (B) diethylene glycol dimethyl ether is 0.0
5-1 and a (meth) acrylic polymer containing at least one of a carboxylic acid group and a polycarboxylic acid anhydride group, (C) a monomer having a (meth) acrylic group,
(D) A photopolymerization initiator. (However, in the general formulas (I) and (II), R ¹ and R ² are 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-mentioned four components (A), (B), (C) and (D) onto a substrate, and if necessary prebaking. However, it is obtained by irradiating ultraviolet rays, etching if necessary, and post-baking if necessary.

In a preferred embodiment of the ultraviolet curable resin composition of the present invention, the component (A) may be glycidyl methacrylate (hereinafter sometimes abbreviated as GMA) and 2-hydroxyl methacrylate (hereinafter simply referred to as HEMA). A) as a main component, and the component (B) is methyl methacrylate (hereinafter sometimes abbreviated as MMA), methacrylic acid (hereinafter sometimes abbreviated as MA), and maleic anhydride. (Hereinafter sometimes 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 these components and a (C) meta (acrylic) group,
The ultraviolet curable resin composition of the present invention can be produced by mixing (D) a photopolymerization initiator and, if necessary, an additive such as a coupling agent, or by dissolving them in an organic solvent as necessary.

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

[Chemical 7]

[Chemical 8] (However, in the general formulas (III) and (IV), R ¹ and R ² are 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. )
It can be obtained by copolymerizing the monomer represented by Of these, the combination of glycidyl methacrylate and 2-hydroxyl ethyl methacrylate is most preferred. It can be easily obtained by polymerizing these monomers in the presence of a radical polymerization initiator. In this case, in order to improve the properties such as solubility or adhesion of the obtained polymer, other (meth) acrylic monomer or a small amount of vinyl monomer may be added for copolymerization.

Other (meth) acrylic monomers include methyl acrylate, ethyl acrylate, and acrylic acid n-
Butyl, 2-ethylhexyl acrylate, acrylic acid 2
-Ethoxyethyl, acrylic acid esters such as 2-hydroxyethyl acrylate, or methyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Examples thereof include methacrylic acid esters such as benzyl and 2-hydroxypropyl methacrylate.
Examples of 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 monomer. 0 to 30% by weight and 0 to 30% by weight of vinyl monomer. It is also possible to add a monomer having a carboxylic acid group or a polyvalent carboxylic acid anhydride group described below within 10% by weight as a part of other (meth) acrylic monomer or vinyl monomer. The component (A) can be easily obtained by carrying out a polymerization reaction of the above monomer in a reaction solvent in the presence of a radical polymerization initiator by a conventional method. The degree of polymerization 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 color filter protective film will deteriorate, and above this range, the solubility in the solvent will decrease, and the selection range of the solvent will be undesirably limited.

As the reaction solvent used here, ketones such as metal ethyl ketone, methyl isobutyl ketone and methyl cyclohexanone, ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Alternatively, esters such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate can be exemplified.

Examples of radical polymerization initiators include organic peroxides such as benzoyl peroxide, t-butyl peroxybenzoate and lauroyl peroxide, and azobisisobutyronitrile.

Component (B) is a component (B) containing at least one of a carboxylic acid group and a polycarboxylic anhydride group (meta).
The acrylic polymer is 10 to 70% by weight of a monomer having a carboxylic acid group or a polycarboxylic acid anhydride group, 30 to 90% by weight of the other (meth) acrylic monomer described above,
It can be obtained by mixing 30% by weight or less of another vinyl-based monomer, if necessary, and polymerizing it by a conventional method using the above-mentioned solvent and radical polymerization initiator.

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

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

Examples of the (meth) acryl group-containing monomer which is 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-hydroxyl ethyl acrylate, 2-hydroxyethyl Methacrylate,
2-hydroxypropyl acrylate, 2-hydroxyl propyl 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 diacrylate, 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.,

Examples of the photopolymerization initiator as the component (D) include the following compounds. 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-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether,
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, camphorquinone, benzanthrone, 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-t-butylcyclohexanone, ethyl-p- (N, N-dimethylamino) bezozoate and the like.

When these components (A), (B), (C) and (D) are mixed, any combination of compounds which dissolve in each other can be used as it is as the composition of the present invention. However, in general, in order to improve the coating property, it is preferable to dissolve these compounds in an organic solvent and use them as a coating liquid. As the organic solvent, the above reaction solvent can be used in any mixing ratio. The mixing ratio of both components (A) and (B) is such that the epoxy group in the component (A) and the carboxylic acid group in the component (B) (calculated as two carboxylic acid anhydride groups are two carboxylic acids) are nearly equivalent. Is preferable, but not so strict. The component (C) is 20 to 300 per 100 parts by weight of the total amount of the components (A) and (B).
Part by weight is preferable, and 50 to 200 parts by weight is particularly preferable. If it is less than this range, curing by ultraviolet rays is insufficient, and if it is more than this range, the physical properties of the cured film deteriorate. The component (D) is 1 to 50 parts by weight, and 5 to 100 parts by weight of the component (C).
20 parts by weight are particularly preferred. If it is less than this range, curing by ultraviolet rays is insufficient, and if it is more than this range, the stability of the coating solution over time is deteriorated, which is not preferable.

In addition to these components, if necessary, a cross-linking aid, a coupling agent and a thermal polymerization inhibitor of 20% by weight or less of the polymer can be added. A compound containing a hydroxyl group, a carboxyl group and an amino group is used as the crosslinking aid. Silane, aluminum, and titanate compounds are used as coupling agents for improving the adhesion to the substrate. Specific examples thereof include silane-based compounds such as 3-aminopropyltriethoxysilane, 3-aminophenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and acetoalkoxyaluminumdiamine. Examples thereof 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,
A coating film is formed by coating on a color filter patterned on a glass substrate by a known method such as dipping or spray printing. Most of the solvent in the coating film is removed by pre-baking the coating film at a temperature of 30 to 150 ° C. using a heating means such as an electric furnace or a hot plate. A negative mask is placed on this coating film and irradiated with actinic rays.
Examples of actinic rays include X-rays, electron rays, ultraviolet rays, and visible rays, and ultraviolet rays or visible rays are particularly preferable. Then, if necessary, the unexposed portion is dissolved and removed by a developing solution to obtain a relief pattern.
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, the rinse can be performed in a non-solvent. Post-baking can also be carried out at a temperature of 150 to 300 ° C., preferably 180 to 250 ° C. by the above heating means in order to accelerate the curing of the polymer of the relief pattern formed by development.

Further, the ultraviolet-curable resin composition of the present invention is prepared by a known method such as spin coating, dipping or spray printing on a silicon wafer, a metal plate, a plastic plate,
It is possible to form a coating film by coating on a substrate such as, and to form a cured film by pre-baking and post-baking in the same way as the formation of the color filter protective film described above, for flattening the substrate surface of electrical parts, etc. Can be used.

The present invention will be specifically described below with reference to synthetic examples and examples, but the present invention is not limited to these synthetic 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 Dissolve 2 parts of nitrile (hereinafter abbreviated as AIBN) in 300 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) 60
After 4 hours at 80 ° C and 12 hours at 80 ° C,
The reaction solution was transferred to a large amount of n-heptane to precipitate the polymer, which was dried under reduced pressure for one day in a filtered vacuum dryer at 50 ° C. to obtain a copolymer of component (A) (referred to as AI). It was The intrinsic viscosity of this polymer measured in a solution of diethylene glycol dimethyl ether (hereinafter abbreviated as DIG) at 30 ° C. was 0.079.

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

Synthesis of (meth) acrylic polymer [component (B)] containing at least one of a carboxylic acid group and a polycarboxylic acid anhydride group: (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 (BI) of 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) as a component (B) having an intrinsic viscosity of 0.14.

Example 1 41 parts of copolymer (AI) as component (A), (B)
59 parts of polymer (BI) as a component, 100 parts of pentaerythritol triacrylate as a component (C),
As the component (D), 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1 was added as 7
Part, ethyl-p- (N, N-dimethylamino) benzoate 2 parts, isopropylthioxanthone 2 parts and silane coupling agent [manufactured by Chisso Corporation: S510] 5
Part of the solvent is diethylene glycol dimethyl ether (D
IG) to 300 parts to prepare an ultraviolet curable resin composition.

These resin compositions were coated on a glass plate and prebaked for 20 minutes on a hot plate kept at 70 ° C. to form a coating film. These coating films were exposed through a mask with an ultra-high pressure mercury lamp (20 mw / cm ² ) for 20 seconds. 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 from this, after the entire surface was exposed under the same conditions, post-baking was performed without immersing in a developing solution to form a coating film.

The film obtained by immersing in the post-exposure developing solution and the film obtained without immersing in the post-exposure developing solution, that is, each film thickness depending on the presence or absence of development were measured, and the residual film rate was calculated by the following formula. ,
The results are shown in Table 1. Residual film rate = [film thickness of exposed area (with development) / film thickness of exposed area (without development)] × 100 Next, transparency, adhesion to substrate, and chemical resistance, which are characteristics required as a color filter protective film. The heat resistance and the 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. The results are shown in Table 1.

The method of measuring the properties required for the color filter protective film is shown 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) Shows transparency after heat treatment at 250 ° C. (Chemical resistance) 3 at room temperature in N-methyl-2-pyrrolidone solution
It was fixed vertically for 0 minutes and immersed, and it was judged whether or not the boundary line between the part submerged in the liquid and the part not so submerged could be visually distinguished. When the boundary line was visible, it was marked with X, and when it was not visible, it was marked with ◯. (Sputter resistance) When an ITO film (indium-tin oxide) having a film thickness of 200 angstrom was formed on a cured film at 200 ° C. by sputtering, it was examined whether or not wrinkles were generated in the film. When there were wrinkles, the result was x, and when there were no wrinkles, the result was ○. (Adhesiveness) A cut was made on the cured film to make 100 square pieces of 1 mm each, and cellophane tape was attached to the surface and immediately peeled off. At that time, when there was peeling of the cured film together with the cellophane tape, it was marked with x, and when it was not peeled, it was marked with o.

Examples 2 to 4 Except that the ingredients are blended as shown in Table 1,
An ultraviolet 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 using a crosslinking agent. Table 1 shows the properties required for the color filter protective film.

[0035]

[Table 1]

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

[0037]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08G 59/20 NHW 8416-4J 59/40 NKF 8416-4J C09D 4/00 PDR 7921-4J G02B 5 / 20 101 7348-2K G03F 7/027 501 7/038 503 G09F 9/00 330 6447-5G

Claims (3)

[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) that has a structural unit represented by as a main structural unit and has an intrinsic viscosity of 0.05 to 1 at 30 ° C. in diethylene glycol dimethyl ether.
The intrinsic viscosity at 30 ° C. in an acrylic copolymer (B) diethylene glycol dimethyl ether is 0.0
5-1 and a (meth) acrylic polymer containing at least one of a carboxylic acid group and a polycarboxylic acid anhydride group, (C) a monomer having a (meth) acrylic group,
(D) A photopolymerization initiator. (However, in the general formulas (I) and (II), R ¹ and R ² are 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. The component (A) is a copolymer containing glycidyl methacrylate and hydroxyl methacrylate as main components, and the component (B) is methyl methacrylate, methacrylic acid and maleic anhydride, methyl methacrylate. 2. The ultraviolet curable resin composition according to claim 1, which is a copolymer containing methacrylic acid or methyl methacrylate and maleic anhydride as main components. 3. An ultraviolet curable resin composition containing the following four components (A), (B), (C) and (D) is applied to a substrate, prebaked if necessary, and irradiated with ultraviolet rays, A color filter protective film obtained by etching if necessary and post-baking if necessary. (A) General formula (I) And a structural unit represented by the general formula (II): An epoxy group-containing (meth) that has a structural unit represented by as a main structural unit and has an intrinsic viscosity of 0.05 to 1 at 30 ° C. in diethylene glycol dimethyl ether.
The intrinsic viscosity at 30 ° C. in an acrylic copolymer (B) diethylene glycol dimethyl ether is 0.0
5-1 and a (meth) acrylic polymer containing at least one of a carboxylic acid group and a polycarboxylic acid anhydride group, (C) a monomer having a (meth) acrylic group,
(D) A photopolymerization initiator. (However, in the general formulas (I) and (II), R ¹ and R ² are 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. .)