JPH06192389A - Heat resistant and radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in mechanical characteristics, chemical resistance, etc., and suitable for a protective film used for optical devices by including a specific copolymer, an ethylenic unsaturated double bond-containing polymerizable compound, an epoxy group-containing compound and a photopolymerization initiator. CONSTITUTION:This resin composition consists of (A) a copolymer of (i) an unsaturated carboxylic acid and unsaturated carboxylic anhydride [e.g. 10-30wt.% (meth)acrylic acid], (ii) an epoxy group-containing radical polymerizable compound [e.g. 20-50wt.% glycidyl methacrylate, (iii) a monoolefin-based unsaturated compound (e.g. 20-50wt.% styrene) and (IV) a conjugated diolefin-based unsaturated compound (e.g. 5-15wt.% 1,3-butadiene), (B) a polymerizable compound having an ethylenic unsaturated double bond [e.g. (meth)acrylate], (C) a compound having at least two epoxy groups (e.g. bisphenol A type epoxy resin) and (D) a photopolymerization initiator (e.g. benzoin methyl ether).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat-resistant radiation-sensitive resin composition suitable as a material for forming a protective film for optical devices.

[0002]

2. Description of the Related Art Optical devices such as display devices and solid-state imaging devices have their surfaces sputtered during the manufacturing process, for example, by dipping in a solvent, an acid, an alkaline solution, etc., or when forming a wiring electrode layer. May be subjected to severe treatment such as locally heated to high temperature. Therefore, these elements may be provided with a protective film in order to prevent deterioration during manufacturing.

This protective film is required to have various characteristics capable of withstanding the above-mentioned treatments. Specifically, it has excellent adhesiveness to the substrate or the lower layer, is smooth and tough, and is transparent. Excellent heat resistance and light resistance to prevent deterioration such as coloring, yellowing and whitening over a long period of time, and chemical resistance such as water resistance, solvent resistance, acid resistance and alkali resistance. It is required to have excellent properties.

In order to meet such requirements, the applicant of the present invention has previously proposed a thermosetting composition containing an epoxy-based copolymer in JP-A-60-217230. It is widely used for forming a surface protective film of a liquid crystal display device or a color solid-state imaging device, and a protective flattening film on the device surface.

[0005]

By the way, the above-mentioned protective film is usually formed by applying a material for a protective film on a substrate by a spin coating method, followed by prebaking to form a coating film, and then curing this coating film. It is formed by

In such a protective film, a protective film capable of flattening the level difference of a color filter which is a base substrate is generally desired. In particular, when manufacturing an STN liquid crystal panel, it is necessary to perform the bonding of the color filter substrate and the counter substrate with extremely high precision, and it is essential to make the cell gap between the substrates uniform. There is. If the protective film cannot flatten the level difference of the color filter which is the base substrate, the accuracy of the cell gap adjustment at the time of sticking the substrates is reduced and the cell gap adjustment work becomes complicated, and the manufacturing yield of the display element is increased. Will decrease.

Therefore, conventionally, the surface of the color filter is previously flattened to some extent with a low-viscosity, high-concentration material, and then the protective film material is applied. Since such a flattening operation is required, the display element panel is required. Manufacturing becomes complicated and the cost is high.

Furthermore, when a protective film is formed by using a conventional protective film material by a spin coating method or the like, the film thickness at the peripheral portion of the substrate becomes thicker than the film thickness at other portions, and also when the substrates are bonded together. This causes a decrease in the accuracy of the cell gap adjustment and a complicated adjustment work.

In recent years, as a mounting method for liquid crystal display panels, COG (Ch
The ip on glass) method is drawing attention, but in order to manufacture a color liquid crystal display panel by this COG method, it is necessary to provide a protective film so that the protective film does not remain on the portion other than the color filter.

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

However, in the dry etching method,
Since the resist used after the dry etching must be removed, the process is complicated and the dry etching may cause defects on the display element.

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

[0013]

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, and (a-2) A radical polymerizable compound having an epoxy group, (a-3) a copolymer of a monoolefinic unsaturated compound and (a-4) a conjugated diolefinic unsaturated compound, and [B] an ethylenic unsaturated diamine It is characterized by comprising 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 moreover, a step of a base substrate (color filter). It is possible to form a protective film that can be planarized.

In addition, the heat-resistant radiation-sensitive resin composition according to the present invention can be easily exposed to light and developed to remove unnecessary portions and easily form a protective film having a predetermined pattern.

[0016]

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

Specific examples of the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a-1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, maleic acid and fumaric acid. Preferable examples include acids, dicarboxylic acids such as 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. Examples of the radical-polymerizable compound having an epoxy group (a-2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate. , Acrylic acid-3,4-epoxybutyl, methacrylic acid-
Examples thereof include 3,4-epoxybutyl, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylic acid and 6,7-epoxyheptyl α-ethyl acrylate.

Of these, glycidyl methacrylate,
Methacrylic acid-6,7-epoxyheptyl and the like are preferably used. These are mono-olefinic unsaturated compounds (a-3) used alone or in combination, for example, methyl methacrylate, ethyl methacrylate, n-
Butyl methacrylate, sec-butyl methacrylate, t-
Methacrylic acid alkyl ester such as butyl methacrylate, methyl acrylate, acrylic acid alkyl ester such as isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate,
Methacrylic acid cyclic alkyl ester such as isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentaoxyethyl acrylate, acrylic acid cyclic alkyl ester such as isobornyl acrylate, phenyl methacrylate, benzyl Methacrylic acid aryl ester such as methacrylate, phenyl acrylate, acrylic acid aryl ester such as benzyl acrylate, diethyl maleate, diethyl fumarate, dicarboxylic acid diester such as diethyl itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. 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.

Further, a 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] composed of the structural units derived from each of the above components, the copolymers composed of the structural units represented by the following formulas (1) to (6) are preferable, and Formula (1), (3), (4), (5), a copolymer consisting of structural units represented by (6) and formula (2), (3), (4), (5), ( 6)
A copolymer comprising a structural unit represented by is preferred.

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

[0024]

[Chemical 1]

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

[0026]

[Chemical 2]

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

[0028]

[Chemical 3]

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

[0030]

[Chemical 4]

(In the formula, R ¹ is a hydrogen atom or a lower alkyl group, and 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]

[Chemical 5]

(In the formula, R ³ is a hydrogen atom or a methyl group.) The copolymer [A] used in the present invention is an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride ( The constituent unit derived from a-1) is preferably contained 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 comprises 10 to 70% by weight, particularly preferably 20 to 70% by weight of a structural unit derived from the radically polymerizable compound (a-2) having an epoxy group. Contains 50% by weight.

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

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

The copolymer [A] comprising the above structural units has appropriate solubility in an alkaline aqueous solution, and a heat-resistant radiation-sensitive resin composition containing this copolymer [A] is It is possible to easily form a protective film having a predetermined pattern without developing residue and no film sticking during development.

The constitutional unit derived from the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride (a-1) is 5
A copolymer having a content of less than wt% becomes difficult to dissolve in an aqueous alkaline solution. In addition, mono-olefin unsaturated compounds (a-3)
Even if it contains more than 70% by weight of the structural unit derived from or the structural unit derived from the conjugated diolefin unsaturated compound (a-4) exceeds 30% by weight, this copolymer Has reduced solubility in aqueous alkaline solutions.
On the other hand, a copolymer containing an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride (a-1) in an amount exceeding 40% by weight tends to have too high solubility in an aqueous alkaline solution.

From the heat-resistant radiation-sensitive resin composition containing the copolymer [A] composed of the above structural units, a protective film having excellent heat resistance can be formed. In such a copolymer, the constitutional unit derived from the radically polymerizable compound (a-2) having an epoxy group is 10% by weight.
Less than or less than mono-olefinic unsaturated compound (a-3)
If the constitutional unit derived from the compound exceeds 70% by weight, or if the constitutional unit derived from the conjugated diolefin unsaturated compound (a-4) exceeds 30% by weight, the heat resistance including this copolymer The heat resistance of the protective film obtained from the radioactive resin composition tends to decrease.

When the heat-resistant 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 alkaline aqueous solution, and has a special property. It can be easily cured by heating without using a curing agent.

Conventionally, a radiation-sensitive resin composition comprising an epoxy group-containing polymer and a carboxylic acid group-containing compound or a carboxylic acid anhydride-containing polymer has been known, but 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 that the protective film obtained from this composition is prone to surface roughness. Further, 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 denaturing step is required and it is difficult to adjust the amount of denaturation.

When the copolymer is produced only from the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (a-1) and the radical-polymerizable compound (a-2) having an epoxy group, the epoxy In some cases, the group reacts with the carboxylic acid group and crosslinks to gelate 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 acid anhydride (a-1) and a radical polymerizable compound (a- In addition to 2), the monoolefin unsaturated compound (a-3) and the conjugated diolefin unsaturated compound (a-4) are copolymerized, and the epoxy group and the carboxylic acid group react with each other. , Cross-linking and gelation are suppressed,
It also has excellent storage stability.

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

Examples of the solvent used at this time include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, cellosolve esters such as methyl cellosolve acetate, aromatic hydrocarbons,
Examples thereof 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 dimethyl valeronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1'-bis- (T-
Examples include organic peroxides such as butylperoxy) cyclohexane and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, it may be used as a redox type initiator by using the peroxide together with a reducing agent. Copolymer [A] as described above
The molecular weight and distribution thereof are 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 monofunctional (meth) acrylates include Aronix M-101, Aronix M-111, and M-111.
114 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD
TC-110S, TC-120S (Nippon Kayaku Co., Ltd.)
Manufactured by Osaka Organic Chemical Industry Co., Ltd. (commercially available), and the like.

Examples of the bifunctional (meth) acrylate include Aronix M-210, Aronix M-240, and M-240.
6200 (manufactured by Toagosei 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 product), and the like.

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

These may be 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 particularly limited as long as it is compatible with other components forming the resin composition. Although not used, preferably, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin , And a glycidyl methacrylate-containing resin composition such as Optoma-SS (manufactured by Japan Synthetic Rubber Co., Ltd.).

Among these, bisphenol A type epoxy resin, cresol novolac 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.

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

As the photo-radical polymerization 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, thioxanthone-4- Sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, benzophenones such as 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, anthraquinone, quinones such as 1,4-naphthoquinone, phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-
Examples thereof include halogen compounds such as triazine and peroxides such as di-t-butyl peroxide.

Further, as the cationic photopolymerization initiator, the following commercial products can be used. Diazonium salts such as Adeka Ultraset PP-33 (manufactured by Asahi Denka Kogyo KK), sulfonium salts such as OPTOMER SP-150, 170 (manufactured by Asahi Denka Kogyo KK), IRGACURE26
1 (manufactured by CIBA-GEIGY) and the like.

When exposure is carried out in an oxygen atmosphere, radical deactivation (decrease in sensitivity) due to oxygen occurs in the photoradical polymerization initiator, and the residual film rate and hardness of the exposed portion cannot be sufficiently obtained. There are cases. When exposure is carried out in such an oxygen atmosphere, all of the above photopolymerization initiators are photocationic polymerization initiators (photocationic polymerization initiators hardly deactivate active species due to oxygen), and A part of the radical polymerization initiator, for example, 2-methyl-
Acetophenones such as [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or phenacyl chloride, Halogen compounds such as tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine can be mentioned as preferable compounds.

Further, it is possible to achieve high sensitivity with little deactivation by oxygen by using these photoradical polymerization initiators in combination with a photocationic polymerization initiator or a photosensitizer.

Heat-Resistant Radiation-sensitive Resin Composition The heat-resistant radiation-sensitive resin composition according to the present invention is a polymer having an ethylenically unsaturated double bond based on 100 parts by weight of the above-mentioned copolymer [A]. Of the organic compound [B], preferably 40 to 200 parts by weight, more preferably 80 to 150
The amount of the compound [C] having at least two epoxy groups in an amount of parts by weight, preferably 30 to 200 parts by weight, more preferably 50 to 120 parts by weight, the photopolymerization initiator [D], preferably 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 characteristics and can flatten the level difference of the color filter as the underlying substrate. It can be easily formed on the protective film having a predetermined pattern by exposure and development.

In particular, the heat-resistant radiation-sensitive resin composition containing the polymerizable compound [B] having an ethylenically unsaturated double bond in the above amount does not lower the radiation sensitivity even in an oxygen atmosphere. . Further, the polymerizable compound [B] having an ethylenically unsaturated double bond in the amount as described above has excellent compatibility with other components, and the heat-resistant radiation-sensitive resin composition containing this compound has a rough film. It is possible to form a protective film that does not have any.

In addition, 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 as described above, the compatibility of the compound [C] with other components is high. A heat-resistant radiation-sensitive resin composition which is excellent and does not deteriorate the coating film forming property and which contains the compound [C] in such an amount is capable of flattening the steps of the color filter as the base substrate. Is a protective material that is possible.

Further, in the heat-resistant radiation-sensitive resin composition according to the present invention which contains the photopolymerization initiator [D] in the above amount, the radiation-sensitive sensitivity is lowered by oxygen (radicals are deactivated). In addition, the heat-resistant radiation-sensitive resin composition is not colored deeply and can be suitably used for a display element such as an LCD.

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 dissolved in an appropriate solvent and used in a solution state. For example, a solution of the copolymer [A], the ethylenic compound [B], the photopolymerization initiator [D], the epoxy compound [C] and other compounding agents are mixed in a predetermined ratio immediately before use to give a solution. The heat-resistant radiation-sensitive resin composition in the state can be prepared.

Examples of such a solvent include [A],
A material that can uniformly dissolve [B], [C] and [D] and does not react with each component is 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, ethylene glycol alkyl ethers such as methyl cellosolve acetate and ethyl cellosolve acetate. Diethylene glycols such as acetates, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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
Examples include 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, benzylethylether, 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, A high boiling point solvent 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 used 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 radiation-sensitive resin composition according to the present invention may contain components other than the above components, if necessary, within the range not impairing the object of the present invention. A surfactant is mentioned as such another component.

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, the same S-113, the same S-131, the same S-141, the same S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, the same-
190, ibid-193, SZ-6032, SF-8428
Fluorine-based surfactants marketed under the names such as (Toray Silicone Co., Ltd.) can be used.

These surfactants are used as the copolymer [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 can 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 means
Examples thereof include silane coupling agents having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, and more specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxy. Examples thereof include silane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

These adhesion promoters 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 A coating film can be formed by applying the heat-resistant radiation-sensitive resin composition according to the present invention to the surface of a substrate and removing the solvent by heating. The method for 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 adopted.

Next, this coating film is heated (prebaked). The heating condition is usually 70 to 90 ° C. for about 5 to 15 minutes, though it varies depending on the kind of each component, the mixing ratio and the like. Next, the prebaked coating film is irradiated with ultraviolet rays or the like through a mask having a predetermined pattern, and then developed with a developing solution to remove unnecessary portions to form a predetermined pattern.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine and 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.

Further, in the above alkaline aqueous solution, methanol,
An aqueous solution containing a water-soluble organic solvent such as ethanol and an appropriate amount of a surfactant may be used as a developer.
The developing time is usually 30 to 180 seconds, and the developing method may be any of a puddle method and a dipping method.
After the development, washing with running water is carried out for 30 to 90 seconds, and by drying with compressed air or compressed nitrogen, unnecessary portions are removed and a pattern is formed. Thereafter, this pattern is subjected to a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, or 30 to 30 in the oven by a heating device such as a hot plate or an oven.
Heat treatment for 90 minutes, heat resistance, transparency,
It is possible to obtain a protective film having excellent hardness.

[0080]

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

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

[0082]

Synthesis Example 1 A flask equipped with a dry ice / methanol reflux was replaced 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. 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, and then gently stirring was started. The temperature of the solution is 8
After raising the temperature to 0 ° C. and maintaining this temperature for 5 hours, 90.
Polymerization was terminated by heating at 0 ° C. for 1 hour.

Then, 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. This redissolving-coagulation operation was performed three times in total, and the obtained coagulated product was vacuum dried at 60 ° C. for 48 hours to obtain the target copolymer. After this, the solid concentration is 2
A copolymer solution was prepared by using diethylene glycol dimethyl ether so as to be 5% by weight.

[0084]

[Synthesis Example 2] A flask equipped with a dry ice / methanol reflux was replaced with nitrogen, and then 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. Styrene 11.25g, methacrylic acid 3
3.75 g, dicyclopentanyl methacrylate 56.
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 this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization.

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

[0086]

Synthesis Example 3 A flask equipped with a dry ice / methanol reflux 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. Successively, 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.
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,
Polymerization was terminated by heating at 90 ° C. for 1 hour.

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

[0088]

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

Then, 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 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 22.5g, methacrylic acid 45.0
g, 2-methylcyclohexyl acrylate 56.25
g, 90.0 g of methacrylic acid-6,7-epoxyheptyl and 11.25 g of 1,3-butadiene were charged, and then gentle stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to terminate the polymerization.

Then, 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) to diethylene glycol dimethyl ether 13.
After diluting 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 Toagosei Chemical Industry Co., Ltd.) 25.0 g,
γ-glycidoxypropyltrimethoxysilane 1.25
g, Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd.)
12.25 g was dissolved and 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 composition solution (1) above was applied onto a SiO ₂ glass substrate using a spinner, and then prebaked at 80 ° C. for 5 minutes on a hot plate to give a film thickness of 2.0 μm. Was formed.

(Ii) Removal of unnecessary portions by exposure / development The coating film obtained in (i) above was exposed to ultraviolet rays having a light intensity of 10 mJ / cm ² at 365 nm for 30 seconds using a predetermined pattern mask. Irradiated. The exposure at this time was performed in an oxygen atmosphere (in air). Then, after developing with 0.14% by weight of tetramethylammonium hydroxide at 25 ° C. for 1 minute, it was rinsed with ultrapure water for 1 minute. By these operations,
Unnecessary parts can be removed and 20μm x 20μm
I was able to resolve the pattern (remaining).

(Iii) Curing of coating film The coating film obtained in (ii) above was heated 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 various properties required.

(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 (i). Then, the whole surface was exposed for 30 seconds, developed with an aqueous solution of tetramethylammonium hydroxide, and rinsed with ultrapure water for 1 minute. It was then heated on a hot plate at 200 ° C. for 20 minutes. The transmittance of 400 to 800 nm of the obtained substrate was measured using a spectrophotometer (150-20 type table beam (Hitachi)). At this time, when the minimum transmittance exceeds 95%, it is ◯, when 90 to 95% is Δ, and when it is less than 90%, it is ×.
And

The results are shown in Table 1. (v) Evaluation of heat resistance The substrate on which the pattern was formed in (iii) above was heated for 1 hour using a hot plate at 250 ° C., and the film thickness before and after heating was measured to evaluate the heat resistance. When the rate of change (remaining film rate) exceeded 95%, it was evaluated as ◯, when 90 to 95% was evaluated as Δ, and when it was less than 90% as ×.

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

The results are shown in Table 1. (vii) Measurement of hardness Using the coating film formed in (iv) above, JIS K-540
According to the 8.4.1 pencil scratch test of 0-1990,
For the evaluation, the pencil hardness was measured by scratching the coating film, and the surface hardness was measured.

The results are shown in Table 1. (viii) Evaluation of flattening property Instead of the SiO ₂ glass substrate used in (i) above,
A coating film was formed in the same manner as in (iii) above, except that a SiO ₂ wafer having a step of 1.0 μm was used. After that, the step difference of the substrate was measured using a stylus type film thickness measuring device.

The results are shown in Table 1.

[0102]

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

The results are shown in Table 1.

[0104]

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

The results are shown in Table 1.

[0106]

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

The results are shown in Table 1.

[0108]

Example 5 Using the copolymer solution obtained in Synthesis Example 5 instead of the copolymer solution obtained in Synthesis Example 1, a composition solution was prepared, filtered and evaluated according to Example 1. did. Tetramethylammonium hydroxide 0.14% aqueous solution 2
A pattern of 0 μm × 20 μm could be resolved.

The results are shown in Table 1.

[0110]

Example 6 In place of the Irgacure369 used in Example 1, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (Irgacure907) was used, and the composition was obtained according to Example 1. The product 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 the Epicoat 828 used in Example 1, Epolite 100MF (manufactured by Kyoeisha Yushi Co., Ltd.)
Was used to prepare and filter a composition solution in accordance with Example 1 and evaluated. Tetramethylammonium hydroxide
A 20 μm × 20 μm pattern could be resolved with a 12% aqueous solution.

The results are shown in Table 1.

[0114]

[Table 1]

[0115]

[Example 8] Irgacure369 used in Example 1 7.
Instead of 5g, Irgacure 3692.0g and Irgacure 9
07 2.0 g were mixed and a composition solution was prepared and filtered according to Example 1 and evaluated. A 20 μm × 20 μm pattern could be resolved with a 0.14% aqueous solution of tetramethylammonium hydroxide.

The results are shown in Table 2.

[0117]

Example 9 Irgacure369 used in Example 1 7.
Instead of 5 g, (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-) (Ir
gacure261 (manufactured by CIBA-GEIGY)) 4.0 g,
A composition solution was prepared and filtered according to Example 1 and evaluated.
A 20 μm × 20 μm pattern could be resolved with a 0.20% aqueous solution of tetramethylammonium hydroxide.

The results are shown in Table 2.

[0119]

Example 10 Irgacure369 used in Example 1
Instead of 7.5 g, tris (trichloromethyl) -s-
A composition solution was prepared and filtered according to Example 1 using 2.5 g of triazine and evaluated. Tetramethylammonium hydroxide 0.20% aqueous solution 20 μm × 20 μm
I was able to resolve the pattern.

The results are shown in Table 2.

[0121]

Example 11 Irgacure369 used in Example 1
Instead of 4.0g, Irgacure 2612.0g and Irgacu
A composition solution was prepared and filtered according to Example 1 using 2.0 g of re369 and evaluated. Tetramethylammonium hydroxide 0.14% aqueous solution 20 μm × 20 μm
I was able to resolve the pattern.

The results are shown in Table 2.

[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 and filtered according to Example 1 and evaluated. A 20 μm × 20 μm pattern could be resolved with a 0.20% aqueous solution of tetramethylammonium hydroxide.

The results are shown in Table 2.

[0125]

Example 13 Aronix M-4 used in Example 1
V-295 instead of 00 (Osaka Organic Chemical Industry Co., Ltd.)
(Manufactured by Mfg. Co., Ltd.) was used to prepare and filter a composition solution in accordance with Example 1 and evaluated. A pattern of 20 μm × 20 μm could be resolved with a 0.40% aqueous solution of tetramethylammonium hydroxide.

The results are shown in Table 2.

[0127]

[Table 2]

[0128]

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

The results are shown in Table 3.

[0130]

[Table 3]

[0131]

The heat-resistant radiation-sensitive resin composition according to the present invention is excellent in various properties required for a protective film for optical devices, 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A) (a-1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a-2) an epoxy group-containing radically polymerizable compound, and (a-3) a monoolefin system. Copolymer of unsaturated compound and (a-4) conjugated diolefin unsaturated compound, [B] polymerizable compound having 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.