JP2880523B2 - Photosensitive resin composition and photosensitive element using the same - Google Patents

Description

The present invention relates to a photosensitive resin composition having excellent heat resistance, adhesiveness, electrical and mechanical properties, and high photosensitivity even when used as a thick film. And a photosensitive element using the same.

(Prior art) Conventionally, heat-resistant polymers typified by polyimide have excellent heat resistance, electrical and mechanical properties, and are therefore used for surface protection films such as interlayer insulating films, passivation films, and buffer coat films of semiconductor devices. In the field of wiring boards, it has been widely used as an interlayer insulating film of a multilayer wiring board.

In the semiconductor industry, inorganic materials have conventionally been used for interlayer insulating films and surface protective films. In recent years, however, organic materials having excellent heat resistance, such as polyimide, have been mainly used by taking advantage of their characteristics. .

By the way, in forming a pattern of a surface protective film or an interlayer insulating film of a semiconductor element or a multilayer wiring board, a resist material is formed on a substrate surface, an exposure is performed on a predetermined portion, an unnecessary portion is removed by etching, and a substrate surface is removed. Since the pattern formation is performed through a complicated and diverse process such as cleaning work, the required portion of the resist material after exposure and development can be used as it is as an insulating material. Development of optical materials is desired.

For these materials, for example, heat-resistant photosensitive materials based on photosensitive polyimide, cyclized polybutadiene, and the like have been proposed. In particular, photosensitive polyimide has excellent heat resistance and eliminates impurities. It is particularly noted because of its ease of use.

As such a photosensitive polyimide, for example, JP-A-58-120636 proposes a photosensitive polyimide precursor in which a photosensitive group is introduced into the polyimide precursor through an ester bond. However, since it is not always good, for example, it is necessary to coat an aminosilane adhesion promoter on the surface of the base material in advance, and the number of pattern formation steps is increased.

Japanese Patent Application Laid-Open No. 60-100143 proposes a method of imparting a photosensitive group by using an isocyanate compound for a polyamic acid, but it has an inherent problem in the optical transparency of the polyamic acid. Therefore, it is difficult to form a thick film.

(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned problems of the prior art, and is excellent in light transmittance and solubility and formed as a final cured film on the surface of a substrate. When you do
An object of the present invention is to provide a photosensitive resin composition capable of forming a thick film having both heat resistance and adhesiveness.

(Means for Solving the Problems) The present invention relates to (A) a compound represented by the general formula (I): (Wherein, R ₁ is a tetravalent residue excluding four carboxyl groups of an aromatic tetracarboxylic acid having a fluorine atom, and a tetravalent residue excluding four carboxyl groups of an aromatic tetracarboxylic acid having a siloxane group. R ₂ is a tetravalent residue excluding the four carboxyl groups of the aromatic tetracarboxylic acid other than the above, and R ₂ is a divalent aromatic diamine having a fluorine atom.
A divalent residue excluding two amino groups, a divalent residue excluding two amino groups of an aromatic diamine having a siloxane group, or a divalent residue excluding two amino groups of an aromatic diamine other than the above.
Y is a monovalent organic group having an ethylenically unsaturated group, n is 0 or 1, m is 1 or 2, n
+ M = 2), in which at least one R ₁ or at least one R ₂ is a group having a fluorine atom,
A photosensitive resin composition comprising: a fluorine atom and siloxane group-containing polyimide precursor, wherein at least one R ₁ or at least one R ₂ is a group having a siloxane group, and (B) a photoinitiator. The present invention relates to a photosensitive element obtained by applying the above-mentioned photosensitive resin composition on a substrate, drying and coating the substrate.

For convenience, hereinafter, a tetravalent residue excluding four carboxyl groups of an aromatic tetracarboxylic acid will be simply referred to as a tetravalent aromatic group, and a divalent residue excluding two amino groups of an aromatic diamine will be simply referred to as two. Abbreviated as valent aromatic group.

The (A) polymer containing a fluorine atom and a siloxane group having a repeating unit represented by the general formula (I) used in the present invention is, for example, a compound represented by the following general formula (II) or (III) Simply referred to as compound I) and an aromatic amine, an aromatic amine having a fluorine atom, or an amine having a siloxane group (hereinafter simply referred to as compound II)
Can be obtained by polycondensation of

(Wherein, R ₃ and R ₄ are a tetravalent aromatic group, a tetravalent aromatic group having a fluorine atom and / or a tetravalent aromatic group having a siloxane group, and X is a halogen atom Alternatively, the hydroxyl group and Y are monovalent groups having an ethylenically unsaturated group.) The fluorine atom and siloxane group-containing polymer of the component (A) used in the present invention has both a fluorine atom and a siloxane group. Have Therefore, in the above-mentioned polycondensation reaction, the raw materials (compound I and / or compound II) used always contain at least one compound having a fluorine atom and at least one compound having a siloxane group. Need to be.

The reaction between compound I and compound II is preferably carried out in an inert organic solvent at a temperature of 0 to 100 ° C.
More preferably, it is carried out at a temperature of ° C.

Compound I and compound II are compound I / compound II at 0.8 / 1 ~
It is preferably used at a ratio of 1.2 / 1 (molar ratio), and more preferably at approximately equimolar.

The reaction between compound I and compound II is promoted by using a carbodiimide-type dehydrating condensing agent, for example, a dehalogenating agent such as dicyclohexylcarbodiimide or an amine, for example, pyridine or triethylamine as a catalyst.

The organic solvent used in the above reaction is (A)
A polar solvent that completely dissolves a fluorine atom- and siloxane group-containing polymer having a repeating unit represented by the general formula (I) is generally preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N , N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, N, N
-Dimethylpropylene urea, N, N-dimethylethylene urea and the like.

In some cases, in order to isolate a polymer from the above reaction mixture, a method of adding the reaction mixture little by little to alcohols or water is preferable.

The solid thus obtained can be purified by dissolving it again in the organic solvent used for the reaction, adding it to alcohols or water, and reprecipitating the solid.

Compound I is, for example, an aromatic tetracarboxylic dianhydride having a fluorine atom, an aromatic tetracarboxylic dianhydride having a siloxane group, or an aromatic tetracarboxylic dianhydride other than the above (collectively, (Hereinafter, simply referred to as compound I ') by half-esterification by fully or partially opening the ring with a hydroxy compound having an ethylenically unsaturated group, or further, the half-esterified product is converted to thionyl chloride or pentachloride. It can be obtained by acid halide with phosphorus or the like. The reaction between the aromatic tetracarboxylic dianhydride and the hydroxy compound having an ethylenically unsaturated group can be promoted by adding, for example, pyridine, dimethylaminopyridine or the like.

In view of the optical transparency of the photosensitive resin composition and the heat resistance and adhesiveness of the resulting coating film, the aromatic tetracarboxylic dianhydride having a fluorine atom constituting the compound I ′ and the siloxane group are used in the present invention. The aromatic tetracarboxylic dianhydride or the aromatic tetracarboxylic dianhydride other than the above is preferably used in the compound I ′ in an amount of 5 to 85 mol%, 5 to 85 mol%, or 10 to 90 mol%, respectively. It is more preferable to use 10 to 75 mol%, 10 to 75 mol%, and 15 to 80 mol%, respectively.

Further, (A) a fluorine atom- and siloxane group-containing polymer having a repeating unit represented by the general formula (I) used in the present invention includes, for example, a fluorine-containing polymer having a repeating unit represented by the general formula (IV). With a polyimide precursor containing a silicon atom and a siloxane group (Wherein, R ₅ has the same meaning as R ₁ in the general formula (I), and R ₆ has the same meaning as R ₂ in the general formula (I)) Isocyanate compound having an ethylenically unsaturated group Can also be obtained by reaction with

The reaction between a fluorine atom-containing siloxane group-containing polyimide precursor having a repeating unit represented by the general formula (IV) and an isocyanate compound having an ethylenically unsaturated group is carried out in an inert organic solvent at 0 to 100 ° C. The reaction is preferably performed at a temperature of 20 to 70 ° C.

The ratio of the isocyanate compound having an ethylenically unsaturated group to the polyimide precursor having a repeating unit containing a fluorine atom and a siloxane group represented by the general formula (IV) depends on the sensitivity of the photosensitive resin composition and the coating film. From the viewpoint of heat resistance, it is usually preferable to react 0.01 to 0.8 equivalent, more preferably 0.1 to 0.5 equivalent, to 1 equivalent of the carboxyl group in the polyimide precursor.

Further, the reaction of an isocyanate compound having an ethylenically unsaturated group with a polyimide precursor having a fluorine atom and a siloxane group having a repeating unit represented by the general formula (IV) is carried out by triethylamine, 1,4-diazobicyclo [2 ,
[2,2] The use of an amine such as octane or a tin compound such as dibutyltin dilaurate or dibutyltin diacetate as a catalyst facilitates the use.

The fluorine atom- and siloxane group-containing polyimide precursor having a repeating unit represented by the general formula (IV) can be obtained by a known method using the compound I 'and the compound II as starting materials.

The fluorine atom and siloxane group-containing polyimide precursor having a repeating unit represented by the general formula (IV) has both a fluorine atom and a siloxane group. Therefore, it is necessary that the starting materials contain at least one kind having a fluorine atom and at least one kind having a siloxane group.

In the above, the reaction between the compound I 'and the compound II is performed in an inert organic solvent at a temperature of 0 to 100 ° C, preferably 10 to 80 ° C, and can be obtained as an organic solvent solution of a polyimide precursor.

The compound I 'and the compound II have the former / the latter of 0.8 / 1
It is preferably used at a ratio of 1.21.2 / 1 (molar ratio), more preferably at an equimolar ratio.

In view of the optical transparency of the photosensitive resin composition and the heat resistance and adhesiveness of the resulting coating film, a fluorine atom-containing aromatic tetracarboxylic dianhydride constituting the compound I 'and an aromatic having a siloxane group The tetracarboxylic dianhydride or other aromatic tetracarboxylic dianhydride is preferably used in the compound I 'in an amount of 5 to 85 mol%, 5 to 85 mol%, or 10 to 90 mol%, respectively. 75mol%, 10 ~ 75mol%, 15
More preferably, it is used in an amount of about 80 mol%.

The organic solvent used in the reaction between the compound I 'and the compound II may be (A) a fluorine atom- and siloxane group-containing polymer having a repeating unit represented by the general formula (I) which is completely formed. Polar solvents that dissolve are generally preferred, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, N , N-dimethylpropyleneurea, N, N-dimethylethyleneurea and the like.

As the aromatic tetracarboxylic dianhydride having a fluorine atom used in the present invention, for example, 2,2-bis (3,4
-Dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,2-
Bis [4- (2,3-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, (trifluoromethyl) pyromellitic dianhydride, bis (trifluoromethyl) pyromellitic dianhydride, 3,3 '-Bis (trifluoromethyl) -4,4', 5,5'-tetracarboxybiphenyl dianhydride, 2,2 ', 5,5'-tetrakis (trifluoromethyl) -3,3', 4 , 4'-tetracarboxybiphenyl dianhydride, 3,3'-bis (trifluoromethyl) -4,
4 ', 5,5'-tetracarboxybiphenyl ether dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,
5'-tetracarboxybiphenyl ether dianhydride, 3,
3'-bis (trifluoromethyl) -4,4 ', 5,5'-tetracarboxybenzophenone dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5 ' -Tetracarboxybenzophenone dianhydride, 1,4-bis [3- (trifluoromethyl) -4,5-dicarboxyphenoxy] benzene dianhydride, 1,4-bis [2- (trifluoro Methyl) -4,
5-Dicarboxyphenoxy) benzene dianhydride, 4,4 '
-Bis [3- (trifluoromethyl) -4,5-dicarboxyphenoxy] biphenyl dianhydride, 1-trifluoromethyl-2,5-bis [3- (trifluoromethyl) -4,5
-Dicarboxyphenoxy) benzene dianhydride, 1,1'-
Bis (trifluoromethyl) -3,3'-bis [3- (trifluoromethyl) -4,5-dicarboxyphenoxy]
Biphenyl dianhydride, 4,4'-bis [3- (trifluoromethyl) -4,5-dicarboxyphenoxy] biphenyl ether dianhydride, 1-trifluoromethyl-3,5-bis (3 , 4-Dicarboxyphenyl) benzene dianhydride, 1,4
-Bis (trifluoromethyl) -3,5-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,2,4,6-tetrakis (trifluoromethyl) -3,5-bis (3 , 4-Dicarboxyphenyl) benzene dianhydride, 1,1'-bis (trifluoromethyl) -3,3 '-(3,4-dicarboxyphenoxy) biphenyl dianhydride, 1,1' , 4,4'-Tetrakis (trifluoromethyl) 3,3 '-(3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [4- (2,3
-Dicarboxybenzoyloxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [3-methyl-4-
(2,3-dicarboxybenzoyloxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (2-
Trifluoromethyl-3,4-dicarboxybenzoyloxy) phenyl] hexafluoropropane dianhydride, 1,5
-Bis [4- (3,4-dicarboxybenzoyloxy)
[Phenyl] decafluoropentane dianhydride, 1,3-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] hexafluoropropane dianhydride, 1,6-bis [4-
(3,4-dicarboxybenzoyloxy) phenyl] dodecafluorohexane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane Anhydride, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] octafluorobutane dianhydride, 2,2-bis [4- (2-trifluoromethyl-3,4-dicarboxy) phenyl] hexafluoropropane dianhydride , 1,3-Bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 1,5-bis [4- (3,4-dicarboxyphenoxy) phenyl] Decafluoropentane dianhydride, 1,6
-Bis [4- (3,4-dicarboxyphenoxy) phenyl] dodecafluoropropane dianhydride;
Among them, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride is commercially available from Central Glass Co., etc., is easily available, and has the heat resistance of the photosensitive resin composition. Preferred from the point.

Examples of the aromatic tetracarboxylic dianhydride having a siloxane group used in the present invention include, for example, And the like.

Other aromatic tetracarboxylic dianhydrides used in the present invention include, for example, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-Biphenyltetracarboxylic dianhydride, meta-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, para-terphenyl-3,3 ", 4,4" -Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) propane dianhydride and the like.

Examples of the aromatic amine having a fluorine atom used in the present invention include 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (3
-Methyl-4-aminophenyl) hexafluoropropane, 2,2-bis (3,5-dimethyl-4-aminophenyl)
Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-
Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 1,4-bis [2- (trifluoromethyl) -4-aminophenoxy) benzene,
4,4'-bis [2- (trifluoromethyl) -4-aminophenoxy) biphenyl, 4,4'-bis [2- (trifluoromethyl) -4-aminophenoxy] diphenylsulfone, 4,4'-bis [4- (4-aminophenylthio)
-Phenyl] biphenyl, 2,2'-bis [4- (4-aminophenylthio) -phenyl] hexafluoropropane, 2,2'-bis [4- (2-trifluoromethyl-4-
Aminophenoxy) phenyl] hexafluoropropane and the like. Among them, 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis [4- (4
-Aminophenoxy) phenyl] hexafluoropropane is commercially available from Central Glass Company, is easily available, and is preferable in view of the heat resistance of the photosensitive resin composition.

Examples of the aromatic amine having a siloxane group used in the present invention include, for example, And the like.

Other aromatic amines used in the present invention include, for example, 4,4'-diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4 '
-Diaminodiphenyl sulfide, benzidine, meta-
Phenylenediamine, para-phenylenediamine, 1,5-
Naphthalenediamine, 2,6-naphthalenediamine, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone and the like are used.

These aromatic amines can be used alone or in combination of two or more.

In addition, a diaminoamide compound represented by the general formula (V) can also be used.

(However, Ar is an aromatic group, Z is shows the SO ₂ or CO, located in one of the ortho positions to each other with an amino group and Z-NH ₂₎ as the compound, e.g., 4,4'-diamino Diphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-
Diaminodiphenyl ether-4-sulfonamide, 4,
4'-diaminodiphenylmethane-3-sulfonamide,
3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4 ' -Diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone-4
-Sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfon-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide , 3,4'-Diaminodiphenylsulfide-4-sulfonamide, 3,3'-
Diaminodiphenyl sulfide-4-sulfonamide, 3,4'-diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenyl ether- 3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether
3'-carbonamide, 3,3'-diaminodiphenyl ether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide , 3,4'-Diaminodiphenylmethane-3'-carbonamide, 3,3'-Diaminodiphenylmethane-4-carbonamide, 4,4'-Diaminodiphenylsulfone-3-carbonamide, 3,4 '-Diaminodiphenylsulfone-4-carbonamide, 3,4'-
Diaminodiphenylsulfone-3'-carbonamide,
3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3 '-Diaminodiphenyl sulphide-4-carbonamide, 3,4'-diaminodiphenyl sulphide-3'-sulphonamide, 1,4-diaminobenzene-2-carbonamide and the like.

Examples of the hydroxy compound having an ethylenically unsaturated group used in the present invention include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethanediacrylate, trimethylolethanedimethacrylate, pentaerythritol triacrylate, and pentaerythritol. Trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate , Allyl alcohol, glycerin diallyl ether, trimethylolpropane diallyl ether, trimethylolethanediallyl ether, Pentaerythritol diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, Axis Lise roll triallyl ether, crotyl alcohol, vinyl phenol, cinnamyl alcohol, allyl phenol, o
-Cinnamyl phenol, And the like.

These hydroxy compounds having an ethylenically unsaturated group can be used alone or in combination of two or more.

Examples of the isocyanate compound having an ethylenically unsaturated group used in the present invention include, for example, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, isocyanatopentyl acrylate, isocyanatohexyl acrylate, isocyanatooctyl acrylate, Isocyanatodecyl acrylate, isocyanatooctadecylacrylate, isocyanatoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatopentyl methacrylate, isocyanatohexyl methacrylate, isocyanatooctyl methacrylate, isocyanatodecyl methacrylate, isocyanatooctadecylmethacrylate , Isocyanatoethyl crotonate, isocyanate propyl crotonate, isocyanate hexyl crotonate And the like. Isocyanatoethyl methacrylate can be obtained as a commercial product from Dow Chemical Co., Showa Rhodia Chemical Co., and the like.

Examples of the (B) photoinitiator used in the present invention include: Michler's ketone, benzoin, 2-methylbenzoyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4, 4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-diethylthioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-
Hydroxycyclohexylphenyl ketone, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-propanone, diacetyl, benzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulphide, anthracene, phenanthrenequinone,
Riboflavin tetrabutyrate, acrylic orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 3,3-carbonyl-bis (7-diethylamino) coumarin, 2,6-bis (p-diethylaminobenzylidene) -4-methyl- 4-azacyclohexanone, 6-
Bis (p-dimethylaminobenzylidene) -cyclopentanone, 2,6-bis (p-diethylaminobenzylidene)
And 4-phenylcyclohexanone, aminostyryl ketone represented by the following formula, and the like.

These (B) photoinitiators can be used alone or in combination of two or more.

These (B) photoinitiators may be used in combination with amines and amino acids as photoinitiating aids.

As the amines, for example, ethyl p-dimethylaminobenzoate, methyl p-diethylaminobenzoate, ethyl p-diethylaminobenzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzo Examples thereof include nitrile and ethyl N, N-dimethylanthranilate.

As amino acids, for example, N-phenylglycine, N-
Methyl-N- (p-chlorophenyl) glycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (n-propyl) -N- (p-chlorophenyl) glycine, N-methyl-N- (p- Bromophenyl) glycine, N-ethyl-N- (p-bromophenyl) glycine, N- (p-cyanophenyl) glycine, N- (p-chlorophenyl) glycine, N- (p-bromophenyl) glycine and the like can be mentioned.

The amount of the photoinitiator and amines and amino acids used as photoinitiating aids is determined by the following formula (A) in view of the sensitivity of the photosensitive resin composition and the heat resistance of the coating film. For 100 parts by weight of polymer having units
It is 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight.

These (B) photoinitiators, amines and amino acids can be used alone or in combination of two or more. In order to improve the thermal stability of the composition, known thermal initiators, amines and amino acids can be used. A polymerization inhibitor can coexist.

Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, chloranil, naphthylamine,
β-naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, p-toluidine, methylene blue, 2,2′-methylenebis (4-methyl-6-t-
Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) and the like.

In the present invention, a polymer unsaturated compound can be used if necessary.

As the polymerizable unsaturated compound, for example, acrylic acid,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carbitol acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl Acrylate, dipropylene glycol diacrylate, 2,2-
Bis- (4-acryloxydiethoxyphenyl) propane, 2,2-bis- (4-acryloxypropylxyphenyl) propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, penta Erythritol triacrylate, triacryl formal, tetramethylol methane tetraacrylate, tris (2-hydroxyethyl) isocyanuric acid, Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2,2-bis- (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate Methacrylate,
Tetramethylolmethanetetramethacrylate, tris (2-hydroxyethyl) isocyanuric acid, And the like.

The photosensitive resin composition of the present invention can contain an organic solvent.

As such an organic solvent, for example, the aforementioned (A)
A solvent or the like that completely dissolves the polymer having the repeating unit represented by the general formula (I) can be used. In such a case, the amount of the organic solvent used is 10
It is preferably set to about 95% by weight, more preferably 30 to 80% by weight.

The photosensitive resin composition of the present invention can be patterned by a usual fine processing technique.

The photosensitive resin composition of the present invention is applied to a support substrate such as a glass substrate, a silicon wafer, or a copper-clad laminate by means of spin coating using a spinner, dipping, spray printing, or the like, and dried to form a coating film. Can be.

The thickness of the coating film can be adjusted by the coating means, the solid content concentration and the viscosity of the varnish of the photosensitive polymer composition of the present invention.

Further, the photosensitive resin composition is coated on a flexible substrate, for example, a polyester film, dried and laminated, and if necessary, a cover sheet of polyethylene or the like is provided thereon, and a photosensitive element having a San Germanti structure is formed in advance. It is also possible to prepare and peel off the cover sheet of this photosensitive element to form a coating on the supporting substrate to be coated.

A relief pattern is obtained by irradiating the coating film with a light source on the supporting substrate and then dissolving and removing the unexposed portions with a developing solution.

At this time, for example, ultraviolet light, visible light, radiation, or the like can be used as the light source.

Examples of the developer include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone , N-benzyl-2-pyrrolidone, N-acetyl-ε-caprolactam, N, N-dimethylpropylene urea, N, N-dimethylethylene urea, or other polar solvent alone or a non-solvent for polyamic acid such as methanol,
Ethanol, isopropyl alcohol, benzene, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, toluene, xylene, methyl cellosolve,
It can be used as a mixture with water, a basic compound, a basic aqueous solution and the like.

Examples of the basic compound include monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, sodium carbonate,
Potassium carbonate, sodium phosphate and the like can be mentioned.

When adjusting the basic aqueous solution, the basic compound is preferably used in an amount of usually 0.0001 to 30 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of water.

Next, the relief pattern formed by development can be washed with a rinsing liquid to remove the developing solution.

As the rinsing liquid, a non-solvent of a polyamic acid having good miscibility with the developing solution is used. For example, methanol, ethanol, isopropyl alcohol, benzene, toluene,
Xylene, methyl cellosolve, water and the like.

The relief pattern obtained by the above process is a precursor of polyimide, and by heating at 150 to 450 ° C,
A heat-resistant relief pattern having an imide ring and other cyclic groups is obtained.

(Examples) Hereinafter, the present invention will be described with reference to examples.

(A) Production examples of a fluorine atom- and siloxane group-containing polymer having a repeating unit represented by the general formula (I) are shown below as Synthesis Examples 1 to 24.

Synthesis Example 1 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 20.7 g (0.04 mol), 1,3-bis (3,4-dicarboxyphenyl) -1,1 2,5.6 g (0.06 mol) of 3,3,3-tetramethyldisiloxane dianhydride and 3,3 ′,
4,4'-benzophenonetetracarboxylic dianhydride 32.2 g
(0.1 mol) were added with 400 ml of N-methyl-2-pyrrolidone and 52.0 g (0.4 mol) of 2-hydroxymethacrylate, and the mixture was stirred at room temperature for 12 hours. To this solution, 70 g of thionyl chloride was added dropwise over 1 hour under ice cooling, and then the mixture was stirred at room temperature for 2 hours. To this solution, 40.0 g (0.2 mol) of 4,4'-diaminodiphenyl ether was added and stirred for 8 hours.

Further, 80 ml of ethanol was added and the mixture was stirred for 3 hours, and then slowly poured into the water of No. 8 to precipitate a polymer as a thread-like solid. This polymer was named PI-1.

Synthesis Example 2 Meta-terphenyl-3,3 ″, 4,4 ″ was used in place of 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride used in Synthesis Example 1. A polymer was obtained in the same manner as in Synthesis Example 1 except that 37.0 g (0.1 mol) of tetracarboxylic dianhydride was used. This polymer was named PI-2.

Synthesis Example 3 Instead of 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride used in Synthesis Example 1, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride 29.4 g
(0.1 mol) and 2,4-bis (4- (4 mol) instead of 40.0 g (0.2 mol) of 4,4'-diaminodiphenyl ether.
A polymer was obtained in the same manner as in Synthesis Example 1 except that 82.1 g (0.2 mol) of -aminophenoxy) phenyl) propane was used. This polymer was named PI-3.

Synthesis Example 4 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 22.2 g (0.05 mol), 1,3-bis (3,4-dicarboxyphenyl) -1,1 21.3 g (0.05 mol) of 3,3,3-tetramethyldisiloxane dianhydride and 3,3 ′,
4,4'-benzophenonetetracarboxylic dianhydride 32.2 g
(0.1 mol) in 250 ml of N-methyl-2-pyrrolidone and then 40.0 g of 4,4'-diaminodiphenyl ether
(0.2 mol) was added and the mixture was stirred at room temperature for 4 hours.

Next, 15.5 g (0.1 mol) of isocyanatoethyl methacrylate was added to the solution, and the mixture was stirred at room temperature for 10 hours.

Further, 80 ml of ethanol was added, and the mixture was poured into water 8. As a result, the polymer was precipitated as a thread-like solid. The polymer was named PI-4.

Synthesis Example 5 In place of 15.5 g (0.1 mol) of isocyanatoethyl methacrylate used in Synthesis Example 4, 29.0 g (0.1 mol) of an isocyanate compound having the following structural formula was used. A coalescence was obtained. This polymer is PI-
No. 5.

Synthesis Example 6 Instead of 40.0 g (0.2 mol) of 4,4'-diaminodiphenyl ether used in Synthesis Example 4, 28.0 g (0.14 mol) of 4,4'-diaminodiphenyl ether and 2,2-bis (4 A polymer was obtained in the same manner as in Synthesis Example 4 except that 20.0 g (0.06 mol) of (-aminophenyl) hexafluoropropane was used. This polymer was named PI-6.

Synthesis Example 7 To 32.2 g (0.1 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added N-methyl-2-pyrrolidone 20.
0 ml and 26.0 g (0.2 mol) of 2-hydroxymethacrylate were added, and the mixture was stirred at room temperature for 12 hours. To this solution, 35 g of thionyl chloride was added dropwise over 1 hour under ice cooling, followed by stirring at room temperature for 2 hours. 2,2-bis (4
-Aminophenyl) hexafluoropropane 10.0 g (0.0
3 mol), 1,3-bis (4-aminophenyl) -1,1,3,3-
6.6 g (0.02 mol) of tetramethyldisiloxane and 4,4-
10.0 g (0.05 mol) of diaminodiphenyl ether was added and stirred for 8 hours.

Further, 75 ml of ethanol was added and the mixture was stirred for 3 hours. Thereafter, the mixture was slowly poured into water of 8 to precipitate a polymer as a thread-like solid. This polymer was named PI-7.

Synthesis Example 8 Instead of 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride used in Synthesis Example 7, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride 37.0 g
(0.1 mol), and the others were the same as in Synthesis Example 7.
A polymer was obtained. This polymer was named PI-8.

Synthesis Example 9 2,2-bis (4-aminophenyl) used in Synthesis Example 7
Instead of 10.0 g (0.03 mol) of hexafluoropropane,
2,2-bis (4- (4-aminophenoxy) phenyl)
A polymer was obtained in the same manner as in Synthesis Example 7 except that 15.5 g (0.03 mol) of hexafluoropropane was used. This polymer was named PI-9.

Synthesis Example 10 33.2 g (0.1 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added to N-methyl-2-pyrrolidone 25
Dissolved in 0 ml and then 10.0 g (0.03 mol) of 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-
6.6 g (0.02 mol) of bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane and 10.0 g (0.05 mol) of 4,4-diaminodiphenyl ether were added and stirred for 4 hours.

Next, 7.7 g (0.05 mol) of isocyanatoethyl methacrylate was added to this solution, and the mixture was stirred at room temperature for 10 hours.

Further, 80 ml of methanol was added and the mixture was stirred for 3 hours, and then poured into water of 8. As a result, a polymer precipitated as a thread-like solid. This polymer was named PI-10.

Synthesis Example 11 2,2-bis (4-aminophenyl) used in Synthesis Example 10
Instead of 10.0 g (0.03 mol) of hexafluoropropane,
2,2-bis (4- (4-aminophenoxy) phenyl)
A polymer was obtained in the same manner as in Synthesis Example 10 except that 15.5 g (0.03 mol) of hexafluoropropane was used. This polymer was designated as PI-11.

Synthesis Example 12 In place of 32.2 g (0.1 mol) of benzophenonetetracarboxylic dianhydride used in Synthesis Example 10, 2,2-bis (3,4-
A polymer was obtained in the same manner as in Synthesis Example 10, except that 22.2 g (0.05 mol) of dicarboxyphenyl) hexafluoropropane dianhydride and 16.1 g (0.05 mol) of benzophenonetetracarboxylic dianhydride were used. . This polymer was designated as PI-12.

Synthesis Example 13 Instead of 32.2 g (0.1 mol) of benzophenonetetracarboxylic dianhydride used in Synthesis Example 10, 2,2-bis (3,4-
A polymer was obtained in the same manner as in Synthesis Example 10 except that 44.4 g (0.1 mol) of dicarboxyphenyl) hexafluoropropane dianhydride was used. This polymer was named PI-13.

Synthesis Example 14 13.3 g (0.03 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride 22.6 g
(0.07 mol), 200 ml of N-methyl-2-pyrrolidone and 26.0 g (0.2 mol) of 2-hydroxymethacrylate were added, and the mixture was stirred at room temperature for 12 hours. To this solution, 35 g of thionyl chloride was added dropwise over 1 hour under ice cooling, followed by stirring at room temperature for 2 hours. To this solution, 14.0 g (0.07 mol) of 4,4'-diaminodiphenyl ether and 1,3-bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane
9.9 g (0.03 mol) was added and the mixture was stirred for 8 hours.

Further, 90 ml of ethanol was added and the mixture was stirred for 3 hours. Thereafter, the mixture was slowly poured into water of 8 to precipitate a polymer as a thread-like solid. This polymer was named PI-14.

Synthesis Example 15 Instead of 22.6 g (0.07 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride used in Synthesis Example 14,
Using meta-terphenyl-3,3 ″, 4,4 ″ -tetracarboxylic dianhydride 25.9 g (0.07 mol), and the other synthesis example 14
A polymer was obtained in the same manner as described above. This polymer was named PI-15.

Synthesis Example 16 Instead of 14.0 g (0.07 mol) of 4,4'-diaminodiphenyl ether used in Synthesis Example 14, 2,2-bis (4- (4
-Aminophenoxy) phenyl) propane 28.7 g (0.07
Mol), and the others were the same as in Synthesis Example 14 to obtain a polymer. This polymer was named PI-16.

Synthesis Example 17 13.3 g (0.03 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride 22.6 g
(0.07 mol) was dissolved in 260 ml of N-methyl-2-pyrrolidone, and then 4,4'-diaminodiphenyl ether 14.0 was dissolved.
g (0.07 mol) and 1,3-bis (4-aminophenyl)-
9.9 g (0.03 mol) of 1,1,3,3-tetramethyldisiloxane
Was added and stirred at room temperature for 4 hours.

Next, 7.7 g (0.05 mol) of isocyanatoethyl methacrylate was added to the solution, and the mixture was stirred at room temperature for 10 hours.

Further, 80 ml of ethanol was added, and the mixture was poured into water 10. As a result, the polymer was precipitated as a thread-like solid. This polymer was designated as PI-17.

Synthesis Example 18 14.5 g (0.05 mol) of an isocyanate compound having the following structural formula was used in place of 7.7 g (0.05 mol) of the isocyanatoethyl methacrylate used in Synthesis Example 17, and a polymer was prepared in the same manner as in Synthesis Example 17 except for the above. Obtained. This polymer is PI-18
It was named.

Synthesis Example 19 1,3-Bis (3,4-dicarboxyphenyl) -1,1,3,3
8.5 g (0.02 mol) of tetramethyldisiloxane dianhydride
And 25.7 g (0.08 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 200 ml of N-methyl-2-pyrrolidone and 26.0 g of 2-hydroxymethacrylate (0.
2 mol) and stirred at room temperature for 12 hours. To this solution, 35 g of thionyl chloride was added dropwise over 1 hour under ice cooling, followed by stirring at room temperature for 2 hours. 14.0 g (0.07 mol) of 4,4'-diaminodiphenyl ether and 2,2-
Bis (4-aminophenyl) hexafluoropropane 1
0.0 g (0.03 mol) was added and the mixture was stirred for 8 hours.

Further, 80 ml of ethanol was added and the mixture was stirred for 3 hours. Thereafter, when the mixture was slowly poured into water of 8, the polymer was precipitated as a thread-like solid. This polymer was named PI-19.

Synthesis Example 20 Meta-terphenyl-3,3 ″, 4,4 ″ was used in place of 25.7 g (0.08 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride used in Synthesis Example 19. -A polymer was obtained in the same manner as in Synthesis Example 19 except that 29.6 g (0.08 mol) of tetracarboxylic dianhydride was used. This polymer was named PI-20.

Synthesis Example 21 Instead of 14.0 g (0.07 mol) of 4,4′-diaminodiphenyl ether and 10.0 g (0.03 mol) of 2,2-bis (4-aminophenyl) hexafluoropropane used in Synthesis Example 19, 4'-diaminodiphenyl ether 10.0 g (0.05
Mol) and 2,2-bis (4- (4-aminophenoxy)
25.9 g (0.05 mol) of phenyl) hexafluoropropane
And a polymer was obtained in the same manner as in Synthesis Example 19 except for the above.
This polymer was named PI-21.

Synthesis Example 22 1,3-Bis (3,4-dicarboxyphenyl) -1,1,3,3
12.8 g (0.03 mol) of tetramethyldisiloxane dianhydride and 22.6 g (0.07 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in 250 ml of N-methyl-2-pyrrolidone After dissolving, 10.0 g (0.03 mol) of 2,2-bis (4-aminophenyl) hexafluoropropane
And 14.0 g (0.07 mol) of 4,4'-diaminodiphenyl ether were added, and the mixture was stirred at room temperature for 4 hours.

Next, 7.7 g (0.1 mol) of isocyanatoethyl methacrylate was added to this solution, and the mixture was stirred at room temperature for 10 hours.

Further, 80 ml of ethanol was added, and the mixture was poured into water 7. As a result, a polymer was precipitated as a thread-like solid. This polymer was named PI-22.

Synthesis Example 23 2,2-bis (4-aminophenyl) used in Synthesis Example 22
Hexafluoropropane 10.0 g (0.03 mol) and 4,4'-
Instead of 14.0 g (0.07 mol) of diaminodiphenyl ether, 25.9 g (0.05 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and 4,
A polymer was obtained in the same manner as in Synthesis Example 22, except that 10.0 g (0.05 mol) of 4'-diaminodiphenyl ether was used.
This polymer was designated as PI-23.

Synthesis Example 24 Except for 14.0 g (0.07 mol) of 4,4'-diaminodiphenyl ether used in Synthesis Example 22, 2,2-bis (4-
A polymer was obtained in the same manner as in Synthesis Example 22, except that 33.4 g (0.1 mol) of (aminophenyl) hexafluoropropane was used. This polymer was named PI-24.

Preparation examples of polymers for comparative examples are shown below as Synthesis Examples 25 to 28.

Synthesis Example 25 To 21.8 g (0.1 mol) of pyromellitic dianhydride, 202 ml of N-methyl-2-pyrrolidone and 26.0 g (0.2 mol) of 2-hydroxymethacrylate were added, and the mixture was stirred at room temperature for 12 hours. To this solution, 35 g of thionyl chloride was added dropwise over 1 hour under ice-cooling, followed by stirring at room temperature for 2 hours.
To this solution 4,4'-diaminodiphenyl ether 20.0 g
(0.1 mol) and stirred for 8 hours.

Further, 80 ml of ethanol was added and the mixture was stirred for 3 hours, and then slowly poured into the water of No. 8 to precipitate a polymer as a thread-like solid. This polymer was named PI-25.

Synthesis Example 26 14.0 g of pyromellitic acid dianhydride used in Synthesis Example 25 (0.1
In the same manner as in Synthesis Example 25, a polymer was obtained, except that 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was used instead of (mol). PI
It was named -26.

Synthesis Example 27 14.0 g (0.1 mol) of pyromellitic dianhydride was dissolved in 250 ml of N-methyl-2-pyrrolidone, and then 10.8 g (0.1 mol) of para-phenylenediamine was added, followed by stirring at room temperature for 4 hours.

Next, 15.5 g (0.1 mol) of isocyanatoethyl methacrylate was added to the solution, and the mixture was stirred at room temperature for 10 hours.

Further, 80 ml of ethanol was added, and the mixture was poured into water 8. As a result, the polymer was precipitated as a thread-like solid. This polymer was named PI-27.

Synthesis Example 28 14.0 g of pyromellitic dianhydride used in Synthesis Example 27 (0.1
Mol) instead of 3,3,4,4'-benzophenonetetracarboxylic dianhydride 32.2 g (0.1 mol) and para-phenylenediamine 10.8 g (0.1 mol) 4,4'- A polymer was obtained in the same manner as in Synthesis Example 27 except that 20.0 g (0.1 mol) of diaminodiphenyl ether was used. This polymer
It was named PI-28.

Examples 1 to 44 Polymers PI-1 to PI-24 obtained in Synthesis Examples 1 to 24 were each 10
The photoinitiator, polymerizable unsaturated compound and solvent shown in Table 1 were added to g, and the mixture was stirred and mixed to obtain a uniform photosensitive resin composition solution to be used in Examples 1 to 44.

Each of the solutions was filtered and dropped on a silicon wafer, and spin-coated at 2000 rpm for 30 seconds.

The obtained coating film was dried at 80 ° C. for 10 minutes, and the thickness of the coating film was measured.

Next, a pattern mask was applied to the coating surface, and an ultra-high pressure mercury lamp (8 m
W / cm ² ) for 70 seconds.

Next, using a spray-type developing machine, development is performed for 50 seconds with a mixture of equal amounts of N, N-dimethylacetamide and tetrahydrofuran, followed by rinsing with isopropanol for 5 seconds to leave the part irradiated by the ultra-high pressure mercury lamp. A relief pattern was obtained by drying with nitrogen spray.

The cured state of the relief pattern was examined by the residual film ratio of the following formula.

Residual film ratio = (film thickness of coating film after development / film thickness of coating film before development) × 100 Next, under nitrogen atmosphere, 100 ° C. for 30 minutes, 200 ° C. for 30 minutes, 350
After heating at ℃ for 30 minutes, a polyimide relief pattern was obtained. Table 1 shows the obtained results.

Further, the solution of the photosensitive resin composition obtained in Examples 1 to 44 was applied to a glass substrate, dried, heated at 350 ° C. for 1 hour, the film was peeled off from the glass plate, and the film properties after curing were as follows. The evaluation was performed according to the method described in Table 1 shows the results.

(1) Tensile strength The above film (film thickness) of 30 cm was made into a test piece having a width of about 1 cm and a length of about 10 cm, and five test pieces were measured for SS curve (10 mm / min) by a tensile tester.

(2) Starting temperature for weight loss Using the above-mentioned film (10 mg), raise the temperature in the air to 10 with a differential thermobalance.
It was measured at ° C / min.

Furthermore, the solution of the photosensitive resin composition obtained in Examples 1 to 44 was spin-coated on a silicon wafer to form a cured film, and the adhesion was evaluated by a grid test. That is, the cross-cut test with a grid pattern of cuts to allow 100 squares in at 1 mm ^□ Katsutanaifu, which was defined in JIS (JIS K540
0) This is a method of peeling with cellophane tape and expressing the number of peeled squares for 100 squares. The adhesiveness was evaluated by the pre-shear car test (condition: 121 ° C, 2 atm).
After the time processing, the number of peeled squares was counted in the grid test. Table 1 shows the results.

(Effect of the Invention) The photosensitive resin composition of the present invention and the photosensitive element using the same have excellent light transmittance and solubility, and when formed as a final cured film on the surface of a substrate, have high heat resistance and adhesion. It is an excellent one that can form a thick film having both properties.

Further, the final cured film has a small dielectric constant and a short signal delay time, and thus is excellent as an insulating film.

Continued on the front page. (72) Inventor Toshiaki Ishimaru 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. (72) Inventor Shigeo Tachiki 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Ibaraki Research Center (72) Inventor Mitsumasa Kojima 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture No. Hitachi Chemical Industries, Ltd. Yamazaki Factory (56) References JP-A-56-110728 (JP, A) JP-A-59-212833 (JP, A) JP-A-61-254547 (JP, A) JP-A Sho 59-172641 (JP, A) JP-A-60-228537 (JP, A) JP-A-1-118513 (JP, A)

Claims (2)

(57) [Claims] (A) The general formula (I) (Wherein, R ₁ is a tetravalent residue excluding four carboxyl groups of an aromatic tetracarboxylic acid having a fluorine atom, and 4 is a tetravalent aromatic tetracarboxylic acid having a siloxane group.
A tetravalent residue excluding four carboxyl groups or 4 excluding four carboxyl groups of an aromatic tetracarboxylic acid other than the above.
R ₂ is a divalent residue excluding two amino groups of an aromatic diamine having a fluorine atom, R ₂ is a divalent residue excluding two amino groups of an aromatic diamine having a siloxane group, Y is a divalent residue excluding the two amino groups of the aromatic diamine other than the above, and Y is a group having an ethylenically unsaturated group.
N is 0 or 1, m is 1 or 2,
n + m = 2), wherein at least one R ₁ or at least one R ₂ is a group having a fluorine atom, and at least one Wherein R ₁ or at least one R ₂ is a group having a siloxane group, comprising: a polyimide precursor containing a fluorine atom and a siloxane group; and (B) a photoinitiator. 2. A photosensitive element obtained by applying the photosensitive resin composition according to claim 1 on a substrate, drying and coating the substrate.