JP3151975B2 - Heat-resistant radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant radiation-sensitive resin composition suitable as a protective film forming material for optical devices.

[0002]

2. Description of the Related Art An optical device such as a display device or a solid-state image pickup device is immersed in, for example, a solvent, an acid, or an alkaline solution during a manufacturing process, or is sputtered when a wiring electrode layer is formed. They may be subjected to severe processing such as local high-temperature heating. For this reason, these elements may be provided with a protective film in order to prevent deterioration during manufacturing.

The protective film is required to have various properties that can withstand the above-mentioned treatments. Specifically, the protective film must have excellent adhesion to a substrate or a lower layer, must be smooth and tough, and must have excellent transparency. Excellent, heat resistance and light resistance to prevent deterioration such as coloring, yellowing, whitening, etc. over a long period, and chemical resistance such as water resistance, solvent resistance, acid resistance and alkali resistance It is required to have excellent properties.

In order to satisfy such a demand, the present applicant has previously proposed a thermosetting composition containing an epoxy copolymer in Japanese Patent Application Laid-Open No. Sho 60-217230. It is widely used to form a surface protection film for a liquid crystal display device or a color solid-state imaging device, and a protection flattening film for the device surface.

[0005]

The above-mentioned protective film is usually formed by coating a material for the protective film on a substrate by spin coating, pre-baking to form a coating film, and then curing the coating film. It is formed by this.

In such a protective film, a protective film capable of flattening a step of a color filter as a base substrate is generally desired. In particular, when manufacturing an STN mode liquid crystal panel, the precision of bonding the color filter substrate and the opposing substrate must be very strictly performed, and it is essential to make the cell gap between the substrates uniform. I have. If the protective film cannot flatten the steps of the color filter, which is the underlying substrate, the accuracy of cell gap adjustment at the time of laminating the substrates will be reduced and the cell gap adjustment operation will be complicated, resulting in a display device manufacturing yield. Will decrease.

Conventionally, the surface of the color filter has been previously flattened to some extent with a low-viscosity, high-concentration material, and then a protective film material has been applied. The production is complicated and the cost is high.

Further, if a protective film is formed by a spin coating method or the like using a conventional material for a protective film, the film thickness at the peripheral portion of the substrate becomes larger than the film thickness at other portions. The accuracy of the cell gap adjustment is lowered and the adjustment work becomes complicated.

In recent years, as a mounting method of a liquid crystal display panel, COG (Ch.
Although the on-glass method has attracted attention, in order to manufacture a color liquid crystal display panel using the COG method, it is necessary to provide a protective film so that the protective film does not remain on portions other than the color filters.

In order to provide a protective film so that the protective film does not remain on portions other than the color filter, conventionally, for example, a resist excellent in dry etching resistance is applied on the coating film formed as described above, The resist is exposed and developed into an appropriate pattern and then dry-etched to remove unnecessary portions of the coating film other than the color filters.

However, in the dry etching method,
The resist used after the dry etching had to be removed, so that the process was complicated and there was a possibility that the dry etching might cause a defect on the display element.

Therefore, while satisfying the above-mentioned various characteristics required for the protective film, it is possible to flatten the steps of the color filter which is the underlying substrate, and furthermore, unnecessary portions (exposure and development) by exposure and development. For example, the appearance of a heat-resistant radiation-sensitive resin composition capable of easily removing a protective film on a portion other than a color filter) has been desired.

[0013]

Means for Solving the Problems The heat-resistant radiation-sensitive resin composition according to the present invention comprises: (A) (a-1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride; A copolymer of a radical polymerizable compound having an epoxy group, (a-3) a monoolefinic unsaturated compound, and (a-4) a conjugated diolefinic unsaturated compound, and [B] an ethylenically unsaturated compound. A polymerizable compound having a heavy bond, [C] a compound having at least two epoxy groups, and [D] a photopolymerization initiator.

The heat-resistant radiation-sensitive resin composition according to the present invention is excellent in various properties required for a protective film for an optical device, such as mechanical properties, chemical resistance and transparency, and has a stepped surface of an underlying substrate (color filter). Can be formed as a protective film capable of flattening.

Further, the heat-resistant radiation-sensitive resin composition according to the present invention can easily form a protective film of a predetermined pattern by removing unnecessary portions by exposure and development.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the heat-resistant radiation-sensitive resin composition according to the present invention will be described. [A] Copolymer The copolymer [A] used in the present invention comprises (a-1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride;
-2) a radical polymerizable compound having an epoxy group, and (a-
3) A copolymer of a monoolefinically unsaturated compound and (a-4) a conjugated diolefinically unsaturated compound.

Specific examples of such unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a-1) include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid. Preferred are dicarboxylic acids such as acid, citraconic acid, mesaconic acid, and itaconic acid, and anhydrides of these dicarboxylic acids.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used. As the radical polymerizable compound (a-2) having an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate , 3,4-epoxybutyl acrylate, methacrylic acid-
Examples include 3,4-epoxybutyl, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, and 6,7-epoxyheptyl α-ethyl acrylate.

Among these, glycidyl methacrylate,
Methacrylic acid-6,7-epoxyheptyl is preferably used. These may be used alone or in combination as monoolefinically unsaturated compounds (a-3), for example, methyl methacrylate, ethyl methacrylate, n-
Butyl methacrylate, sec-butyl methacrylate, t-
Alkyl methacrylate such as butyl methacrylate, methyl acrylate, alkyl acrylate such as isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate,
Cyclic alkyl esters of methacrylic acid such as isobornyl methacrylate, cycloalkyl acrylates such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentaoxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, benzyl Aryl methacrylates such as methacrylate, aryl acrylates such as phenyl acrylate and benzyl acrylate, dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like Hydroxyalkyl ester, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene Emissions, vinyl toluene, p- methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Of these, styrene, dicyclopentanyl methacrylate, p-methoxystyrene and 2-methylcyclohexyl acrylate are preferred. These may be used alone or in combination.

The conjugated diolefin unsaturated compound (a-
Examples of 4) include 1,3-butadiene, isoprene, and 2,3-dimethylbutadiene. These may be used alone or in combination.

Among the copolymers [A] comprising the constitutional units derived from the above components, copolymers comprising the constitutional units represented by the following formulas (1) to (6) are preferable. (1), (3), (4), (5), a copolymer composed of structural units represented by (6) and formulas (2), (3), (4), (5), (5) 6)
A copolymer comprising a structural unit represented by

Formula (1) is a structural unit derived from an unsaturated carboxylic acid, formula (2) is a structural unit derived from an unsaturated carboxylic anhydride (a-1), and formula (3) is It is a structural unit derived from a radical polymerizable compound (a-2) having an epoxy group, and the formulas (4) and (5) are structural units derived from the monoolefinically unsaturated compound (a-3). Yes, Equation (6)
Is a structural unit derived from the conjugated diolefin-based unsaturated compound (a-4).

[0024]

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(In the formula, R ¹ is a hydrogen atom or a lower alkyl group.)

[0026]

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(In the formula, R ¹ is a hydrogen atom or a lower alkyl group, and n is an integer of 1 to 10.)

[0028]

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(In the formula, R ¹ is a hydrogen atom or a lower alkyl group.)

[0030]

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Wherein R ¹ is a hydrogen atom or a lower alkyl group; R ² is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms; The group may have a substituent.)

[0032]

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(In the formula, R ³ is a hydrogen atom or a methyl group.) The copolymer [A] used in the present invention may be an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride ( The structural unit derived from a-1) is contained preferably in an amount of 5 to 40% by weight, particularly preferably 10 to 30% by weight.

The copolymer [A] used in the present invention preferably contains 10 to 70% by weight, more preferably 20 to 70% by weight of a structural unit derived from the radical polymerizable compound (a-2) having an epoxy group. It contains 50% by weight.

The copolymer [A] used in the present invention contains the structural unit derived from the monoolefinically unsaturated compound (a-3) in an amount of preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight. %.

The copolymer [A] used in the present invention preferably contains 3 to 30% by weight, more preferably 5 to 15% by weight of a structural unit derived from the conjugated diolefin unsaturated compound (a-4). % By weight.

The copolymer [A] composed of the above structural units has appropriate solubility in an aqueous alkali solution, and the heat-resistant radiation-sensitive resin composition containing the copolymer [A] is as follows: A protective film having a predetermined pattern can be easily formed without developing residue during film development and without film thinning.

The structural unit derived from the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride (a-1) is 5 units.
Copolymers that are less than weight percent are less soluble in aqueous alkaline solutions. Monoolefinically unsaturated compounds (a-3)
The copolymer derived from the conjugated diolefin unsaturated compound (a-4) in an amount exceeding 70% by weight or a copolymer derived from the conjugated diolefin unsaturated compound (a-4) in an amount exceeding 30% by weight. Has a reduced solubility in an aqueous alkali solution.
On the other hand, a copolymer containing an unsaturated carboxylic acid or an unsaturated carboxylic anhydride (a-1) in an amount exceeding 40% by weight tends to have too high a solubility in an aqueous alkali solution.

A protective film having excellent heat resistance can be formed from the heat-resistant radiation-sensitive resin composition containing the copolymer [A] comprising the above structural units. In such a copolymer, 10% by weight of a structural unit derived from the radical polymerizable compound (a-2) having an epoxy group is contained.
Less than or monoolefinically unsaturated compound (a-3)
When the amount of the structural unit derived from styrene exceeds 70% by weight, or the amount of the structural unit derived from the conjugated diolefin-based unsaturated compound (a-4) exceeds 30% by weight, the heat-resistant composition containing this copolymer is used. The heat resistance of the protective film obtained from the radiation resin composition tends to decrease.

When the heat-sensitive radiation-sensitive resin composition containing the copolymer [A] is applied on a color filter having a step on the surface, the step can be flattened. .

As described above, the copolymer [A] used in the present invention has a carboxylic acid group or a carboxylic anhydride group and an epoxy group, is soluble in an aqueous alkali solution, and has a special property. It can be easily cured by heating without using a curing agent.

Heretofore, a radiation-sensitive resin composition comprising an epoxy group-containing polymer and a carboxylic acid group-containing compound or a carboxylic anhydride-containing polymer has been known. However, in this radiation-sensitive resin composition, There are problems that the compatibility of each component is inferior, the storage stability of the composition is inferior, and the protective film obtained from this composition tends to have a rough surface. A modified polymer containing an epoxy group and a carboxyl group, which is obtained by modifying an epoxy group-containing polymer with a carboxylic acid (carboxylic anhydride), is also known. There is a problem that a denaturation step is required and it is difficult to adjust the amount of denaturation.

When a copolymer is produced from only an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (a-1) and a radical polymerizable compound (a-2) having an epoxy group, an epoxy In some cases, the group reacts with the carboxylic acid group and crosslinks to gel the polymerization system.

On the other hand, the copolymer [A] used in the present invention comprises an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (a-1) and a radical polymerizable compound (a- In addition to 2), the monoolefinically unsaturated compound (a-3) and the conjugated diolefinically unsaturated compound (a-4) are copolymerized, and the epoxy group reacts with the carboxylic acid group. , Cross-linking and gelation are suppressed,
Also, it has excellent storage stability.

The copolymer [A] can be obtained by using (a-1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride as described above, and (a-2) a radical polymerizable compound having an epoxy group. , (A-3) monoolefinically unsaturated compound and (a
-4) It can be obtained by radical polymerization of a conjugated diolefin-based unsaturated compound in a solvent in the presence of a catalyst (polymerization initiator).

Examples of the solvent used here include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, cellosolve esters such as methyl cellosolve acetate, aromatic hydrocarbons, and the like.
Examples include ketones and esters.

As the catalyst, those generally known as radical polymerization initiators can be used. For example, 2,2 ′
-Azobisisobutyronitrile, 2,2'-azobis- (2,4-
Azo compounds such as dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- (T-
Organic peroxides such as butylperoxy) cyclohexane and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox type initiator. Copolymer [A] as described above
Is not particularly limited as long as the solution of the composition of the present invention can be uniformly applied.

[B] Having an ethylenically unsaturated double bond
Polymerizable Compound As the polymerizable compound [B] having an ethylenically unsaturated double bond used in the present invention, specifically, a monofunctional or polyfunctional (meth) acrylate is preferably exemplified.

Examples of the monofunctional (meth) acrylate include Aronix M-101, M-111 and M-111.
114 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARAD
TC-110S, TC-120S (Nippon Kayaku Co., Ltd.)
V-158, V-2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available).

Examples of the bifunctional (meth) acrylate include Aronix M-210, M-240 and M-240.
6200 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARA
DHDDA, HX-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), V260, V312, V335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available).

Examples of trifunctional or higher functional (meth) acrylates include, for example, Aronix M-309 and M-400.
M-405, M-450, M-7100, M-
8030, M-8060 (Toa Gosei Chemical Industry Co., Ltd.)
KAYARAD TMPTA, DPCA-2
0, -30, -60, and -120 (Nippon Kayaku Co., Ltd.)
V-295, -300, -360, -GP
T, -3PA, -400 (Osaka Organic Chemical Industry Co., Ltd.)
(Commercially available).

These are used alone or in combination. [C] Compound having at least two epoxy groups The compound [C] having at least two epoxy groups used in the present invention is not particularly limited as long as it has compatibility with other components forming the resin composition. It is preferably used without bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin And glycidyl methacrylate-containing resin compositions such as Optoma-SS (manufactured by Nippon Synthetic Rubber Co., Ltd.).

Among these, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are preferably used.

[D] Photopolymerization Initiator As the photopolymerization initiator [D] used in the present invention, a photoradical polymerization initiator or a photocationic polymerization initiator can be used.

In using these photopolymerization initiators, it is necessary to consider exposure conditions (whether in an oxygen atmosphere or in an oxygen-free atmosphere). Specifically, when the exposure is performed in an oxygen-free atmosphere, any general types of photoradical polymerization initiators and cationic photopolymerization initiators can be used.

As the radical photopolymerizing agent, for example,

Α-diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, 2,4-diethylthioxanthone and thioxanthone-4- Benzophenones such as sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2 , 2'-Dimethoxy-
2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1
Acetophenones such as-(4-morpholinophenyl) -butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl chloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-
Halogen compounds such as triazine, peroxides such as di-t-butyl peroxide and the like can be mentioned.

As the cationic photopolymerization initiator, commercially available products as shown below can be used. Diazonium salts such as Adeka Ultraset PP-33 (manufactured by Asahi Denka Kogyo KK), sulfonium salts such as OPTOMER SP-150 and 170 (manufactured by Asahi Denka Kogyo KK), IRGACURE26
1 (manufactured by CIBA-GEIGY (company)).

When exposure is performed in an oxygen atmosphere, radicals are deactivated (sensitivity is lowered) by oxygen in the photo-radical polymerization initiator, and the residual film ratio and hardness of the exposed portion cannot be sufficiently obtained. There are cases. When exposure is performed in such an oxygen atmosphere, all of the above-mentioned photo-cationic polymerization initiators (the photo-cationic polymerization initiator hardly deactivates active species by oxygen) and light Some of the radical polymerization initiators, for example, 2-methyl-
Acetophenones such as [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or phenacyl chloride; Halogen compounds such as tribromomethylphenylsulfone and tris (trichloromethyl) -s-triazine can be mentioned as preferred compounds.

It is also possible to achieve high sensitivity with little deactivation by oxygen by using these radical photopolymerization initiators and cationic photopolymerization initiators or photosensitizers in combination.

Heat-Resistant Radiation-Sensitive Resin Composition The heat-resistant radiation-sensitive resin composition according to the present invention comprises a polymer having an ethylenically unsaturated double bond based on 100 parts by weight of the copolymer [A]. Active compound [B], preferably 40 to 200 parts by weight, more preferably 80 to 150 parts by weight.
The compound [C] having at least two epoxy groups is preferably used in an amount of 30 to 200 parts by weight, more preferably 50 to 120 parts by weight, and the photopolymerization initiator [D] is used in an amount of 100 parts by weight. Is contained in an amount of 1.0 to 50 parts by weight, particularly preferably 5 to 30 parts by weight.

The protective film obtained from the heat-resistant radiation-sensitive resin composition having such a composition is excellent in various properties and can flatten a step of a color filter as a base substrate. It can be easily formed on a protective film of a predetermined pattern by exposure and development.

In particular, the heat-sensitive radiation-sensitive resin composition containing the polymerizable compound [B] having an ethylenically unsaturated double bond in the above-described amount does not decrease the radiation sensitivity even in an oxygen atmosphere. . Further, the polymerizable compound [B] having an ethylenically unsaturated double bond in the above-described amount has excellent compatibility with other components, and the heat-resistant radiation-sensitive resin composition containing the compound has a rough surface. Protective films without defects can be formed.

In the heat-resistant radiation-sensitive resin composition according to the present invention containing the compound [C] having at least two epoxy groups in the amount described above, the compatibility between the compound [C] and other components is reduced. The heat-resistant and radiation-sensitive resin composition which is excellent, does not deteriorate the film-forming property, and contains the compound [C] in such an amount can flatten the steps of the color filter as the base substrate. Is a possible protective material.

Further, in the heat-resistant radiation-sensitive resin composition according to the present invention containing the photopolymerization initiator [D] in the above amount, the radiation sensitivity is reduced (radicals are deactivated) by oxygen. Further, the heat-sensitive radiation-sensitive resin composition does not have a strong coloration and can be suitably used for display elements such as LCDs.

The heat-resistant radiation-sensitive resin composition according to the present invention can be easily prepared by uniformly mixing the above components. Such a heat-resistant radiation-sensitive resin composition is usually used in the form of a solution after being dissolved in an appropriate solvent. For example, a solution of the copolymer [A], an ethylenic compound [B], a photopolymerization initiator [D], an epoxy compound [C], and other compounding agents are mixed at a predetermined ratio immediately before use to obtain a solution. A heat-resistant radiation-sensitive resin composition in a state can be prepared.

Examples of such a solvent include [A],
[B], [C] and [D] which can be uniformly dissolved and do not react with each component are used. Specifically, for example, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and ethylene glycol alkyl ethers such as methyl cellosolve acetate and ethyl cellosolve acetate Acetates, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycols such as diethylene glycol dimethyl ether,
Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone; cyclohexanone; 4-hydroxy-4-methyl-
Ketones such as 2-pentanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyate, 2-hydroxy-3
Esters such as methyl-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate.

Further, together with these, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl Ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, High boiling solvents such as phenyl cellosolve acetate can also be used.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol alkyl ethers such as ethyl cellosolve acetate are preferred because of their solubility, reactivity with each component, and ease of forming a coating film. Acetates, esters such as ethyl 2-hydroxypropionate, and diethylene glycols such as diethylene glycol monomethyl ether are preferably used.

The heat-resistant and radiation-sensitive resin composition according to the present invention may contain components other than those described above, if necessary, as long as the object of the present invention is not impaired. Such other components include surfactants.

As the surfactant, for example, BM-1
000, BM-1100 (manufactured by BM Chemie), Megafac F142D, F172, F173, F183
(Manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-
135, FC-170C, FC-430, FC-
431 (Sumitomo 3M Limited), Surflon S-1
12, S-113, S-131, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA,
190, -193, SZ-6032, SF-8428
A commercially available fluorine-based surfactant such as (Toray Silicone Co., Ltd.) can be used.

These surfactants are copolymers [A] 10
It is preferably used in an amount of 5 parts by weight or less, more preferably 0.01 to 2 parts by weight, based on 0 parts by weight. Further, an adhesion aid may be used to improve the adhesion to the substrate. As such an adhesion aid, a functional silane coupling agent is preferable.

Here, the functional silane coupling agent is
Examples include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group, and more specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, and vinyltriacetoxy. Examples include silane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

These adhesion aids can be used alone or in combination of two or more. The adhesion aid is used in an amount of preferably 20 parts by weight or less, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the copolymer [A].

The composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm. Formation of Protective Film When the heat-resistant and radiation-sensitive resin composition according to the present invention is applied to the surface of a substrate and the solvent is removed by heating, a coating film can be formed. The method of applying the heat-resistant radiation-sensitive resin composition to the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method, and a spin coating method can be employed.

Next, this coating film is heated (prebaked). The heating conditions vary depending on the type of each component, the mixing ratio, and the like, but are usually at 70 to 90 ° C. for about 5 to 15 minutes. Next, the prebaked coating film is irradiated with ultraviolet rays or the like via a mask having a predetermined pattern, and then developed with a developer to remove unnecessary portions to form a predetermined pattern.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine,
Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-
Aqueous solutions of alkalis such as diazabicyclo [5,4,0] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonane can be used.

In addition, methanol,
An aqueous solution to which a suitable amount of a water-soluble organic solvent such as ethanol or a surfactant has been added can also be used as the developer.
The development time is usually from 30 to 180 seconds, and the development method may be any of a puddle method and a dipping method.
After the development, washing with running water is performed for 30 to 90 seconds, and air drying with compressed air or compressed nitrogen removes unnecessary portions to form a pattern. Thereafter, the pattern is formed by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 30 to
By heat treatment for 90 minutes, heat resistance, transparency,
A protective film excellent in hardness and the like can be obtained.

[0080]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

In the examples, unless otherwise specified,% indicates% by weight.

[0082]

Synthesis Example 1 After a flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 22.5 g of styrene, 45.0 g of methacrylic acid, 45.0 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate, and 22.5 g of 1,3-butadiene were charged, followed by gentle stirring. Set the solution temperature to 8
After raising the temperature to 0 ° C. and maintaining this temperature for 5 hours, 90.degree.
The polymerization was terminated by heating at 0 ° C. for 1 hour.

Thereafter, the reaction product was dropped into a large amount of methanol to solidify the reaction product. This coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of methanol. After performing the re-dissolution-coagulation operation a total of three times, the obtained coagulated product was vacuum-dried at 60 ° C. for 48 hours to obtain a target copolymer. After this, the solid content concentration becomes 2
A copolymer solution was prepared using diethylene glycol dimethyl ether so as to be 5% by weight.

[0084]

Synthesis Example 2 After a flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved was charged. It is. Subsequently, 11.25 g of styrene and 3 of methacrylic acid were added.
3.75 g, dicyclopentanyl methacrylate
25 g, glycidyl methacrylate 101.25 g and
After charging 22.5 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and after maintaining this temperature for 5 hours, the solution was heated at 90 ° C. for 1 hour to terminate the polymerization.

Thereafter, a copolymer was obtained in the same manner as in Synthesis Example 1.

[0086]

Synthesis Example 3 After a flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 12.37 g of styrene, 49.5 g of methacrylic acid, 56.25 g of dicyclopentanyl methacrylate, 90.0 g of glycidyl methacrylate and 16.8 of 1,3-butadiene were used.
After charging 8 g, gentle stirring was started. After raising the temperature of the solution to 80 ° C. and maintaining this temperature for 5 hours,
The polymerization was terminated by heating at 90 ° C. for 1 hour.

Thereafter, a copolymer was obtained in the same manner as in Synthesis Example 1.

[0088]

[Synthesis Example 4] After replacing the flask equipped with a dry ice / methanol reflux condenser with nitrogen, 459.0 g of a methyl 3-methoxypropionate solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. It is. Continue with styrene 2
After 2.5 g, 45.0 g of maleic anhydride, 67.5 g of dicyclopentanyl methacrylate, 67.5 g of glycidyl methacrylate, and 22.5 g of 1,3-butadiene, gentle stirring was started. The temperature of the solution was raised to 80 ° C., and after maintaining this temperature for 5 hours, the solution was heated at 90 ° C. for 1 hour to terminate the polymerization.

Thereafter, a copolymer was obtained in the same manner as in Synthesis Example 1.

[0090]

Synthesis Example 5 A flask equipped with a dry ice / methanol reflux condenser was purged with nitrogen, and then 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Continue p-
Methoxystyrene 22.5 g, methacrylic acid 45.0
g, 2-methylcyclohexyl acrylate 56.25
g, 90.0 g of 6,7-epoxyheptyl methacrylate and 11.25 g of 1,3-butadiene, and then stirring was started slowly. The temperature of the solution was raised to 80 ° C., and after maintaining this temperature for 5 hours, the solution was heated at 90 ° C. for 1 hour to terminate the polymerization.

Thereafter, a copolymer was obtained in the same manner as in Synthesis Example 1.

[0092]

Example 1 Preparation of Composition (1) 100 g of the copolymer solution obtained in Synthesis Example 1 (Copolymer 2
5 g) of diethylene glycol dimethyl ether13.
After dilution with 64 g, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butan-1-one (Irgac
ure369 (manufactured by CIBA-GEIGY) 4.0 g, Aronix M-400 (manufactured by Toa Gosei Chemical Industry Co., Ltd.) 25.0 g,
γ-glycidoxypropyltrimethoxysilane 1.25
g, Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.)
After dissolving 12.25 g, the solution was filtered through a Millipore filter having a pore size of 0.22 μm to prepare a composition solution (1).

(I) Formation of Coating Film The above composition solution (1) was coated on a SiO ₂ glass substrate using a spinner, and then prebaked on a hot plate at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm. Was formed.

(Ii) Removal of Unnecessary Portion by Exposure and Development Using a predetermined pattern mask on the coating film obtained in (i) above, an ultraviolet ray having a light intensity at 365 nm of 10 mJ / cm ² for 30 seconds. Irradiated. The exposure at this time was performed in an oxygen atmosphere (in air). Then, the film was developed with 0.14% by weight of tetramethylammonium hydroxide at 25 ° C. for 1 minute, and then rinsed with ultrapure water for 1 minute. By these operations,
Unnecessary parts can be removed, and 20 μm × 20 μm
Was able to be resolved.

(Iii) Curing of the coating film The coating film obtained in the above (ii) was cured on a hot plate for 20 minutes.
By heating at 0 ° C. for 20 minutes, the coating film was cured to give the protective film necessary properties.

(Iv) Evaluation of Transparency In the above (i), except that Corning 7059 (manufactured by Corning) was used instead of the SiO ₂ glass substrate.
A coating film was formed in the same manner as in (i). Next, the entire surface was exposed for 30 seconds, developed with an aqueous solution of tetramethylammonium hydroxide, and then rinsed with ultrapure water for 1 minute. Then, it was heated at 200 ° C. for 20 minutes on a hot plate. The transmittance of the obtained substrate was measured at 400 to 800 nm using a spectrophotometer (150-20 type double beam (Hitachi, Ltd.)). At this time, the case where the minimum transmittance exceeds 95% is Δ, the case where the minimum transmittance is 90 to 95% is Δ, and the case where the minimum transmittance is less than 90% is ×.
And

Table 1 shows the results. (v) Evaluation of heat resistance The substrate on which the pattern was formed in the above (iii) was heated for 1 hour using a hot plate at 250 ° C, and the film thickness before and after the heating was measured to evaluate the heat resistance. The case where the rate of change (remaining film ratio) exceeds 95% is marked with Δ, the case where it is 90 to 95% is marked with Δ, and the case where it is less than 90% is marked with ×.

Table 1 shows the results. (vi) Evaluation of heat discoloration resistance The substrate formed in the above (iv) was heated on a hot plate at 250 ° C. for 1 hour, and the heat resistance was evaluated by a change in transmittance before and after heating. At this time, the rate of change was less than 5%, the rate was 5 to 10%, and the rate of change exceeding 10% was rated x. The transmittance was determined in the same manner as in (iv) Evaluation of transparency.

Table 1 shows the results. (vii) Measurement of hardness Using the coating film formed in the above (iv), JIS K-540
0-1990 8.4.1 Pencil Scratch Test,
For evaluation, the pencil hardness was measured based on the scratches of the coating film, and the surface hardness was measured.

Table 1 shows the results. (viii) Evaluation of flatness Instead of the SiO ₂ glass substrate used in (i) above,
A coating film was formed in the same manner as in the above (iii) except that an SiO ₂ wafer having a step of 1.0 μm was used. Thereafter, the step of the substrate was measured using a stylus-type film thickness measuring instrument.

Table 1 shows the results.

[0102]

Example 2 A composition solution was prepared and filtered according to Example 1 using the copolymer solution obtained in Synthesis Example 2 in place of the copolymer solution obtained in Synthesis Example 1 and evaluated. did. 20% with 1.0% aqueous solution of tetramethylammonium hydroxide
A pattern of μm × 20 μm could be resolved.

Table 1 shows the results.

[0104]

Example 3 A composition solution was prepared and filtered according to Example 1 using the copolymer solution obtained in Synthesis Example 3 instead of the copolymer solution obtained in Synthesis Example 1, and evaluated. did. 2 with 0.14% aqueous solution of tetramethylammonium hydroxide
A pattern of 0 μm × 20 μm could be resolved.

Table 1 shows the results.

[0106]

Example 4 A composition solution was prepared and filtered according to Example 1 using the copolymer solution obtained in Synthesis Example 4 instead of the copolymer solution obtained in Synthesis Example 1, and evaluated. did. 20% with 1.2% aqueous solution of tetramethylammonium hydroxide
A pattern of μm × 20 μm could be resolved.

Table 1 shows the results.

[0108]

Example 5 A composition solution was prepared and filtered according to Example 1 using the copolymer solution obtained in Synthesis Example 5 in place of the copolymer solution obtained in Synthesis Example 1 and evaluated. did. 2 with 0.14% aqueous solution of tetramethylammonium hydroxide
A pattern of 0 μm × 20 μm could be resolved.

Table 1 shows the results.

[0110]

Example 6 A composition similar to that of Example 1 was obtained by using 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (Irgacure907) instead of Irgacure 369 used in Example 1. The solution was prepared, filtered and evaluated. Tetramethylammonium hydroxide 0.14%
A 20 μm × 20 μm pattern could be resolved with the aqueous solution.

The results are shown in Table 1.

[0112]

Example 7 Instead of Epicoat 828 used in Example 1, Epolite 100MF (manufactured by Kyoeisha Yushi Co., Ltd.)
, A composition solution was prepared, filtered and evaluated according to Example 1. Tetramethylammonium hydroxide 0.
A 20 μm × 20 μm pattern could be resolved with a 12% aqueous solution.

Table 1 shows the results.

[0114]

[Table 1]

[0115]

Example 8 Irgacure 369 used in Example 1
Instead of 5 g, Irgacure 3692.0 g and Irgacure 9
07 g, and the composition solution was prepared, filtered and evaluated according to Example 1. A 20 μm × 20 μm pattern could be resolved with a 0.14% aqueous solution of tetramethylammonium hydroxide.

Table 2 shows the results.

[0117]

Example 9 Irgacure 369 used in Example 1
Instead of 5 g, (1-6- [eta] -cumene) ([eta] -cyclopentadienyl) iron (1+) hexafluorophosphate (1-) (Ir
gacure 261 (CIBA-GEIGY)) 4.0 g,
A composition solution was prepared, filtered and evaluated according to Example 1.
A pattern of 20 μm × 20 μm could be resolved with a 0.20% aqueous solution of tetramethylammonium hydroxide.

Table 2 shows the results.

[0119]

Example 10 Irgacure 369 used in Example 1
Instead of 7.5 g, tris (trichloromethyl) -s-
Using 2.5 g of triazine, a composition solution was prepared, filtered and evaluated according to Example 1. 20 μm × 20 μm with 0.20% aqueous solution of tetramethylammonium hydroxide
Could be resolved.

Table 2 shows the results.

[0121]

Example 11 Irgacure 369 used in Example 1
Instead of 4.0 g, Irgacure 2612.0 g and Irgacu
Using 2.0 g of re369, a composition solution was prepared, filtered and evaluated according to Example 1. 20 μm × 20 μm with 0.14% aqueous solution of tetramethylammonium hydroxide
Could be resolved.

Table 2 shows the results.

[0123]

Example 12 Aronix M-4 used in Example 1
Using KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) instead of 00, a composition solution was prepared, filtered and evaluated according to Example 1. A pattern of 20 μm × 20 μm could be resolved with a 0.20% aqueous solution of tetramethylammonium hydroxide.

Table 2 shows the results.

[0125]

Example 13 Aronix M-4 used in Example 1
V-295 instead of 00 (Osaka Organic Chemical Industry Co., Ltd.)
) Was prepared, filtered and evaluated according to Example 1. A pattern of 20 μm × 20 μm could be resolved with a 0.40% aqueous solution of tetramethylammonium hydroxide.

Table 2 shows the results.

[0127]

[Table 2]

[0128]

Examples 14 to 20 0.625 g of a 1.0% solution of SH-28PA (manufactured by Toray Silicone Co., Ltd.) in diethylene glycol dimethyl ether was added to the composition solutions shown in Examples 1 to 7 as other ingredients. It was prepared, filtered and evaluated according to Example 1.

Table 3 shows the results.

[0130]

[Table 3]

[0131]

The heat-resistant radiation-sensitive resin composition according to the present invention is excellent in various properties required for an optical device protective film such as mechanical properties, chemical resistance and transparency, and has a flat surface. Can be formed.

The heat-resistant radiation-sensitive resin composition of the present invention can easily form a protective film having a predetermined pattern by removing unnecessary portions during exposure and development.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G02B 5/20 101 G02B 5/20 101 (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Stock In-company (56) References JP-A-61-221218 (JP, A) JP-A-62-256806 (JP, A) JP-A-2-180921 (JP, A) JP-A-2-300215 (JP, A) JP-A-4-7310 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/42 C08G 59/20 G02B 5/20 101 C08F 220/04 C08F 220/08 C08F 220/32

Claims (1)

(57) [Claims] (A) (a-1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (a-2) an epoxy group-containing radical polymerizable compound, and (a-3) a monoolefin-based compound. A copolymer of an unsaturated compound and (a-4) a conjugated diolefin-based unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated double bond, [C] having at least two epoxy groups A heat-resistant radiation-sensitive resin composition comprising a compound and [D] a photopolymerization initiator.