JP2003330180A - Photosensitive resin composition and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having good suitability to coating and good storage stability and for forming a film having excellent transparency, heat resistance, developability, and flatness, and to provide a pattern forming method using the same. <P>SOLUTION: The photosensitive resin composition comprises (a) a copolymer of an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and an epoxy-containing polymerizable unsaturated compound, (b) a copolymer of an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and another monoolefinically unsaturated compound, (c) a quinonediazide- containing compound, and (d) an organic solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a method for forming a pattern using the same, more specifically, a protective film or interlayer for an electronic part such as a liquid crystal display device, an integrated circuit device, a solid-state image pickup device. The present invention relates to a photosensitive resin composition suitable for forming an insulating film and a pattern forming method using the same.

[Prior art]

Conventionally, a protective film for preventing deterioration and damage of electronic parts such as liquid crystal display devices, integrated circuit devices, and solid-state image pickup devices, and an interlayer insulating film provided for insulating between wirings arranged in layers Photosensitive resin compositions have been used to form Among them, in the case of a liquid crystal display element, for example, in a TFT type liquid crystal display element, a polarizing plate is provided on a glass substrate,
Transparent conductive circuit layers such as ITO and thin film transistors (TF)
T) is formed and covered with an interlayer insulating film to form a back plate, a polarizing plate is provided on a glass plate, and a black matrix layer and a color filter layer pattern are formed if necessary, and a transparent conductive circuit layer is further formed. , An interlayer insulating film is sequentially formed to form a top plate, and the back plate and the top plate are opposed to each other with a spacer interposed between them so that liquid crystal is sealed between the both plates. The material is required to be able to form a film having excellent transparency, heat resistance, developability and flatness.

[0003]

As the above-mentioned photosensitive resin composition, for example, JP-A-5-165214 discloses (A) (a) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (b). A resin soluble in an alkaline aqueous solution which is a copolymer of a radically polymerizable compound having an epoxy group and (c) another radically polymerizable compound, and (B)
A radiation-sensitive resin composition containing a radiation-sensitive acid-forming compound also contains an alkali-soluble acrylic polymer binder, a quinonediazide group-containing compound, a crosslinking agent and a photo-acid generator in JP-A-10-153854. Photosensitive resin compositions and the like have been proposed. However, the radiation-sensitive resin composition described in JP-A-5-165214 has good transparency, flatness, and heat resistance, and unnecessary portions can be easily removed by exposure and development. Since it is a terpolymer of an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, a radically polymerizable compound having an epoxy group, and another radically polymerizable compound, it is difficult to prepare a coating solution, and uniform coating is possible. It is difficult to form a uniform coating film on a film, especially on a large-sized substrate, and storage stability is poor and there is a drawback that the quality changes during storage. In addition, JP-A-1
Although the photosensitive resin composition described in JP-A No. 0-153854 has excellent transparency, flatness and developability, it cannot be said that the heat resistance is sufficient, and the heat resistance required for recent protective films and interlayer insulating films is not satisfied. I was not satisfied.

In view of the above situation, the inventors of the present invention have conducted extensive studies, and as a result, identified a binary copolymer of unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride and an epoxy group-containing polymerizable unsaturated compound. It is obtained without causing gelation by polymerizing in an organic solvent containing a compound of this binary copolymer, unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and other mono-olefinic unsaturated compounds By containing a copolymer as a resin component, transparency, heat resistance and flatness required for a protective film or an interlayer insulating film can be secured, and developability and coatability are excellent, and a uniform film, particularly The present invention has been completed by finding that it is possible to obtain a photosensitive resin composition which is easy to form a uniform film on a large-sized substrate and has good storage stability and excellent workability. That is,

An object of the present invention is to provide a photosensitive resin composition which is capable of forming a film having excellent transparency, heat resistance, developability and flatness, and which has excellent coatability and storage stability.

Another object of the present invention is to provide a method for forming a pattern using the above photosensitive resin composition.

[0007]

Means for Solving the Problems The present invention, which achieves the above objects, comprises: (a) a copolymer of an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and an epoxy group-containing polymerizable unsaturated compound; A photosensitive resin containing an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid anhydride and another monoolefinic unsaturated compound, (c) a quinonediazide group-containing compound, and (d) an organic solvent. The present invention relates to a composition and a method for forming a pattern using the composition.

The present invention will be described in detail below. The photosensitive resin composition of the present invention comprises the component (a) as described above.
Although the photosensitive resin composition contains the component (d), the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride as the component (a) is specifically a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid. Carboxylic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Examples of unsaturated carboxylic acid anhydrides include maleic anhydride and itaconic anhydride.

Examples of the epoxy group-containing polymerizable unsaturated compound as the component (a) include aliphatic epoxy group-containing polymerizable unsaturated compounds and alicyclic epoxy group-containing polymerizable unsaturated compounds. An alicyclic epoxy group-containing polymerizable unsaturated compound capable of forming a coating film having excellent heat resistance is preferable. Specific examples of the aliphatic epoxy group-containing polymerizable unsaturated compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n.
-Glycidyl propyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6-methacrylic acid 7
-Epoxyheptyl, α-ethylacrylic acid-6,7-
Epoxyheptyl, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3,
Examples thereof include 5-dimethylphenylpropyl] acrylamide, and specific examples of the alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (2) to (32).

[0010]

[Chemical 2]

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16]

[0025]

[Chemical 17]

[0026]

[Chemical 18]

[0027]

[Chemical 19]

[0028]

[Chemical 20]

[0029]

[Chemical 21]

[0030]

[Chemical formula 22]

[0031]

[Chemical formula 23]

[0032]

[Chemical formula 24]

[0033]

[Chemical 25]

[0034]

[Chemical formula 26]

[0035]

[Chemical 27]

[0036]

[Chemical 28]

[0037]

[Chemical 29]

[0038]

[Chemical 30]

[0039]

[Chemical 31]

[0040]

[Chemical 32] (In the formula, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ₅ represents 1 to 8 carbon atoms.
20 divalent hydrocarbon groups are shown, R ₃ , R ₄ and R ₅ may be the same or different, and w is a number from 0 to 10. )

The copolymerization ratio of the epoxy group-containing polymerizable unsaturated compound in the component (a) is 5 to 90 mols based on all components,
The range of 10 to 80 mol% is preferable. If it deviates from the above range, the heat resistance and the dissolution resistance decrease, which is not preferable.

The component (a) has the general formula 33

[0043]

[Chemical 33] (However, R ₁ represents a hydrocarbon group having 1 to 4 carbon atoms, R ₂
Represents a hydrocarbon group having 1 to 4 carbon atoms or a divalent hydrocarbon group, m represents 0 or 1, and n represents an integer of 3 to 5. In a polymerization solvent containing at least the compound represented by the formula (1), preferably in a polymerization solvent containing the compound in the range of 10 to 70% by weight, radical polymerization using a polymerization catalyst can be performed without gelation. .

Specific examples of the compound represented by the above chemical formula 33 are propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butyl alcohol, and 3. -Ethoxy-1-butyl alcohol, 3-propoxy-1-butyl alcohol, 3-methoxy-1-methylpropyl alcohol, 3-ethoxy-1-methylpropyl alcohol, 3-propoxy-1-methylpropyl alcohol, 2-methoxy -1-ethylethyl alcohol, 2-ethoxy-1-ethylethyl alcohol, 2
-Propoxy-1-ethylethyl alcohol, 5-methoxypentyl alcohol, 5-ethoxypentyl alcohol, 5-propoxypentyl alcohol, 4-methoxy-1-methylbutyl alcohol, 4-ethoxy-1-
Methylbutyl alcohol, 4-propoxy-1-methylbutyl alcohol, 3-methoxy-1-ethylpropyl alcohol, 3-ethoxy-1-ethylpropyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, methyl ethylene Examples thereof include glycol monomethyl ether and methyl ethylene glycol monoethyl ether. Further, as the other organic solvent of the polymerization solvent, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, ethylene glycol nomomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene Recall methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate,
Dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monoble ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2
-Methyl-3-methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ketone, methyl butyl ketone, dipropyl ketone,
Cyclohexanone, -n-butyl acetate, amyl acetate,
Examples thereof include ethyl lactate and l-n-butyl lactate, and these can be used alone or in combination of two or more kinds.

The polymerization catalyst to be used may be a usual radical polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2, Azo compounds such as 2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and hydrogen peroxide are preferable. When hydrogen peroxide is used as a radical polymerization initiator, it may be a redox type polymerization initiator combined with a reducing agent.

Other mono-olefinic unsaturated compounds forming the component (b) of the photosensitive resin composition of the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate and isopropyl. Acrylate, isopropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, tert-
Butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobonyl acrylate, isobonyl Methacrylate, tricyclo [5,2,1.0 ^2.6 ] decanyl acrylate, tricyclo [5,2,1.0 ^2.6 ] decanyl methacrylate, styrene, α-styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc. These can be used alone or in combination of two or more, but control of mechanical properties and solubility in alkaline aqueous solution It is two or more thereof ease. The copolymerization ratio of the monoolefin unsaturated compound in the component (b) is in the range of 20 to 95 mol%, preferably 30 to 90 mol% of the total components. When the amount is out of the above range, the alkali solubility becomes insufficient or becomes too large to form a good pattern.

The component (c) of the present invention is not particularly limited as long as it is a compound which can be used as a photosensitive component.
For example, naphthoquinone-1,2-diazide-4-sulfonic acid, naphthoquinone-1,2-diazide-5-sulfonic acid and other naphthoquinone-1,2-diazide sulfonyl halides, and esterified products of phenolic hydroxy compounds It is preferably used. Specifically, 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-
Diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone naphthoquinone-1,2-diazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone naphthoquinone-1,2-diazide- Ester compounds of trihydroxybenzophenone and naphthoquinone-1,2-diazide sulfonic acid such as 4-sulfonic acid ester and naphthoquinone-1,2-diazide-5-sulfonic acid ester of 2,4,6-trihydroxybenzophenone Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 4,4'-
Tetrahydroxybenzophenone naphthoquinone-1,
2-diazide-5-sulfonate, 2,3,4
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 3'-tetrahydroxybenzophenone, 2,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 3,4,3'-tetrahydroxybenzophenone, Naphthoquinone-1,2-diazide-4-sulfonic acid of 2,3,4,4'-tetrahydroxybenzophenone Ester, naphthoquinone-1,2-diazide-5-sulfonate of 2,3,4,4'-tetrahydroxybenzophenone, naphthoquinone-1,2-diazide of 2,3,4,2'-tetrahydroxybenzophenone Four
-Sulfonic acid ester, naphthoquinone of 2,3,4,2'-tetrahydroxybenzophenone-1,2-diazide-5-sulfonic acid ester, naphthoquinone of 2,3,4,4'-tetradoxy-3'-methoxybenzophenone Tetrahydroxybenzophenone and naphthoquinone such as -1,2-diazide-5-sulfonate
Ester compound with 1,2-diazidosulfonic acid; 2,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 3,4,2 ', 4'-pentahydroxybenzophenone, Naphthoquinone-1,2-of 2,3,4,2', 4'-pentahydroxybenzophenone Diazide-5
Sulfonic acid ester, 2,3,4,2 ′, 6′-naphthoquinone-1,2-diazide-4-sulfonic acid ester of pentahydroxybenzophenone, 2,3,4,2 ′,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 6'-pentahydroxybenzophenone, such as pentahydroxybenzophenone and naphthoquinone-1,2.
-Ester compounds with diazide sulfonic acid; 2,4
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, naphthoquinone of 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone 1,2-diazide-5-sulfonic acid ester, 3,4,5,3 ′,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 4 ', 5'-hexahydroxybenzophenone,
Hexahydroxybenzophenone and naphthoquinone-1,2-diazide sulfonic acid such as naphthoquinone-1,2-diazide-5-sulfonic acid ester of 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone And an ester compound with 2,2′-dihydroxydiphenylmethane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 2,2′-dihydroxydiphenylmethane naphthoquinone-1,2-diazide-5-sulfonic acid ester, 2 , 4'-Dihydroxydiphenylmethane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 2,4'-dihydroxydiphenylmethane naphthoquinone-1,2-diazide-5-sulfonic acid ester,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 4,4′-dihydroxydiphenylmethane, 4,
Naphthoquinone of 4'-dihydroxydiphenylmethane-
Ester compounds of dihydroxydiphenylmethane and naphthoquinone-1,2-diazide sulfonic acid such as 1,2-diazide-5-sulfonic acid ester; 1- (2-hydroxyphenyl) -1- (2'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of ethane, 1- (2-hydroxyphenyl) -1-
Naphthoquinone of (2'-hydroxyphenyl) ethane-
1,2-diazide-5-sulfonic acid ester, 1- (2
-Hydroxyphenyl) -1- (4'-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-4-
Sulfonic acid ester, 1- (2-hydroxyphenyl)
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of -1- (4'-hydroxyphenyl) ethane, 1
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of-(4-hydroxyphenyl) -1- (4'-hydroxyphenyl) ethane, 1- (4-hydroxyphenyl) -1- (4'-hydroxyphenyl) ) Naphthoquinone-1,2-diazide-5-sulfonate of ethane, 1-phenyl-1- (2,4-dihydroxyphenyl) naphthoquinone-1,2-diazide-4-sulfonate of ethane, 1-phenyl Naphthoquinone-1,2-diazide-5-sulfonic acid ester of -1- (2,4-dihydroxyphenyl) ethane, 1-phenyl-1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,6-dihydroxyphenyl) ethane, 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenyl-1- (2,6-dihydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -2-
Naphthoquinone of (2'-hydroxyphenyl) ethane-
1,2-diazide-4-sulfonic acid ester, 1- (2
-Hydroxyphenyl) -2- (2'-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-5-
Sulfonic acid ester, 1- (2-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2- (4'-hydroxyphenyl) ethane, 1
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(2-hydroxyphenyl) -2- (4'-hydroxyphenyl) ethane, 1- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) ) Naphthoquinone-1,2-diazide-4-sulfonic acid ester of ethane, Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) ethane , 1-phenyl-2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,4-dihydroxyphenyl) ethane, 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenyl-2- (2,4-dihydroxyphenyl) ethane, Naphthoquinone-1,2-phenyl-1-phenyl-2- (2,6-dihydroxyphenyl) ethane Diazide
4-sulfonic acid ester, 1-phenyl-2- (2,6
-Dihydroxyphenyl) ethane naphthoquinone-1,
An ester compound of diphenylhydroxyethane and naphthoquinone-1,2-diazidosulfonic acid such as 2-diazide-5-sulfonic acid ester; 1- (2-hydroxyphenyl) -1- (2'-hydroxyphenyl) propane Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1- (2-hydroxyphenyl) -1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2'-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2-hydroxyphenyl) -1- (4'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -1- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, 1- (4-hydroxyphenyl) -1- (4'-
Hydroxyphenyl) propane naphthoquinone-1,2
-Diazide-4-sulfonic acid ester, 1- (4-hydroxyphenyl) -1- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, 1-phenyl-1- (2,4-dihydroxyphenyl) naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 1-phenyl- 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2,4-dihydroxyphenyl) propane, 1
-Phenyl-1- (2,6-dihydroxyphenyl) propane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 1-phenyl-1- (2,6-dihydroxyphenyl) propane naphthoquinone-1,2 -Diazide-5-sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1- (2-dihydroxyphenyl) -2- (2'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) ) -2-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2'-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -2- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-5-sulfonic acid ester of propane, 2- (2-hydroxyphenyl) -1- (4 '
-Hydroxyphenyl) propane naphthoquinone-1,
2-Diazide-4-sulfonic acid ester, naphthoquinone-1,2-diazide-5-of 2- (2-hydroxyphenyl) -1- (4'-hydroxyphenyl) propane
Sulfonic acid ester, 1- (4-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2- (4′-hydroxyphenyl) propane,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 1-phenyl-2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,4-dihydroxyphenyl) propane, 1
-Phenyl-2- (2,4-dihydroxyphenyl) propane naphthoquinone-1,2-diazide-5-sulfonate, 2-phenyl-1- (2,4-dihydroxyphenyl) propane naphthoquinone-1,2 -Diazide-4-sulfonic acid ester, 2-phenyl-1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2,4-dihydroxyphenyl) propane, 1
-Phenyl-2- (2,6-dihydroxyphenyl) propane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 1-phenyl-2- (2,6-dihydroxyphenyl) propane naphthoquinone-1,2 -Diazide-5-sulfonic acid ester, 2-phenyl-1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,6-dihydroxyphenyl) propane, 2
-Phenyl-1- (2,6-dihydroxyphenyl) propane naphthoquinone-1,2-diazide-5-sulfonate, 2- (2-hydroxyphenyl) -2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2'-hydroxyphenyl) propane, 2-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2-hydroxyphenyl) -2- (2'-hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -2- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 2- (2-hydroxyphenyl) -2- (4'-
Hydroxyphenyl) propane naphthoquinone-1,2
-Diazide-5-sulfonic acid ester, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 2- (4-hydroxyphenyl) -2
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(4'-hydroxyphenyl) propane, 2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of phenyl-2- (2,4-dihydroxyphenyl) propane, Naphthoquinone-1,2-phenyl-2-phenyl-2- (2,4-dihydroxyphenyl) propane Diazide-5-sulfonic acid ester, 2-phenyl-2-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,6-dihydroxyphenyl) propane, 2
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of -phenyl-2- (2,6-dihydroxyphenyl) propane, 1- (2-hydroxyphenyl) -3-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2'-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of (2-hydroxyphenyl) -3- (2'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -3- (4'-hydroxyphenyl) Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 1- (2-hydroxyphenyl) -3- (4'-
Hydroxyphenyl) propane naphthoquinone-1,2
-Diazide-5-sulfonic acid ester, 1- (4-hydroxyphenyl) -3- (4'-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of propane, 1- (4-hydroxyphenyl) -3
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of-(4'-hydroxyphenyl) propane, 1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of phenyl-3- (2,4-dihydroxyphenyl) propane, Naphthoquinone-1,2-phenyl-1-phenyl-3- (2,4-dihydroxyphenyl) propane Diazide-5-sulfonic acid ester, 1-phenyl-3-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (2,6-dihydroxyphenyl) propane, 1
An ester compound of dihydroxyphenylpropane and naphthoquinone-1,2-diazidesulfonic acid, such as naphthoquinone-1,2-diazide-5-sulfonic acid ester of -phenyl-3- (2,6-dihydroxyphenyl) propane; Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 2,2 ', 2 "-trihydroxytriphenylmethane, Naphthoquinone-1,2-diazide of 2,2', 2" -trihydroxytriphenylmethane 5-
Sulfonic acid ester, naphthoquinone-1,2 ', 4 "-trihydroxytriphenylmethane-1,2-diazide-4-sulfonic acid ester, naphthoquinone-1,2,2', 4" -trihydroxytriphenylmethane naphthoquinone-1, 2-diazide-5-sulfonic acid ester, naphthoquinone-1,2,4 ′, 4 ″ -trihydroxytriphenylmethane,
2-diazide-4-sulfonic acid ester, 2, 4 ',
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 4 "-trihydroxytriphenylmethane, 4,
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 4 ', 4 "-trihydroxytriphenylmethane, Naphthoquinone-1,2-diazide-5 of 4,4', 4" -trihydroxytriphenylmethane Sulfonic acid ester, naphthoquinone-1,2 ', 2 "-trihydroxytriphenylethane-1,2-diazide-4-sulfonic acid ester, naphthoquinone-1,2,2', 2" -trihydroxytriphenylethane naphthoquinone-1, 2-diazide-5
-Sulfonic acid ester, naphthoquinone of 2,2 ', 4 "-trihydroxytriphenylethane-1,2-diazide-4-sulfonic acid ester, naphthoquinone-1 of 2,2', 4" -trihydroxytriphenylethane , 2-
Diazide-5-sulfonic acid ester, 2,4 ', 4 "-
Naphthoquinone of trihydroxytriphenylethane-
1,2-diazide-4-sulfonic acid ester, 2,
Naphthoquinone-1,2-diazide-5-sulfonate of 4 ', 4 "-trihydroxytriphenylethane, Naphthoquinone-1,2-diazide-4- of 4,4', 4" -trihydroxytriphenylethane Sulfonic acid ester, naphthoquinone-1,4,4 ', 4 "-trihydroxytriphenylethane-1,2-diazide-5-sulfonic acid ester, 2,2', 2" -trihydroxytriphenylpropane naphthoquinone-1, 2-Diazide-4-sulfonic acid ester, naphthoquinone-1,2,2 ', 2 "-trihydroxytriphenylpropane
-Diazide-5-sulfonate, 2,2 ', 4 "
-Naphthoquinone-1,2-diazide-4-sulfonic acid ester of trihydroxytriphenylpropane, 2,
Naphthoquinone-1,2-diazide-5-sulfonate of 2 ', 4 "-trihydroxytriphenylpropane, Naphthoquinone-1,2-diazide-4- of 2,4', 4" -trihydroxytriphenylpropane Sulfonate, 2,4 ', 4 "-Trihydroxytriphenylpropane naphthoquinone-1,2-diazide-5-
Sulfonic acid ester, naphthoquinone-1,4,4 ', 4 "-trihydroxytriphenylpropane-1,2-diazide-4-sulfonic acid ester, naphthoquinone-1,4,4', 4" -trihydroxytriphenylpropane Two
-Diazide-5-sulfonic acid ester, 4- [1,1-
Dimethyl-1- (o-hydroxymethyl) phenyl]-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of bis (o-hydroxyphenyl) methane, 4-
[1,1-Dimethyl-1- (o-hydroxymethyl) phenyl] -bis (o-hydroxyphenyl) methane naphthoquinone-1,2-diazide-5-sulfonate, 4- [1,1-dimethyl- Naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1- (o-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl) methane, 4- [1,1-dimethyl-1- (o-hydroxymethyl) ) Phenyl] -bis (p-hydroxyphenyl) methane naphthoquinone-1,2-diazide-5-
Sulfonic acid ester, 4- [1,1-dimethyl-1-
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of (p-hydroxymethyl) phenyl] -bis (o-hydroxyphenyl) methane, 4- [1,1-dimethyl-1- (p-hydroxymethyl) phenyl ] -Bis (o-hydroxyphenyl) methane naphthoquinone-
1,2-diazide-5-sulfonic acid ester, 4-
[1,1-Dimethyl-1- (p-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl) methane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 4- [1,1-dimethyl- 1- (p-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl)
Methane naphthoquinone-1,2-diazide-5-sulfonic acid ester, [4- (o-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane naphthoquinone-1,2-diazide-4-sulfonic acid Ester, [4- (o-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane naphthoquinone-1,2-diazide-5-sulfonate, [4- (o-hydroxyphenylmethyl) phenyl] -Naphthoquinone-1,2-diazide-4-sulfonic acid ester of bis (p-hydroxyphenyl) methane,
[4- (o-hydroxyphenylmethyl) phenyl]-
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of bis (p-hydroxyphenyl) methane, [4-
Naphthoquinone of (p-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane-
1,2-diazide-4-sulfonic acid ester, [4-
Naphthoquinone of (p-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane-
1,2-diazide-5-sulfonic acid ester, [4-
Naphthoquinone of (p-hydroxyphenylmethyl) phenyl] -bis (p-hydroxyphenyl) methane-
1,2-diazide-4-sulfonic acid ester, [4-
Naphthoquinone of (p-hydroxyphenylmethyl) phenyl] -bis (p-hydroxyphenyl) methane-
1,2-diazide-5-sulfonic acid ester, 1- {4
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of-[1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane, 1- Naphthoquinone-1,2-diazide-5-sulfonic acid ester of {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane, Naphthoquinone of 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane-
1,2-diazide-4-sulfonic acid ester, 1- {4
-[1,1-Dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-5-sulfonate, 1- Naphthoquinone-1,2-diazide-4-sulfonic acid ester of {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (p-
Naphthoquinone of hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane-
1,2-diazide-5-sulfonic acid ester, 1- {4
-[1,1-Dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 1- Naphthoquinone-1,2-diazide-5-sulfonic acid ester of {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenylmethyl)
Phenyl] -1,1-bis (o-hydroxyphenyl)
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of ethane, 1- [4- (o-hydroxyphenylmethyl) phenyl] -1,1-bis (o-hydroxyphenyl) ethane naphthoquinone-1,2- Diazide-5
Sulfonic acid ester, naphthoquinone-1,2-diazide-4-sulfonic acid ester of 1- [4- (o-hydroxyphenylmethyl) phenyl] -1,1-bis (p-hydroxyphenyl) ethane, 1- [4 -(O-Hydroxyphenylmethyl) phenyl] -1,1-bis (p-
Hydroxyphenyl) ethane naphthoquinone-1,2-
Diazide-5-sulfonic acid ester, 1- [4- (p-
Hydroxyphenylmethyl) phenyl] -1,1-bis (o-hydroxyphenyl) ethane naphthoquinone-
1,2-diazide-4-sulfonic acid ester, 1- [4
-(P-hydroxyphenylmethyl) phenyl] -1,
Naphthoquinone-1,2-diazide-5-sulfonic acid ester of 1-bis (o-hydroxyphenyl) ethane, 1
-[4- (p-hydroxyphenylmethyl) phenyl]
Naphthoquinone-1,2-diazide-4-sulfonic acid ester of -1,1-bis (p-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenylmethyl) phenyl] -2,2-bis (o -Hydroxyphenyl) ethane naphthoquinone-1,2-diazide-5-sulfonic acid ester, 1- [4- (o-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ethane naphthoquinone- 1,2-Diazide-4-sulfonic acid ester, 1- [4- (o-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-
5-sulfonic acid ester, 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ethane naphthoquinone-1,2-diazide-4-sulfonic acid ester, 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (p
-Hydroxyphenyl) ethane naphthoquinone-1,2
-Diazide-5-sulfonic acid ester and the like.
These may be used alone or in combination of two or more.

The component (d) of the present invention has the same general formula 33:
Examples of the organic solvent containing at least the compound described above include the same compounds as the above-mentioned polymerization solvent and other organic solvents. Since the component (d) is the same as the polymerization solvent, the photosensitive resin composition contains the component (d) as it is. When the content is out of the range of 10 to 70% by weight, the compound of the general formula 33 or another organic solvent is preferably added to adjust the content to the above range. As a result, the photosensitive resin composition of the present invention exhibits excellent coatability and can form a uniform film even on a large substrate.

The component (a) in the photosensitive resin composition of the present invention is 5 to 5 parts by weight based on 100 parts by weight of the total of the components (a) to (d).
90 parts by weight, preferably 20 to 60 parts by weight, and the component (b) is 5 parts with respect to 100 parts by weight of the total of the components (a) to (d).
-90 parts by weight, preferably 20-60 parts by weight, (c)
The component is 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total of components (a) to (d), and the component (d) is 100 parts by weight of the total of components (a) to (d). Against 4
It is preferable that the content is 000 parts by weight or less, preferably 3000 parts by weight or less. When the content of the component (a) is less than 5 parts by weight, heat resistance is poor, and when it exceeds 90 parts by weight, coatability and flatness are poor, which is not preferable. Further, if the content of the component (b) is less than 5 parts by weight, the mechanical properties will be poor, and if it exceeds 90 parts by weight, the heat resistance will be poor, such being undesirable. Furthermore, (c)
If the content of the components is less than 5 parts by weight, poor development may occur, resulting in 6
If it exceeds 0 parts by weight, transparency, insulation and flatness are deteriorated, which is not preferable.

In addition to the above, the photosensitive resin composition of the present invention contains, if necessary, an ultraviolet absorber, a sensitizer, a sensitization aid,
Additive components such as a plasticizer, a thickener, an organic solvent, a dispersant, a defoaming agent, an adhesion promoter, and an organic or inorganic suspending agent can be added.

Specific examples of the plasticizer include dibutyl phthalate (DBP), dioctyl phthalate (DOP), polyethylene glycol, glycerin and dibutyl tartrate.

Examples of the defoaming agent include alkylene glycol type defoaming agents such as polyethylene glycol (molecular weight 400 to 800), silicone type, higher alcohol type defoaming agents and the like.

As the adhesion promoter, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane,
Examples thereof include silane coupling agents such as γ-methacryloxypropyltrialkoxysilane and titanium coupling agents. These may be used alone or in combination of two or more.

Next, as a method for forming a pattern using the photosensitive resin composition of the present invention, (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and an epoxy group-containing polymerizable unsaturated compound are formed on a substrate. The copolymer of (b) unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and other monoolefinic unsaturated compound, (c) quinonediazide group-containing compound and (d) organic solvent The photosensitive resin composition is applied using a spinner, a roll coater, a spray or the like to form a photosensitive resin composition layer, a predetermined mask pattern is placed on the photosensitive resin composition layer, and active light rays are radiated through the mask. Examples of the method include a method of exposing, developing and forming an image pattern, followed by heating and curing. Examples of the substrate include a black matrix layer, a polarizing plate provided with a color filter layer and a glass plate provided with a transparent conductive circuit layer, if necessary, in the production of a liquid crystal display device. Examples of the light source that emits the actinic rays include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and an excimer laser generator. Examples of the developer used in the developing treatment include hydroxides, carbonates, bicarbonates, phosphates, pyrophosphates, benzylamine, butylamine and other primary amines of alkali metals such as lithium, sodium and potassium, and dimethyl. Secondary amines, dibenzylamine, diethanolamine, etc.
Tertiary amines such as primary amines, trimethylamine, triethylamine and triethanolamine, cyclic amines such as morpholine, piperazine and pyridine, polyamines such as ethylenediamine and hexamethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzyl Ammonium hydroxide, ammonium hydroxide such as trimethylphenylbenzylammonium hydroxide, trimethylsulfonium hydroxide, trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, dimethylbenzylsulfonium hydroxide and other sulfonium hydroxides, choline, silicic acid Examples include salt-containing buffer solutions. Further, the heat curing temperature is in the range of 150 ° C to 250 ° C.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION Next, examples of the present invention will be described, but the present invention is not limited thereto.

[0056]

EXAMPLES (Synthesis of Copolymer) Synthesis Example 1 (Synthesis of Copolymer P1) Proper glycol was flushed with nitrogen gas in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with propylene glycol monomethyl ether. 200 parts by weight of acetate was added and the mixture was stirred. Further, 18 parts by weight of methyl methacrylate, 60 parts by weight of styrene, 22 parts by weight of methacrylic acid, 7 parts by weight of a polymerization initiator 2,2′-azobisisobutyronitrile and 30 parts by weight of propylene glycol monomethyl ether acetate were mixed and dissolved. The solution was placed in the dropping funnel. Then, the liquid temperature in the flask was kept at 80 ° C., and the mixed solution was dropped into the flask from the dropping funnel over 2 hours with stirring. Further, the same temperature was maintained for 4 hours under stirring. Then, it was cooled to room temperature and the copolymer (P1) (concentration 30%, polystyrene-converted weight average molecular weight Mw 8.0)
00) was obtained.

Synthesis Example 2 (Synthesis of Copolymer P2) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen in an appropriate amount to replace the atmosphere with nitrogen, and 200 parts by weight of 3-methoxyacetic acid butylacetate was added. Stirring was performed.
Further, 7 parts by weight of methyl methacrylate, 70 parts by weight of styrene, 23 parts by weight of methacrylic acid, 6 parts by weight of a polymerization initiator 2,2′-azobisisobutyronitrile and 30 parts by weight of 3-methoxyacetic acid butyl acetate were mixed and dissolved. The prepared solution was placed in the dropping funnel. Next, the liquid temperature in the flask is set to 90 ° C.
The mixed solution was added dropwise from the dropping funnel to the flask over 2 hours with stirring. Further, the same temperature was maintained for 4 hours under stirring. Then, it cooled to room temperature and obtained the copolymer (P2) (concentration 30%, polystyrene conversion weight average molecular weight Mw11,000).

Synthetic Example 3 (Synthesis of Copolymer P3) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen in an appropriate amount to replace the atmosphere with nitrogen, and 200 parts by weight of propylene glycol monomethyl ether acetate was added and stirred. I went. Further, methyl methacrylate 18 parts by weight, styrene 32 parts by weight, α-methylstyrene 30 parts by weight, methacrylic acid 20 parts by weight, polymerization initiator 2,2′-azobisisobutyronitrile 7 parts by weight and propylene glycol monomethyl ether. A solution prepared by mixing and dissolving 30 parts by weight of acetate was placed in the dropping funnel. Then, the liquid temperature in the flask was kept at 80 ° C., and the mixed solution was dropped into the flask from the dropping funnel over 2 hours with stirring. Further, the same temperature was maintained for 4 hours under stirring. Then, it cooled to room temperature and obtained the copolymer (P3) (concentration 30%, polystyrene conversion weight average molecular weight Mw10,000).

Synthesis Example 4 (Synthesis of Copolymer P4) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen in an appropriate amount to replace the atmosphere with nitrogen, and 200 parts by weight of propylene glycol monomethyl ether acetate was added and stirred. I went. Further, 8 parts by weight of methacrylic acid, 60 parts by weight of isobornyl methacrylate, 22 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 6 parts by weight of 2,2′-azobisisobutyronitrile as a polymerization initiator, and propylene glycol monomethyl ether. Acetate 3
A solution prepared by mixing and dissolving 0 part by weight was placed in the dropping funnel.
Then, the liquid temperature in the flask was kept at 80 ° C., and the mixed solution was dropped into the flask from the dropping funnel over 2 hours with stirring. Further, the same temperature was maintained for 4 hours under stirring. Then, it was cooled to room temperature and the copolymer (P4) (concentration 30
%, Polystyrene equivalent weight average molecular weight Mw 12,000
0) was obtained.

Synthesis Example 5 (Synthesis of Copolymer P5) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen in an appropriate amount to replace the atmosphere with nitrogen, and 200 parts by weight of 3-methoxybutylacetate was added and stirred. I went. Also, 35 parts by weight of isobornyl methacrylate, 35 parts by weight of tricyclo [5,2,1.0 ^2.6 ] decanyl acrylate, 26 parts by weight of methacrylic acid, and 4 parts of methyl methacrylate.
A solution prepared by mixing and dissolving 6 parts by weight of a polymerization initiator 2,2′-azobisisobutyronitrile and 30 parts by weight of propylene glycol monomethyl ether acetate was placed in a dropping funnel. Then, the liquid temperature in the flask was maintained at 85 ° C., and the mixed solution was added dropwise from the dropping funnel to the flask over 2 hours with stirring. Further, the same temperature was maintained for 4 hours under stirring. Then, the mixture is cooled to room temperature and the copolymer (P
5) (concentration 30%, polystyrene equivalent weight average molecular weight M
w15,000) was obtained.

Synthesis Example 6 (Synthesis of Copolymer Q1) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was purged with nitrogen in an appropriate amount to replace the atmosphere with nitrogen, and 100 parts by weight of propylene glycol monomethyl ether acetate and propylene glycol monomethyl were added. 100 parts by weight of ether was added and the mixture was stirred. Also, 20 parts by weight of methacrylic acid,
80 parts by weight of (3,4-epoxycyclohexyl) methyl methacrylate, polymerization initiator 2,2′-azobis (2,2
4-Dimethylvaleronitrile) 11 parts by weight, propylene glycol monomethyl ether acetate 15 parts by weight, and propylene glycol monomethyl ether 15 parts by weight were mixed and dissolved into a dropping funnel. Then, the liquid temperature in the flask was maintained at 70 ° C., and the mixed solution was added dropwise from the dropping funnel to the flask over 3 hours with stirring.
Further, the same temperature was maintained for 4 hours under stirring. Then, it cooled to room temperature and obtained the copolymer (Q1) (concentration 30%, polystyrene conversion weight average molecular weight Mw10,000).

Synthesis Example 7 (Synthesis of Copolymer Q2) An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, and 100 parts by weight of 3-methoxybutyl acetate and 3-methoxy were used. 100 parts by weight of -1-butyl alcohol was added and stirred. Further, methacrylic acid 28 parts by weight, (3,4-epoxycyclohexyl) methyl methacrylate 72 parts by weight, polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) 12 parts by weight, 3-methoxybutyl acetate 15
A solution in which 1 part by weight and 15 parts by weight of 3-methoxy-1-butyl alcohol were mixed and dissolved was placed in a dropping funnel. Then, the liquid temperature in the flask was maintained at 70 ° C., and the mixed solution was added dropwise from the dropping funnel to the flask over 3 hours with stirring. Furthermore, the same temperature was maintained for 4 hours. Then, it cooled to room temperature and obtained the copolymer (Q2) (concentration 30%, polystyrene conversion weight average molecular weight Mw12,000).

Synthesis Example 8 (Synthesis of Copolymer Q3) An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with nitrogen, and 60 parts by weight of 3-methoxybutyl acetate and propylene glycol monomethyl were added. 140 parts by weight of ether was added, and the mixture was stirred. Further, 18 parts by weight of methacrylic acid, 82 parts by weight of (3,4-epoxycyclohexyl) methyl methacrylate, 13 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile), 15 parts of 3-methoxybutyl acetate.
A solution in which 1 part by weight and 15 parts by weight of 3-methoxy-1-butyl alcohol were mixed and dissolved was placed in a dropping funnel. Then, the liquid temperature in the flask was maintained at 70 ° C., and the mixed solution was added dropwise from the dropping funnel to the flask over 3 hours with stirring. Furthermore, the same temperature was maintained for 4 hours. Then, it cooled to room temperature and obtained the copolymer (Q3) (concentration 30%, polystyrene conversion weight average molecular weight Mw 7,000).

Synthesis Example 9 (Synthesis of Copolymer Q4) An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, and 100 parts by weight of propylene glycol monomethyl ether acetate and propylene glycol monomethyl were added. 100 parts by weight of ether was added and the mixture was stirred. 22 parts by weight of methacrylic acid,
Glycidyl methacrylate 78 parts by weight, polymerization initiator 2,
A solution in which 8 parts by weight of 2'-azobisisobutyronitrile and 20 parts by weight of propylene glycol monomethyl ether acetate were mixed and dissolved was put in a dropping funnel. Then
The liquid temperature in the flask was maintained at 70 ° C., and the mixed liquid was added dropwise from the dropping funnel to the flask over 2 hours with stirring. Further, the same temperature was maintained for 4 hours under stirring. Then, it cooled to room temperature and obtained the copolymer (Q4) (concentration 30%, polystyrene conversion weight average molecular weight Mw12,000).

Comparative Synthesis Example 1 (Synthesis of Copolymer R1) A flask equipped with a reflux condenser, a dropping funnel and a stirrer was flushed with an appropriate amount of nitrogen to replace the atmosphere with nitrogen, and 200 parts by weight of propylene glycol monomethyl ether acetate was added. Stirring was performed. Further, 13 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 22 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and a polymerization initiator 2,
A solution in which 8 parts by weight of 2'-azobisisobutyronitrile and 20 parts by weight of propylene glycol monomethyl ether acetate were mixed and dissolved was put in a dropping funnel. Then, the reaction solution was heated to 70 ° C. while being stirred and added dropwise from the dropping funnel into the flask over 2 hours, and was kept at the same temperature for 4 hours. After that, it is cooled to room temperature and the copolymer (R1)
(Concentration 30%, polystyrene equivalent weight average molecular weight Mw3
5,000) was obtained.

Example 1 Copolymer (P1) (30% concentration) 4 obtained in Synthesis Example 1
0 part by weight, 40 parts by weight of the copolymer (Q1) obtained in Synthesis Example 6, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] 6 parts by weight of benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester and 40 parts by weight of propylene glycol monomethyl ether acetate were mixed and dissolved by stirring with a mixer, followed by degassing under reduced pressure to prepare a photosensitive resin composition. did. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The above-mentioned photosensitive resin composition solution was applied to the glass substrate 1.
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and a film thickness of 3 μm with a spinner, and then dried on a hot plate for 3 minutes at 90 ° C.
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, it is immersed in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained.

The coated film obtained above was exposed to the whole surface again using an ultrahigh pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven.
The substrate having the cured film of the obtained photosensitive resin composition was measured with a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) to find that the minimum transmittance at a wavelength of 400 nm to 800 nm was 92.8%. Moreover, the pattern collapse did not occur.

Further, in order to examine the heat resistance, the coating film was heat-cured in a clean oven at 200 ° C. for 30 minutes, and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability of the above-mentioned photosensitive resin composition, the photosensitive resin composition was stored at room temperature for one month and then the viscosity was measured. For the viscosity after preparation,
The case where the rate of increase in viscosity after storage at room temperature for 1 month was less than 3% was marked with ◯, and the case where it was 3% or more was marked with x. The above results are shown in Table 1.

Example 2 Copolymer (P2) (30% concentration) 4 obtained in Synthesis Example 2
0 part by weight, 40 parts by weight of the copolymer (Q1) obtained in Synthesis Example 6, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] 6 parts by weight of benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester and 40 parts by weight of 3-methoxybutylacetate were mixed and dissolved by stirring with a mixer, followed by degassing under reduced pressure to prepare a photosensitive resin composition. did. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The above-mentioned photosensitive resin composition solution was applied to the glass substrate 1
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and a film thickness of 3 μm with a spinner, and then dried on a hot plate for 3 minutes at 90 ° C.
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, the substrate is immersed in a 0.5% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained.

The coated film obtained above was exposed to the whole surface again using an ultra-high pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven.
Using a spectrophotometer UV-2500PC (manufactured by Shimadzu Corp.), the obtained substrate with a cured film of the photosensitive resin composition was measured at a wavelength of 4
When the minimum transmittance of 00 nm to 800 nm was measured, it was 9
It was 2.2%. Moreover, the pattern collapse did not occur.

Further, in order to examine the heat resistance, the coating film was heated and cured at 200 ° C. for 30 minutes in a clean oven, and then again heat-treated at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability of the above-mentioned photosensitive resin composition, the photosensitive resin composition was stored at room temperature for 1 month and then the viscosity was measured. For the viscosity after preparation,
The case where the rate of increase in viscosity after storage at room temperature for 1 month was less than 3% was marked with ◯, and the case where it was 3% or more was marked with x. The above results are shown in Table 1.

Example 3 Copolymer (P3) (30% concentration) 4 obtained in Synthesis Example 3
0 parts by weight, 40 parts by weight of the copolymer (Q2) obtained in Synthesis Example 7, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] 6 parts by weight of benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester and 40 parts by weight of 3-methoxybutylacetate were mixed and dissolved by stirring with a mixer, followed by degassing under reduced pressure to prepare a photosensitive resin composition. did.

The above-mentioned photosensitive resin composition is applied to the glass substrate 173.
7 (Corning Co., Ltd .: 0.7 mm thickness × 150 mm diameter) was coated with a spinner to a film thickness of 2.5 μm, and then dried on a hot plate at 90 ° C. for 3 minutes, and 10
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, the substrate is immersed in a 0.5% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained.

The coated film obtained above was exposed to the whole surface again using an ultrahigh pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven. The obtained substrate with a cured film of the photosensitive resin composition is spectrophotometer U
V-2500PC (made by Shimadzu Corp.) is used and the wavelength is 4
When the minimum transmittance of 00 nm to 800 nm was measured, it was 9
It was 3.8%. Moreover, the pattern collapse did not occur.

Further, in order to measure the heat resistance, the coating film was heat-cured in a clean oven at 200 ° C. for 30 minutes and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability, the above-mentioned photosensitive resin composition was stored at room temperature for 1 month, and then the viscosity was measured. When the viscosity increase rate after storage at room temperature for 1 month is less than 3% relative to the viscosity after preparation, ○ is 3% or more.
And The above results are shown in Table 1.

Example 4 Copolymer (P4) (30% concentration) 3 obtained in Synthesis Example 4
5 parts by weight, 45 parts by weight of the copolymer (Q2) obtained in Synthesis Example 7, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] 6.4 parts by weight of benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester and 40 parts by weight of 3-methoxybutylacetate were mixed and dissolved by stirring with a mixer, followed by degassing under reduced pressure to obtain a photosensitive resin composition. Was prepared. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The above-mentioned photosensitive resin composition solution was applied to the glass substrate 1.
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and applied with a spinner to a film thickness of 2 μm, and dried on a hot plate for 3 minutes at 90 ° C.
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, it is immersed in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained.

The coating film obtained above was exposed to the whole surface again using an ultra-high pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 200 ° C. for 30 minutes in a clean oven.
The substrate having the cured film of the obtained photosensitive resin composition was measured with a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) to find that the minimum transmittance at a wavelength of 400 nm to 800 nm was 94.1%. Moreover, the pattern collapse did not occur.

Further, in order to measure the heat resistance, the coating film was heat-cured in a clean oven at 200 ° C. for 30 minutes and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability, the above-mentioned photosensitive resin composition was stored at room temperature for 1 month, and then the viscosity was measured. When the viscosity increase rate after storage at room temperature for 1 month is less than 3% relative to the viscosity after preparation, ○ is 3% or more.
And The above results are shown in Table 1.

Example 5 Copolymer (P5) (30% concentration) 4 obtained in Synthesis Example 5
5 parts by weight, 35 parts by weight of the copolymer (Q3) obtained in Synthesis Example 8, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] Benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester 3 parts by weight, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2
2.2 parts by weight of 2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate and 50 parts by weight of 3-methoxybutylacetate were added to 3-methoxy-1.
-Butyl alcohol (20 parts by weight) was mixed, dissolved by stirring with a mixer, and then degassed under reduced pressure to prepare a photosensitive resin composition. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The above-mentioned photosensitive resin composition solution was applied to the glass substrate 1
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and applied with a spinner to a film thickness of 2 μm, dried at 90 ° C. for 2 minutes on a hot plate, and
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, it is immersed in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained.

The coating film obtained above was exposed to the whole surface again using an ultra-high pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven.
The substrate having the cured film of the obtained photosensitive resin composition was measured with a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) to find that the minimum transmittance at a wavelength of 400 nm to 800 nm was 94.4%. Moreover, the pattern collapse did not occur.

In order to measure heat resistance, the coating film was heat-cured in a clean oven at 200 ° C. for 30 minutes, and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability, the above-mentioned photosensitive resin composition was stored at room temperature for 1 month, and then the viscosity was measured. When the viscosity increase rate after storage at room temperature for 1 month is less than 3% relative to the viscosity after preparation, ○ is 3% or more.
And The above results are shown in Table 1.

Example 6 Copolymer (P5) (30% concentration) 3 obtained in Synthesis Example 5
0 parts by weight, 50 parts by weight of the copolymer (Q2) obtained in Synthesis Example 7, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] Benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester 3 parts by weight, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2
-Hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester 3 parts by weight, 3-methoxybutyl acetate 50 parts by weight and 3-methoxy-1-
20 parts by weight of butyl alcohol was mixed, dissolved by stirring with a mixer, and then degassed under reduced pressure to prepare a photosensitive resin composition. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The photosensitive resin composition solution was added to the glass substrate 1
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and applied with a spinner to a film thickness of 2 μm, dried at 90 ° C. for 2 minutes on a hot plate, and
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Next, after immersion in a 0.3% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute for development, and rinsing with pure water to remove unnecessary portions,
A pattern of 10 μm line / 10 μm space was obtained.

The coated film obtained above was exposed to the whole surface again using an ultrahigh pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven.
The substrate having the cured film of the obtained photosensitive resin composition was measured with a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) to find that the minimum transmittance at a wavelength of 400 nm to 800 nm was 94.5%. Moreover, the pattern collapse did not occur.

Further, in order to measure heat resistance, the coating film was heated and cured at 200 ° C. for 30 minutes in a clean oven, and then again heat-treated at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability, the above-mentioned photosensitive resin composition was stored at room temperature for 1 month, and then the viscosity was measured. When the viscosity increase rate after storage at room temperature for 1 month is less than 3% relative to the viscosity after preparation, ○ is 3% or more.
And The above results are shown in Table 1.

The copolymer (P1) (3) obtained in Synthesis Example 1
0% concentration) 40 parts by weight, 40 parts by weight of the copolymer (Q4) obtained in Synthesis Example 9, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4- Hydroxyphenyl) ethyl] benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester (6 parts by weight) and propylene glycol monomethyl ether acetate (40 parts by weight) were mixed and dissolved by stirring with a mixer, followed by degassing under reduced pressure to obtain a photosensitive resin. A composition was prepared. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The above-mentioned photosensitive resin composition solution was applied to the glass substrate 1.
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and a film thickness of 3 μm with a spinner, and then dried on a hot plate for 3 minutes at 90 ° C.
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, it is immersed in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained.

The coated film obtained above was exposed to the whole surface again using an ultrahigh pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven.
The substrate having the cured film of the obtained photosensitive resin composition was measured with a spectrophotometer UV-2500PC (manufactured by Shimadzu Corp.) to find that the minimum transmittance at a wavelength of 400 nm to 800 nm was 93.6%. Moreover, the pattern collapse did not occur.

Further, in order to examine the heat resistance, the coating film was heat-cured in a clean oven at 200 ° C. for 30 minutes, and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability of the above-mentioned photosensitive resin composition, the photosensitive resin composition was stored at room temperature for 1 month, and then the viscosity was measured. For the viscosity after preparation,
The case where the rate of increase in viscosity after storage at room temperature for 1 month was less than 3% was marked with ◯, and the case where it was 3% or more was marked with x. The above results are shown in Table 1.

Comparative Example 1 80 parts by weight of the copolymer (R1) (30% concentration) obtained in Comparative Synthesis Example 1, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1 -Bis (4-hydroxyphenyl) ethyl] benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester 6.4 parts by weight, propylene glycol monomethyl ether acetate 40
After mixing parts by weight and dissolving with stirring with a mixer, degassing under reduced pressure was performed to prepare a photosensitive resin composition. Then, filtration was performed with a filter having a pore size of 0.1 μm to obtain a photosensitive resin composition.

The photosensitive resin composition solution was added to the glass substrate 1
737 (Corning: 0.7 mm thickness x 150 mm
Diameter) and a film thickness of 3 μm with a spinner, and then dried on a hot plate for 3 minutes at 90 ° C.
Exposure was performed using a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) through a positive mask pattern of μm line pattern / 10 μm space pattern. Then, it is immersed in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide for 1 minute for development, and rinsed with pure water to remove unnecessary portions.
A pattern of μm line / 10 μm space was obtained, but a residue was found in a part.

The coating film obtained above was exposed to the whole surface again using an ultra-high pressure mercury lamp without passing through a positive mask pattern, and then heat-cured at 220 ° C. for 30 minutes in a clean oven.
The substrate having the cured film of the obtained photosensitive resin composition was measured with a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) to find that the minimum transmittance at a wavelength of 400 nm to 800 nm was 90.1%. Moreover, the pattern collapse did not occur.

Further, in order to measure the heat resistance, the coating film was heat-cured in a clean oven at 200 ° C. for 30 minutes and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment was calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C. for 30 minutes. 230
○ when the film thickness reduction rate after heating at ℃ for 1 hour is less than 3%,
The case of 3% or more was marked with x.

Further, in order to examine the storage stability, the above-mentioned photosensitive resin composition was stored at room temperature for 1 month, and then the viscosity was measured. When the viscosity increase rate after storage at room temperature for 1 month is less than 3% relative to the viscosity after preparation, ○ is 3% or more.
And The above results are shown in Table 1.

[0106]

[Table 1]

[0107]

The photosensitive resin composition of the present invention is transparent,
In addition to forming a protective film and an interlayer insulating film with excellent heat resistance and flatness, and also with excellent coatability and developability, a uniform film can be easily formed even on a large substrate. Work can be done efficiently due to good storage stability.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA02 AA04 AA10 AA11 AA18                       AB14 AB16 AB17 AC01 AD03                       BE01 CB13 CB14 CB16 CB41                       CC03 FA17 FA29                 4J100 AB07P AE18P AJ01Q AJ02Q                       AJ08Q AJ09Q AK31Q AL08P                       AL08Q AL10Q AM21P AM21Q                       AQ01P BA03P BA04P BA14P                       BA15P BA21P BA38P BC03P                       BC54P BC59P CA04 JA38

Claims (8)

[Claims] 1. A copolymer of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and an epoxy group-containing polymerizable unsaturated compound, and (b) unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and others. 2. A photosensitive resin composition comprising the monoolefin unsaturated compound copolymer, the (c) quinonediazide group-containing compound, and the (d) organic solvent. 2. The photosensitive resin composition according to claim 1, wherein the epoxy group-containing polymerizable unsaturated compound is an alicyclic epoxy group-containing polymerizable unsaturated compound. 3. The general formula 1 in which the component (d) is (e) (However, R ₁ represents a hydrocarbon group having 1 to 4 carbon atoms, R ₂
Represents a hydrocarbon group having 1 to 4 carbon atoms or a divalent hydrocarbon group, and R ₁ and R ₂ may be the same or different. Also, m is 0
Alternatively, 1 and n represent an integer of 3 to 5. 3. The photosensitive resin composition according to claim 1, which is an organic solvent containing at least the compound represented by the formula (1). 4. The photosensitive resin composition according to claim 3, wherein the component (d) contains the component (e) in an amount of 10 to 70% by weight. 5. The photosensitive resin composition according to claim 1, wherein the component (a) is a copolymer obtained by polymerization in a polymerization solvent containing the component (e). 6. The content of the component (e) in the polymerization solvent is 10 to 10.
70% by weight is the photosensitive resin composition according to claim 5. 7. The method for forming a pattern using the photosensitive resin composition according to claim 1, wherein the content of the component (e) in the photosensitive resin composition is 10 to 70% by weight of the component (d). A method for forming a pattern, which comprises coating on a substrate after adjustment, selectively exposing through a mask pattern, developing to form an image pattern, and then heating to crosslink and cure the image pattern. 8. The method for forming a pattern according to claim 7, wherein the substrate is a glass substrate on which a polarization generating material, a transparent conductive circuit layer and / or a thin film transistor are formed on a glass plate.