JPH0643643A - Heat resistant radiosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition capable of easily removing an unnecessary part by exposure and development while satisfying various characteristics of a protective film by allowing a base polymer of an alkali aq. solution soluble resin to contain a group originating from carboxylic acid or carboxylic acid anhydride, which is an alkali soluble component, and epoxy group in the same molecule. CONSTITUTION:This composition contains the alkali aq. solution soluble resin which is a copolymer of an unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, a radical polymerizable compound, having epoxy group, and another radical polymerizable compound. Furthermore, a polymerizable compound having at least one ethylenic unsaturated double bond and a photopolymerization initiator are contained. A thermosetting resin is preferably used as the alkali aq. solution soluble resin and the resin is obtained by copolymerizing the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and the radical polymerizable compound having epoxy group with another radical polymerizable compound in a solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a heat resistant radiation sensitive resin composition. More specifically, it relates to a heat-resistant radiation-sensitive resin composition which is suitable as a material for forming a coating film used in an optical device and which has various excellent physical properties.

[0002]

2. Description of the Related Art Conventionally, a protective film layer has been widely formed in order to prevent deterioration or damage of a display device or a solid-state image pickup device. The protective film layer, a solvent, acid, during the manufacturing process of the display element, it is necessary to be immersed in an alkaline solution or the like, because the surface locally takes a high temperature during film formation by the sputtering process of the wiring electrode layer, A thin film layer provided to prevent the element from deteriorating due to the above-mentioned stimulation, and an organic film having excellent resistance to these treatments is usually used.
In such a protective film, the adhesiveness to the substrate or the lower layer is high, the coating film is smooth and tough, transparent, has high heat resistance and light resistance, and has long-term coloring, yellowing, whitening, etc. Performances such as no deterioration and excellent water resistance, solvent resistance, acid resistance, and alkali resistance are required.

As a material capable of forming a protective film satisfying such requirements, a composition as disclosed in JP-A-60-217230 is known, and a color liquid crystal display incorporating a color separation filter is known. It is widely used as a protective film on the surface of a device or a color solid-state imaging device, a protective flattening film on the device surface, and the like.

[0004]

However, when these materials are applied by a general spin coating method, the film thickness at the peripheral portion of the substrate becomes thicker than the film thickness at other portions. This deteriorates the accuracy of the cell gap adjustment, which is indispensable when the substrates are bonded together when manufacturing the display element, and causes problems such as a decrease in the yield of the display element manufacturing and the complexity of the work process associated with the cell gap adjustment. ing. Further, regarding the adhesiveness between the sealant and the protective film, the reliability of the display element is also a problem because the adhesiveness with the protective film changes depending on the type of the sealant.

In order to solve the above problems,
It is necessary to remove the protective film in the portions that are not needed during panel production (portions with different film thicknesses, portions that come into contact with the sealant). As a conventionally used method, for example, a resist having excellent dry / etch resistance is applied on the protective film,
After exposing and developing the resist to an appropriate pattern, dry
Etching may be performed to remove an unnecessary portion of the protective film.

However, the disadvantage of this method is that the resist used after the dry etching must be removed, which complicates the panel manufacturing process, and the dry etching causes defects on the display element. May occur.

Therefore, in the present invention, while satisfying the various characteristics required for the conventional protective film in order to solve the above-mentioned problems, an unnecessary portion which is a problem when manufacturing a panel is exposed. -The purpose is to provide a radiation-sensitive resin composition that can be easily removed by development.

[0008]

That is, the heat-resistant radiation-sensitive resin composition of the present invention has (A) (a) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, and (b) epoxy group. A resin soluble in an alkaline aqueous solution which is a copolymer of a radically polymerizable compound and (c) another radically polymerizable compound, (B) a polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter, "Ethylene compound")
And (C) a photopolymerization initiator, which is a heat-resistant radiation-sensitive resin composition.

The most characteristic feature of the above composition is that the base polymer, which is a resin soluble in an alkaline aqueous solution, contains a group derived from a carboxylic acid or a carboxylic acid anhydride, which is an alkali-soluble component, and an epoxy group in the same molecule. It is to have. Conventionally, there are known examples in which a radiation-sensitive resin composition contains an epoxy group and a carboxylic acid or a carboxylic acid anhydride.

However, these compositions are a mixture of a compound containing an epoxy group and a compound containing a carboxylic acid or a carboxylic acid anhydride, or a compound modified by a polymer reaction. A drawback of these conventional compositions is that when they are a mixture, they have problems to be solved such as compatibility of the two kinds of compounds, storage stability of the composition, and roughness of the coating film. When it ’s a compound,
There is a problem to be solved in reproducibility due to complicated synthesis and difficulty in quantifying reaction. Then, based on such a background, as a result of earnestly researching in consideration of the conventional problems, the inventors have found that the above problems can be solved, and arrived at the present invention. The components of the present invention will be described below.

1. Resin soluble in aqueous alkaline solution: The resin soluble in aqueous alkaline solution used in the present invention is preferably a resin which can be cured by heating, that is, a thermosetting resin. Such a resin comprises (a) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride and (b) a radically polymerizable compound having an epoxy group, and (c) another radically polymerizable compound in a solvent for radical copolymerization. It can be obtained by polymerization.

Preferred unsaturated carboxylic acids (a) are, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Can be mentioned. Further, as the unsaturated carboxylic acid anhydride, for example, maleic anhydride, itaconic anhydride and the like can be mentioned as preferable ones.

Examples of the radically polymerizable compound (b) having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate,
α-n-Propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylic acid, 6,7-epoxyheptyl acrylate, methacrylic acid −
6,7-epoxyheptyl, α-ethylacrylic acid-6,
7-epoxyheptyl etc. can be mentioned.

As a method for obtaining a resin soluble in an alkaline aqueous solution (hereinafter referred to as "copolymer I") in the present invention, the above-mentioned unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride and an epoxy group are used. In the radical polymerization in a two-component system with the radically polymerizable compound, the epoxy group reacts with the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride during the polymerization reaction, resulting in crosslinking and gelation of the polymerization system. .

Therefore, in order to obtain the copolymer I, it is necessary to suppress the reaction between the epoxy group and the carboxylic acid or acid anhydride by using another radically polymerizable compound as the third component. As such other radically polymerizable compound (c), a monoolefin unsaturated compound is preferable.

Further, by incorporating the monoolefin unsaturated compound into the copolymer, the mechanical properties of the copolymer can be appropriately controlled and the solubility in an alkaline aqueous solution can be adjusted.

Examples of the monoolefin unsaturated compound include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; acrylic acid such as methyl acrylate and isopropyl acrylate. Alkyl ester; methacrylic acid cyclic alkyl ester such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopenta Nyl acrylate, dicyclopentanyloxyethyl acrylate,
Cyclic alkyl esters of acrylic acid such as isobornyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acids such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl Diesters of acids; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene. , Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like can be used.

The copolymerization ratio of the radically polymerizable compound having an epoxy group of the copolymer I is preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight. When it is less than 10% by weight, the reaction with the acid generated by irradiating the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride or the radiation-sensitive acid-forming compound with radiation is difficult to sufficiently proceed, and thus it is obtained from the composition. It becomes difficult for the heat resistance of the formed pattern to be sufficient. On the other hand, when it exceeds 70% by weight, a problem tends to occur in the storage stability of the copolymer I.

The copolymerization ratio of unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride of copolymer I is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight. If the amount is less than 5% by weight, the resulting copolymer becomes difficult to dissolve in an alkaline aqueous solution, so that a development residue is likely to occur and it is difficult to form a sufficient pattern. On the other hand, if it exceeds 40% by weight, the solubility of the resulting copolymer in an alkaline aqueous solution becomes too large, and it becomes difficult to prevent dissolution of the irradiated portion, that is, film loss development.

The copolymerization ratio of the other radically polymerizable compound of the copolymer I is preferably 10 to 70% by weight, particularly preferably 30 to 50% by weight. If it is less than 10% by weight, gelation tends to occur during the polymerization reaction. Again 70
When the content exceeds 50% by weight, the amount of the radically polymerizable compound having an epoxy group, the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride becomes relatively small, so that the solubility of the resin in the alkaline aqueous solution is decreased or the composition is The resulting pattern may have insufficient heat resistance.

As the solvent used for polymerizing the copolymer I, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether; cellosolve ester such as methyl cellosolve acetate. In addition, aromatic hydrocarbons, ketones, esters and the like can be mentioned.

As a polymerization catalyst in radical polymerization, a usual radical polymerization initiator can be used, for example, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis-
Azo compounds such as (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate,
Examples thereof include organic peroxides such as 1,1-bis- (t-butylperoxy) cyclohexane and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, a reducing agent may be combined to form a redox type initiator.

The molecular weight of the above copolymer I and its distribution are not particularly limited as long as the solution of the composition of the present invention can be uniformly applied. Then,
The copolymer I is represented by the following formulas (1), (2), (2 ') and (3).
Those having the structural units represented by and (4) are preferred.

[0024]

[Chemical 1]

[0025]

[Chemical 2]

[0026]

[Chemical 3]

[0027]

[Chemical 4]

[0028]

[Chemical 5]

Of the above structural units, (1), (2),
A copolymer comprising structural units represented by (3) and (4) and the above (1), (2 '), (3) and (4)
A copolymer having a structural unit represented by is particularly preferable as the copolymer I.

2. Ethylenic compound: As the polymerizable compound having at least one ethylenically unsaturated double bond used in the present invention, monofunctional or polyfunctional acrylic acid or methacrylic acid ester is preferred. Can be mentioned.

As the monofunctional (meth) acrylate, commercially available products such as Aronix M-101 and Aronix M-1 are available.
11, the same M-114 (manufactured by Toagosei Chemical Industry Co., Ltd.), K
AYARAD TC-110S, the same TC-120S (made by Nippon Kayaku Co., Ltd.), V158, V2311 (made by Osaka Organic Chemical Industry Co., Ltd.) etc. can be mentioned. As the bifunctional (meth) acrylate, commercially available products such as Aronix M-210, M-240 and M-6200 are available.
(Manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD HDD
A, HX-220, R-604 (Nippon Kayaku Co., Ltd.)
Manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like. Further, as trifunctional or higher functional (meth) acrylates, commercially available products such as Aronix M-400, Aronix M-405, and M-45 are available.
0, the same M-7100, the same M-8030, the same M-8060
(Toagosei Chemical Industry Co., Ltd.), KAYARAD ™
PTA, DPCA-20, -30, -60, and-
Examples include 120 (manufactured by Nippon Kayaku Co., Ltd.) and VGPT (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

These compounds may be used alone or in combination of two or more, and preferably 40 to 200 parts by weight, more preferably 80 parts by weight with respect to 100 parts by weight of the copolymer I.
~ 150 parts by weight. If it is less than 40 parts by weight, the sensitivity tends to be reduced particularly in an oxygen atmosphere, and if it exceeds 200 parts by weight, the compatibility with the copolymer I is deteriorated and the film surface may be roughened after the film is formed. is there.

3. Photopolymerization initiator: The photopolymerization initiator used in the present invention is a photoradical polymerization initiator capable of reacting an ethylenic compound, or a copolymer I.
A photocationic polymerization initiator or the like capable of reacting the epoxy group therein can be used. Examples of the photoradical polymerization initiator include 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, 4,
Benzophenones such as 4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl −
[4- (methylthio) phenyl] -2-morpholino-
1-propanone, 2-benzyl-2-dimethylamino-
Acetophenones such as 1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s- Halogen compounds such as triazine; and di-
Examples thereof include peroxides such as t-gtyl peroxide.

As the cationic photopolymerization initiator, the following commercial products can be used. ADEKA ULTRASET PP-33 (made by Asahi Denka Co., Ltd.) which is a diazonium salt, OPTOMER which is a sulfonium salt
SP-150, 170 (manufactured by Asahi Denka Co., Ltd.), IRGACURE 261 (CIBA) which is a metallocene compound.
-GEIGY (made by company) can be mentioned.

When using these photopolymerization initiators, it is necessary to consider the exposure conditions (oxygen atmosphere or oxygen-free atmosphere). That is, when exposure is performed in an oxygen-free atmosphere, various photocationic polymerization initiators and photoradical polymerization initiators described above can be used. However, when exposure is performed 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. Occurs (the cationic photopolymerization initiator hardly deactivates active species due to oxygen).

Among the above-mentioned various photopolymerization initiators, preferred compounds include 2-radical photopolymerization initiators.
Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-
Examples thereof include acetophenones such as 1-one or halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine, and photocationic polymerization initiators.
The amount used is 1.0 with respect to 100 parts by weight of the copolymer I.
-50 parts by weight is preferable, and 5-30 parts by weight is particularly preferable. When it is less than 1 part by weight, deactivation of radicals (decrease in sensitivity) due to oxygen is apt to occur, and when it exceeds 50 parts by weight, the color density of the solution becomes high and it may be unsuitable for display elements such as LCD. .

Further, these photopolymerization initiators (radical type)
It is also possible to achieve high sensitivity with little inactivation by oxygen by using a combination of a cationic photopolymerization initiator and a photosensitizer.

4. Organic solvent: The composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components. When mixing, it is usually dissolved in an appropriate solvent and used in the form of a solution. As the solvent to be used, a solvent which can uniformly dissolve the copolymer I, the ethylenic compound and the photopolymerization initiator and which does not react with each component is used.

Examples of such a solvent include methanol,
Alcohols such as ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether,
Glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol methyl ether acetate, propylene Propylene glycol alkyl ether acetates such as glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate , 2-hydroxy-2-methylpropionic acid , Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid ethyl,
Esters such as methyl 3-ethoxypropionate, ethyl acetate and butyl acetate can be used.

Furthermore, N-methylformamide, N, N
-Dimethylformamide, N-methylformanilide,
N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
It is also possible to add a high boiling point solvent such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate.

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

In preparing the composition solution, for example, a solution of the copolymer I, a solution of the ethylenic compound and the photopolymerization initiator, and a solution of other compounding agents are separately prepared, and these are prepared immediately before use. It is also possible to mix the solutions in predetermined proportions. The composition solution prepared as described above can be used after being filtered using a Millipore filter or the like having a pore size of 0.2 μm.

5. Other compounding agents: In the composition of the present invention, a surfactant can be compounded. Examples of the surfactant include BM-1000 and BM-1100.
(Manufactured by BM Chemie), Megafac F142
D, the same F172, the same F173, the same F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, the same F
C-170C, FC-430, FC-431 (Sumitomo 3M Limited), Surflon S-112, S-
113, S-131, S-141, S-145
Commercially available fluorochemical surfactants such as (Asahi Glass Co., Ltd.) can be used. The amount of these surfactants used is preferably 5 parts by weight or less, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the copolymer I.

Further, an adhesion aid can be used to improve the adhesion to the substrate. A functional silane coupling agent is effective as the adhesion aid used.
Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, and specific examples include trimethoxysilylbenzoic acid and γ.
-Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ
-Isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-
Examples thereof include epoxycyclohexyl) ethyltrimethoxysilane and the like. These adhesion aids can be used alone or in combination of two or more. In general, it is suitable that the amount thereof is 20 parts by weight or less, particularly 0.05 to 10 parts by weight, based on 100 parts by weight of the copolymer I.

In the present invention, the base polymer (1),
Since it has an epoxy group in (2), it is basically to cause a curing reaction when the coating film is heated to impart heat resistance and solvent resistance. However, when sufficient heating conditions (temperature, time) cannot be set, it is also effective to use a catalyst in combination to cause a curing reaction in order to accelerate the reaction. As the catalyst to be used, an amine known as a curing agent for epoxy compounds can be used, but a latent curing agent is preferable from the viewpoint of storage stability of the solution. Preferred examples of such a latent curing agent are dicyandiamide, organic acid hydrazide, amine imide, tertiary amine salt, 1-substituted imidazole and imidazole salt which are activated by heating. The amount of these curing catalysts used is preferably 10 parts by weight or less, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the copolymer I. If it exceeds 10 parts by weight, the storage stability of the solution may be reduced. Further, an accelerator such as an acid anhydride may be used in combination with these curing catalysts.

Method for producing coating film: In the present invention, a desired coating film can be formed by applying the above-mentioned composition solution on a predetermined substrate surface and removing the solvent by heating. The coating method on the substrate surface is not particularly limited,
For example, various methods such as a spray method, a roll coating method and a spin coating method can be adopted.

The heating conditions for the coating film of the composition of the present invention are usually 70 to 90 ° C. for about 5 to 15 minutes, although they vary depending on the type and mixing ratio of each component. Next, the obtained coating film is irradiated with, for example, ultraviolet rays through a mask having a predetermined pattern, and then developed with a developing solution to remove unnecessary portions to form a pattern. Examples of the developer in the present invention 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-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. Aqueous solutions of alkalis such as 3.0] -5-nonane can be used. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous solution of alkalis can be used as a developing solution.

The developing time is usually 30 to 180 seconds,
Further, the developing method may be any of a puddle method and a dipping method. After development, wash with running water for 30 to 90 seconds,
By air-drying with compressed air or compressed nitrogen, unnecessary parts can be removed and a pattern can be formed. After that, for example, by irradiating with an ultraviolet ray, the acid-generating compound remaining in the pattern which is the unexposed portion is converted into an acid. Further, using a heating device such as a hot plate or an oven, heat treatment is performed at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate or 30 to 90 minutes in an oven. By doing so, a protective film having excellent heat resistance, transparency, hardness and the like can be obtained.

[0049]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Also, unless otherwise specified
% Means% by weight.

Synthesis Example 1 After purging the inside of the flask 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, 67.5 g of dicyclopentanyl methacrylate and 90.0 g of glycidyl methacrylate were charged, and then gently 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, the reaction product solution 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 this redissolution-coagulation operation was carried out three times in total,
The obtained coagulated product was vacuum dried at 60 ° C. for 48 hours to obtain a target copolymer. Thereafter, a copolymer solution was prepared by using diethylene glycol so that the solid content concentration became 25% by weight.

Synthesis Example 2 After replacing the inside of the flask with nitrogen, 2,2'-azobis-
Diethylene glycol dimethyl ether solution 459.0 in which 9.0 g of (2,4-dimethylvaleronitrile) was dissolved
I charged g. Subsequently, 45.0 g of methacrylic acid, 90.0 g of dicyclopentanyl methacrylate and 90.0 g of glycidyl methacrylate were charged, and then gently 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 solution was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 3 After purging the inside of the flask 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, 56.2 g of methacrylic acid, 101.25 g of sec-butyl methacrylate and 67.5 g of glycidyl methacrylate 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 solution was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 4 After purging the inside of the flask with nitrogen, 459.0 g of a methyl 3-methoxypropionate solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was charged. Continuing,
Methacrylic acid 56.25 g, methyl methacrylate 90.
0 g and 3,4,4-epoxybutyl methacrylate 78.
After charging 75 g, gentle stirring was started. 80 ° C
Polymerization was started at 90 ° C and maintained at this temperature for 5 hours.
The polymerization was terminated by heating for 1 hour. Then, a copolymer solution was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 5 After purging the inside of the flask 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, 45.0 g of maleic anhydride, 112.5 g of benzyl methacrylate and α-ethylacrylic acid-6,7.
After charging 67.5 g of epoxyheptyl, gentle stirring was started. Polymerization was initiated at 80 ° C and the temperature was raised to 5
After holding for a time, the mixture was heated at 90 ° C. for 1 hour to terminate the polymerization. Then, a copolymer solution was obtained in the same manner as in Synthesis Example 1.

Example 1 (1) Preparation of Composition 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) -butane-1-
On (IRGACURE 369 (CIBA-GEIG
Y)), 7.5 g, Aronix M-400 (produced by Toagosei Kagaku Kogyo Co., Ltd.) 25.0 g, and γ-glycidoxypropyltrimethoxysilane 2.5 g are dissolved, and the pore size is 0.2.
A composition solution (1) was prepared by filtering with a 2 μm Millipore filter.

(2) Formation of coating film The above composition solution (1) was applied onto a wafer having a silicon oxide film by a spinner and then prebaked at 80 ° C. for 5 minutes on a hot plate to give a film thickness of 2.0 μm. A coating film was formed.

(3) Removal of unnecessary portions by exposure / development Using the resist film obtained in (2) above with a predetermined pattern mask, the light intensity at 365 nm is 10 mJ / cm ^2.
UV light for 30 seconds. The exposure at this time was performed in an oxygen atmosphere (in air). Then, the resist film was developed with a 0.14% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 2 minutes, and then rinsed with ultrapure water for 1 minute. By these operations, unnecessary parts can be removed and 20μ
An m × 20 μm pattern (remaining) could be resolved.

(4) Curing of coating film The coating film obtained in (3) above was placed on a hot plate for 20 minutes.
The coating was cured by heating at 0 ° C. for 20 minutes to give the protective film the necessary properties.

(5) Evaluation of Transparency In the above (2), the same coating film as the above (2) except that a transparent substrate (Corning 7059: manufactured by Corning) was used instead of the wafer having the silicon oxide film. Was formed. 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. Then on a hot plate at 200 ° C
Heated for 20 minutes. The obtained substrate was put into a spectrophotometer (15
0-20 type double beam: manufactured by Hitachi Ltd. 40
The transmittance of 0 to 800 nm was measured. At this time, the case where the minimum transmittance exceeded 95% was marked with ◯, the case of 90 to 95% was marked with Δ, and the case where it was less than 90% was marked with x. The results are shown in Table 1.

(6) Evaluation of heat resistance The substrate on which the pattern was formed in the above (3) was heated to 250 ° C.
After heating for 1 hour using the hot plate of, the film thickness was measured. Then, using the residual film rate with respect to the film thickness of the substrate on which the pattern formed in (3) above is used, the residual film rate is 9
When it exceeds 5%, it is ○, when it is 90 to 95%, it is △ and 90.
When less than%, it was defined as x. The results are shown in Table 1.

(7) Evaluation of heat discoloration resistance The substrate on which the pattern was formed in the above (4) was heated to 250 ° C.
After heating for 1 hour on the hot plate of (1), the change rate of transmittance was determined using a spectrophotometer in the same manner as (4) Evaluation of transparency. When the rate of change at this time is less than 5%, it is ○, and 5
The case of 10% was marked with Δ, and the case of exceeding 10% was marked with x. The results are shown in Table 1.

(8) Measurement of hardness JIS K-54 was used by using the substrate prepared in the above (4).
According to the 8.4.1 pencil scratch test of 00-1990,
For evaluation, the pencil hardness was measured by scratches on the coating film, and the surface hardness was measured. The results are shown in Table 1.

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 and evaluated according to Example 1. . A 20 μm × 20 μm pattern could be resolved with a 0.20% aqueous solution of tetramethylammonium hydroxide. The other evaluation results are shown in Table 1.

Example 3 A composition solution was prepared and evaluated according to Example 1 except that the copolymer solution obtained in Synthesis Example 3 was used instead of the copolymer solution obtained in Synthesis Example 1. . A 20 μm × 20 μm pattern could be resolved with a 0.16% aqueous solution of tetramethylammonium hydroxide. The other evaluation results are shown in Table 1.

Example 4 A composition solution was prepared and evaluated according to Example 1 except that the copolymer solution obtained in Synthesis Example 4 was used instead of the copolymer solution obtained in Synthesis Example 1. . A 20 μm × 20 μm pattern could be resolved with a 0.14% tetramethylammonium hydroxide aqueous solution. The other evaluation results are shown in Table 1.

Example 5 A composition solution was prepared and evaluated according to Example 1 except that the copolymer solution obtained in Synthesis Example 5 was used instead of the copolymer solution obtained in Synthesis Example 1. . A pattern of 20 μm × 20 μm could be resolved with a 1.0% aqueous solution of tetramethylammonium hydroxide. The other evaluation results are shown in Table 1.

Example 6 Instead of IRGACURE®369 used in Example 1, 2-methyl- [4- (methylthio) phenyl] -2
-Morpholino-1-propanone (IRGACURER
907) was prepared and evaluated according to Example 1 using 7.5 g. Tetramethylammonium hydroxide 0.14
% Aqueous solution, a pattern of 20 μm × 20 μm could be resolved. The other evaluation results are shown in Table 1.

[0070]

[Table 1]

Example 7 7.5 g of IRGACURE 369 used in Example 1
Instead of 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (IRGAC
URE 907) 3.75g and IRGACURE 369
3.75 g were mixed and prepared and evaluated according to Example 1. Tetramethylammonium hydroxide 0.14
% Aqueous solution, a pattern of 20 μm × 20 μm could be resolved. The other evaluation results are shown in Table 2.

Example 8 Instead of IRGACURE 369 used in Example 1, (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-) (IRGACU
It was prepared and evaluated according to Example 1 using 7.5 g of RE 261 (manufactured by CIBA GEIGY). Tetramethylammonium hydroxide 0.18% aqueous solution 20 μm
A pattern of × 20 μm could be resolved. The other evaluation results are shown in Table 2.

Example 9 100 g of the copolymer solution obtained in Synthesis Example 1 (Copolymer 2
5 g) to diethylene glycol dimethyl ether 13.
IRGACURE 2615.0 after dilution with 64 g
g, γ-glycidoxypropyltrimethoxysilane 2.
5 g was dissolved and filtered using a millibore filter having a pore size of 0.22 μm to prepare a composition, which was then evaluated according to Example 1. Tetramethylammonium hydroxide 0.
A 20 μm × 20 μm pattern could be resolved with a 30% aqueous solution. The other evaluation results are shown in Table 2.

Example 10 IRGACURE 261 was replaced with IRGACURE 261 (3.75 g) instead of IRGACURE 369 used in Example 1.
RE 369 (3.75 g) was mixed and prepared and evaluated according to Example 1. A 20 μm × 20 μm pattern could be resolved with a 0.14% tetramethylammonium hydroxide aqueous solution. The other evaluation results are shown in Table 2.

Example 11 7.5 g of IRGACURE 369 used in Example 1
Was prepared and evaluated according to Example 1 using 5.0 g of tris (trichloromethyl) -s-triazine instead of. A 20 μm × 20 μm pattern could be resolved with a 0.16% aqueous solution of tetramethylammonium hydroxide. The other evaluation results are shown in Table 2.

Example 12 Aronix M-400 25.0 used in Example 1
25.0 g of KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) was used instead of g, and was prepared and evaluated according to Example 1. A 20 μm × 20 μm pattern could be resolved with a 0.14% tetramethylammonium hydroxide aqueous solution. The other evaluation results are shown in Table 2.

[0077]

[Table 2]

Examples 13 to 18 In addition to the composition solutions shown in Examples 1 to 6, imidazole 2 which is a curing catalyst for epoxy compounds was added as another compounding agent.
E4MZ-CN (manufactured by Shikoku Chemicals Co., Ltd.) was added and 0.25 g was added and prepared and evaluated according to Example 1. The results are shown in Table 3.

[0079]

[Table 3]

[0080]

In the past, in order to remove an unnecessary portion of the protective film, dry etching had to be performed, and there were problems that the panel manufacturing process was complicated and the display element had a defect due to dry etching. It was However, by using the radiation-sensitive resin composition of the present invention, it becomes possible to easily remove unnecessary portions by exposure / development while satisfying various characteristics required for the protective film. I am able to solve the problem.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location G03F 7/032 501 7/40 501 7124-2H (72) Inventor Bessho Nobuo Tsukiji, Chuo-ku, Tokyo No. 11-24 Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (A) (a) unsaturated carboxylic acid and /
Or a resin soluble in an alkaline aqueous solution which is a copolymer of an unsaturated carboxylic acid anhydride, (b) a radical-polymerizable compound having an epoxy group and (c) another radical-polymerizable compound, (B) at least one A heat-resistant radiation-sensitive resin composition comprising a polymerizable compound having an ethylenically unsaturated double bond and (C) a photopolymerization initiator.