JP2000039710A - Photosensitive resin composition and production of relief pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. applicable to the production of a printed circuit board by incorporating a specified ethylenically unsatd. group-contg. polyimide precursor, a photopolymerizable unsatd. compd. and a photopolymn. initiator. SOLUTION: The photosensitive resin compsn. contains (A) an ethylenically unsatd. group-contg. polyimide precursor obtd. by allowing (a) a tetracarboxylic acid dianhydride of formula I or its deriv. to react with (b) a diamine of the formula H2N-R2-NH2 and (c) an aminobenzimidazole of formula II or its deriv., and allowing the resultant polyimide precursor to react with (d) a compd. having one isocyanato group and one or more ethylenic unsatd. groups in one molecule, (B) a photopolymerizable unsatd. compd. having one or more ethylenic unsatd. groups and (C) a photopolymn. initiator. In the formulae R1 is a tetravalent 2-30C org. group, R2 is a divalent 1-30C org. group, (n) is an integer of 1-4 and 3 is H, halogen, nitro or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition and a method for producing a relief pattern using the same.

[0002]

2. Description of the Related Art In recent years, in response to the miniaturization, weight reduction, multifunctionality, high reliability, and low price of electronic devices, printed circuit boards have been required to use conductive patterns without using component holes called surface mounting methods. A component mounting method for electrically connecting a component to a substrate on the surface of a semiconductor device is rapidly expanding. In the manufacture of printed wiring boards, photosensitive solder resist has been used for the purpose of limiting the soldering position and protecting the wiring, but the photosensitive solder resist used for printed wiring boards using the surface mounting method has been used. Is required to have better heat resistance, moisture resistance and adhesiveness. In the case of a conventional photosensitive solder resist containing an epoxy resin as a main component, when a pressure cooker test (hereinafter abbreviated as PCT) is performed, the resist becomes There is a problem that blistering or peeling occurs and heat resistance, moisture resistance and adhesion are insufficient. In addition, when PCT is performed, there is a problem in that electrical insulation is broken due to copper migration, and reliability is lacking.

In addition, a conventional photosensitive solder resist using a polyimide precursor has a high heat curing temperature of 350 ° C. or more after image formation by a photographic method, and is used for a printed wiring board in terms of heat resistance of a substrate or the like. There is a problem that can not be. Further, a photosensitive solder resist using an aromatic polyimide maintains high heat resistance, but has a problem in safety and work environment because an organic solvent is used for a developer.

[0004]

According to the first aspect of the present invention, PCT resistance, low-temperature curing property, solder heat resistance, plating solution resistance, An object of the present invention is to provide a photosensitive resin composition having excellent chemical resistance, electrical insulation, storage stability, and work environment. The invention according to claim 2 provides the effect of the photosensitive resin composition according to claim 1 and provides a photosensitive resin composition having excellent PCT resistance and high sensitivity. The invention according to claim 3 has the effect of the photosensitive resin composition according to claim 2, and has more excellent PCT resistance and more excellent developability.
It is intended to provide a photosensitive resin composition having higher sensitivity.
The invention according to claim 4 is excellent in PCT resistance, low-temperature curing property, solder heat resistance, plating solution resistance, chemical resistance, electrical insulation, work environment, etc., and is suitable for a relief pattern suitable for an interlayer insulating film and the like. It provides a manufacturing method.

[0005]

The present invention provides (A) and (a)
General formula (I)

Embedded image (Wherein, R ¹ represents a tetravalent organic group having 2 to 30 carbon atoms) or a derivative thereof (b) a general formula (II)

Embedded image (Wherein R ² represents a divalent organic group having 1 to 30 carbon atoms) and (c) a general formula (III)

Embedded image (Wherein n is an integer of 1 to 4, R ³ represents a hydrogen atom, a halogen atom, a nitro group or an alkyl group having 1 to 9 carbon atoms) or a derivative thereof. (D) 1
Ethylenically unsaturated group-containing polyimide precursor obtained by reacting a compound having one isocyanate group and one or more ethylenically unsaturated groups in a molecule, (B) photopolymerization having one or more ethylenically unsaturated groups The present invention relates to a photosensitive resin composition containing a water-soluble unsaturated compound and (C) a photopolymerization initiator.

[0006] The present invention also provides (D) a blocked isocyanate resin and (E) a heterocyclic compound having at least one thiol group in addition to the (A), (B) and (C) components. It relates to the photosensitive resin composition contained.

In the present invention, the component (A) may be used in an amount of 20 to 100 parts by weight based on the total amount of the components (A) and (B).
95 parts by weight, component (B) is 5 to 80 parts by weight, with the total amount of components (A) and (B) being 100 parts by weight, (C)
Component is 0.01 to 20 parts by weight based on 100 parts by weight of the total of component (A) and component (B), and component (D) is
0 to 40 parts by weight of the component (E) and 100 parts by weight of the component (E), based on 100 parts by weight of the total amount of the components (A) and (B), The present invention relates to the photosensitive resin composition having a mixing ratio of 0 to 20 parts by weight.

[0008] The present invention also relates to a method for producing a relief pattern, comprising forming a layer of the photosensitive resin composition on a substrate, exposing it imagewise, and then developing.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive resin composition of the present invention will be described in detail. The photosensitive resin composition of the present invention comprises (A) an ethylenically unsaturated group-containing polyimide precursor,
It comprises (B) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group and (C) a photopolymerization initiator.

The polyimide precursor containing an ethylenically unsaturated group, which is the component (A), comprises (a) a tetracarboxylic dianhydride represented by the above general formula (I) and (b) a tetracarboxylic dianhydride represented by the above general formula (II)
And (c) the general formula (III)
(D) a compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule reacted with a polyimide precursor obtained by reacting with aminobenzimidazole represented by .

R ¹ in the above general formula (I) is, for example, the following general formula (IV)

Embedded image (Wherein Y is a single bond, -O-, -S-, -CO-,-
_{SO 2 -, - CONH -,} - CH 2 -, - C (CH 3) 2 -,
—C (CF ₃ ) ₂ — or

Embedded image And Y in the general formula (IV) is a single bond, -O-, -C
_{O -, - SO 2 -,} - C (CH 3) 2 - or -C (CF _{3) 2} -
Are preferred from the viewpoint of low-temperature curability and PCT resistance.

(A) Examples of the tetracarboxylic dianhydride represented by the above general formula (I) include 3,3 ', 4,4
4'-benzophenonetetracarboxylic acid, 3,3 ',
4,4'-biphenyltetracarboxylic acid, 2,3 ',
3,4'-biphenyltetracarboxylic acid, 2,3 ',
4,4'-biphenyltetracarboxylic acid, 3,3 ',
4,4'-diphenylethertetracarboxylic acid, 3,
Tetracarboxylic dianhydrides such as 3 ', 4,4'-diphenylsulfonetetracarboxylic acid are preferred. These are used alone or in combination of two or more.

As a part of such tetracarboxylic dianhydride, pyromellitic acid, 1,2,5,6-
Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, m-terphenyl-3,3 ', 4
4'-tetracarboxylic acid, p-terphenyl-3,
3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,
3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, , 2-bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 1,1,
1,3,3,3-hexafluoro-2,2-bis [4 ′
-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic acid, 4,4 Dianhydrides of aromatic tetracarboxylic acids such as' -bis (2,3-dicarboxyphenoxy) diphenylmethane; the following general formula (V)

Embedded image (Wherein, R ⁴ and R ⁵ represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different, and m
Is an integer of 1 or more), an aromatic tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, Aliphatic tetracarboxylic dianhydrides such as butenetetracarboxylic acid and butanetetracarboxylic acid can also be used.

R ² in the general formula (II) is, for example, the following general formula (VI)

Embedded image (Wherein X is a single bond, -O-, -S-, -CO-,-
_{SO 2 -, - CONH -,} - CH 2 -, - C (CH 3) 2 -,
—C (CF ₃ ) ₂ — or

Embedded image Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent 1 carbon atom
Represents an alkyl group or a halogen atom, and p, q, r
And s each independently represent an integer of 0 to 4), etc., from the viewpoint of low-temperature curability and PCT resistance.

In the above general formula (VI), the number of carbon atoms is 1-6.
Examples of the alkyl group include a methyl group, an ethyl group,
Examples include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, and a hexyl group. In the general formula (VI), examples of the halogen atom include fluorine, chlorine,
Bromine, iodine, astatine and the like can be mentioned.

(B) As the diamine component represented by the general formula (II), for example, 2,2-bis- [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis- [3- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) Phenyl] sulfone, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-
Bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy)] biphenyl, bis [1- (4- Aminophenoxy)] biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4 -(4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy)] benzophenone, bis [4- (3-
Aminophenoxy)] benzophenone, bis [4- (4
-Aminophenoxy)] benzanilide, bis [4-
(3-aminophenoxy)] benzanilide, 9,9-
Bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene and the like are preferred. These may be used in combination of two or more, and may be used in combination with a small amount of an aromatic diamine other than these diether-based diamines.

Other aromatic diamines include, for example,
4,4'- (or 3,4'-, 3,3'-, 2,4 '
-, 2,2 '-) diaminodiphenyl ether, 4,
4'- (or 3,4'-, 3,3'-, 2,4'-,
2,2 '-) diaminodiphenylmethane, 4,4'-
(Or 3,4'-, 3,3'-, 2,4'-, 2,2 '
-) Diaminodiphenyl sulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine , P-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone, 4,4'-methylene-bis- (2,6-
Diethylaniline), 4,4'-methylene-bis-
(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4 ′
-Benzophenone diamine, 1,1,1,3,3,3-
Hexafluoro-2,2-bis (4-aminophenyl)
Propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, benzidine, 2,6
-Diaminopyridine, 3,3'-dimethoxybenzidine, 1,4-bis (4-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 4,
4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 3,5
-Diaminobenzoic acid and the like.

In addition, for example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2-diaminocyclohexane, the following general formula (VII)

Embedded image (Wherein, R ¹⁰ and R ¹¹ each independently represent 1 to 3 carbon atoms.
0 represents a divalent hydrocarbon group, R ¹² and R ¹³ each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, and t is an integer of 1 or more) Diaminopolysiloxane, 1,3-bis (aminomethyl) cyclohexane, Jeffamine D-23 manufactured by San Techno Chemical Co., Ltd.
0, D-400, D-2000, D-4000, ED-
600, ED-900, ED-2001, EDR-14
An aliphatic diamine component such as polyoxyalkylene diamine such as 8 may be used.

In R ³ in the general formula (III), examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Tert-butyl, amyl, isoamyl, hexyl, heptyl, octyl, 2
-Ethylhexyl group, nonyl group and the like. In R ³ in the general formula (III), the halogen atom includes
For example, fluorine, chlorine, bromine, iodine, astatine and the like can be mentioned.

(C) Examples of the aminobenzimidazole represented by the general formula (III) include 2-aminobenzimidazole, 2-amino-6-methyl-benzimidazole, 2-amino-6-ethyl-benzimidazole , 2-amino-6-butyl-benzimidazole, 2
-Amino-6-nitro-benzimidazole and the like are used. From the viewpoint of PCT resistance and developability, 2-aminobenzimidazole is particularly preferred.

(A) a tetracarboxylic dianhydride represented by the general formula (I), (b) a diamine component represented by the general formula (II), and (c) a diamine component represented by the general formula (III) (D) a compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule, which is reacted with a polyimide precursor obtained by reacting with aminobenzimidazole to be produced, for example, 2- ( Examples thereof include (meth) acryloyloxyethyl isocyanate and (meth) acrylic acid isocyanate, and 2-methacryloyloxyethyl isocyanate is preferred from the viewpoint of PCT resistance and plating solution resistance.

In the present invention, (A) the polyimide precursor having an ethylenically unsaturated group is represented by the following general formula (I):
(B) a diamine component represented by the general formula (II) and (c) an aminobenzimidazole represented by the general formula (III) in a solvent, A compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule is added to a polyimide precursor obtained by reacting at 100 ° C. for 1 to 20 hours.
It can be produced by reacting at 0 ° C to 100 ° C for 1 to 20 hours.

The solvent used here must be inert to the polyimide precursor. For example, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone, Lactones such as heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl) , Dibutyl) ether, ethers such as tetraethylene glycol (or diethyl, dipropyl, dibutyl) ether;
Carbonates such as ethylene carbonate and propylene carbonate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol dimethyl (or monomethyl) ether, triethylene glycol dimethyl (or monomethyl) Alcohols such as ether and tetraethylene glycol dimethyl (or monomethyl) ether; phenols such as phenol, cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; toluene, xylene, diethylbenzene and cyclohexane Hydrocarbons such as trichloroethane, tetrachloroethane, mono Halogenated hydrocarbons such as chlorobenzene, dimethylsulfoxide, is a nitrogen-containing solvent N-
Methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used, but non-nitrogen-containing solvents which are highly volatile and can impart low-temperature curability are preferable, and γ-butyrolactone is used. Is more preferred. These can be used alone or in combination of two or more.

The amount of the solvent used is preferably 1 to 10 times (weight ratio) the polyimide precursor to be produced. If it is less than 1 time, the viscosity at the time of synthesis tends to be too high and the synthesis tends to be difficult due to inability to stir. If it exceeds 10 times, the reaction rate tends to decrease.

When synthesizing the polyimide precursor of the component (A), the amount of (c) the aminobenzimidazole represented by the general formula (III) and the derivative thereof is determined by the components (b) and (c). Is preferably 0.1 to 10 mol% based on the total amount of If the amount of the component (c) is less than 0.1 mol%, the PCT resistance tends to be inferior, and 10 mol%
When it exceeds, the developability and the storage stability tend to decrease. Further, the total amount of the components (b) and (c) used,
(A) The ratio of the amount of the tetracarboxylic dianhydride represented by the general formula (I) is 1.5 / 1.0 to the former / the latter.
It is preferable to be in the range of 1.05 / 1.0 (equivalent ratio). When the total amount of the component (b) and the component (c) exceeds this range, the molecular weight of the polyimide precursor does not tend to increase, and the heat resistance and the like tend to decrease. If the amount is less than this range, the PCT resistance and the plating solution resistance tend to decrease.

The amount of the compound (d) having one isocyanate group and one or more ethylenically unsaturated groups in one molecule is 0.1 to 1.
It is preferable to set the range to 0 mol. When the amount of the component (d) is less than 0.1 mol, PCT resistance and plating solution resistance tend to decrease, and when it exceeds 1.0 mol, developability and storage stability tend to decrease. .

Examples of the polyimide precursor (A) having an ethylenically unsaturated group in the present invention which can be obtained as described above include compounds represented by the following general formula (VIII):

Embedded image (Wherein R ¹ and R ² represent the general formulas (I) and (II)
And a is an integer of 1 or more).

The weight average molecular weight of the (A) ethylenically unsaturated group-containing polyimide precursor in the present invention is 10,000.
It is preferable to set it to 0 to 200,000. If the weight average molecular weight is less than 10,000, PCT resistance and chemical resistance tend to decrease, and if it exceeds 200,000, developability and resolution tend to decrease. The weight average molecular weight was measured by gel permeation chromatography (using a mixed solution of N, N-dimethylformaldehyde / tetrahydrofuran (1/1) (weight ratio) as an eluent), and a standard polystyrene calibration curve was used. It is a value converted by using.

The photopolymerizable unsaturated compound (B) having at least one ethylenically unsaturated group in the present invention includes, for example, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, Benzyl acrylate, benzyl methacrylate,
Compounds obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, bisphenol A (or F) polyoxyethylene diacrylate or bisphenol A (or F) polyoxyethylene dimethacrylate, and a compound containing a glycidyl group , A compound obtained by adding a β-unsaturated carboxylic acid, a polycarboxylic acid (such as phthalic anhydride) and a substance having a hydroxyl group and an ethylenically unsaturated group (such as β-hydroxyethyl acrylate and β hydroxyethyl methacrylate) And alkyl esters of acrylic acid or methacrylic acid, urethane acrylate or urethane methacrylate.

Examples of the compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol include, for example, polyethylene glycol diacrylate or polyethylene glycol dimethacrylate (where the number of ethylene groups is 2 to 14).
), Trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropaneethoxytriacrylate, trimethylolpropaneethoxytrimethacrylate, trimethylolpropanepropoxytriacrylate, trimethylolpropane Methylol propane propoxy trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, polypropylene glycol diacrylate or polypropylene glycol dimethacrylate (where the number of propylene groups is 2 to 14)
), Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

Bisphenol A (or F) polyoxyethylene diacrylate or bisphenol A (or F)
Examples of polyoxyethylene dimethacrylate include bisphenol A (or F) dioxyethylene diacrylate, bisphenol A (or F) dioxyethylene dimethacrylate, bisphenol A (or F) trioxyethylene diacrylate, and bisphenol A
(Or F) trioxyethylene dimethacrylate, bisphenol A (or F) decaoxyethylene diacrylate, bisphenol A (or F) decaoxyethylene dimethacrylate, and the like.

Examples of the compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound include trimethylolpropane triglycidyl ether triacrylate and bisphenol A (or F) diglycidyl ether diacrylate. No.

Examples of the alkyl esters of acrylic acid or methacrylic acid include methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-acrylic acid
Examples include ethylhexyl ester and 2-ethylhexyl methacrylate.

Examples of the urethane acrylate or urethane methacrylate include a reaction product of tolylene diisocyanate with 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, trimethylhexamethylene diisocyanate, cyclohexanedimethanol and 2-hydroxyethyl. Reaction products with acrylic acid esters or 2-hydroxyethyl methacrylic acid esters are exemplified.

Among these (B) photopolymerizable unsaturated compounds having an ethylenically unsaturated group, an organic isocyanate compound (tolylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc.) and a hydroxyl group-containing acrylate or hydroxyl group (B) having a urethane bond such as urethane acrylate or urethane methacrylate obtained by reacting a group-containing methacrylate (such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate) with a chain extender (such as cyclohexane dimethanol), if necessary. The photopolymerizable unsaturated compound having an ethylenically unsaturated group is preferred from the viewpoints of (A) compatibility between the ethylenically unsaturated group-containing polyimide precursor and other resist components, PCT resistance, and the like. Mentioned further in view of such photosensitivity, a reaction product of trimethylhexamethylene diisocyanate and cyclohexanedimethanol and 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate as the more preferable.

Examples of the photopolymerization initiator (C) in the present invention include benzoin ethers (benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin phenyl ether, etc.) and benzophenones (benzophenone, N , N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, etc.), benzyl ketals (benzyldimethyl ketal (Ciba.
Geigy, Irgacure 651), benzyl diethyl ketal, etc.), acetophenones (2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloroacetophenone, p-dimethylaminoacetophenone, etc.), xanthones (2,4 -Dimethylthioxanthone, 2,4-diisopropylthioxanthone, etc.), hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
Examples thereof include 1-one (manufactured by Merck, Darocure 1116) and 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Merck, Darocure 1173). These are used alone or in combination of two or more.

In addition to the photopolymerization initiator (C) described above, for example, 2,4,5-triallylimidazole dimer and 2-mercaptobenzoxazole, leuco crystal violet, tris (4-diethylamino-2) −
A combination with (methylphenyl) methane or the like can also be used, and there is no photoinitiation by itself, but in combination with the above substance, a sensitizer system having better photoinitiation performance as a whole is obtained. Such additives (such as tertiary amines such as triethanolamine for benzophenone) and the like can also be used.

Among these (C) photopolymerization initiators, those having no amine structure in the molecular structure are preferred from the viewpoint of particularly improving the storage stability of the photosensitive resin composition. For example, benzophenone Or benzophenone derivatives, benzyl ketals (benzyldimethyl ketal (manufactured by Ciba Geigy, Irgacure 651), benzyl diethyl ketal, etc.), acetophenones (2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloroacetophenone, p-dimethylaminoacetophenone, etc., xanthones (2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, etc.), hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 1- (4-isopropylphenyl) -2-hi Droxy-2-methylpropane-1
-One (manufactured by Merck, Darocure 1116), 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Merck, Darocure 1173) and the like are more preferable. Dimethyl ketal is particularly preferred.

The photosensitive resin composition of the present invention contains, in addition to the components (A), (B) and (C), a PC-resistant resin.
From the viewpoints of T properties, sensitivity and the like, it is preferable to further contain (D) a blocked isocyanate resin and (E) a heterocyclic compound having at least one thiol group.

The blocked isocyanate resin as the component (D) is obtained by reacting a compound having an active hydrogen (blocking agent) with the isocyanate resin, and is stable at normal temperature. The resin is used for a thermosetting reaction as a resin. Examples of the (D) blocked isocyanate resin include, for example, tolylene diisocyanate, hexamethylene diisocyanate, triisocyanurate composed of hexamethylene diisocyanate, diphenylmethane diisocyanate, Compounds having active hydrogen such as phenol, alcohol, oxime, β-dicarbonyl compound, lactam, amine imide, nitrile carbonate, isocyanate dimer, etc. in isocyanate resin such as isophorone diisocyanate Obtained by reacting a blocking agent) and the like, which are used alone or in combination of two or more. From the viewpoint of compatibility and PCT resistance, hexamethylene diisocyanate or triisocyanurate of hexamethylene diisocyanate is preferably a blocked isocyanate obtained by reacting methyl ethyl ketoxime as a blocking agent, and triisocyanurate of hexamethylene diisocyanate is preferred. A blocked isocyanate obtained by reacting methyl ethyl ketoxime as a blocking agent is particularly preferred.

Examples of the heterocyclic compound having one or more thiol groups as the component (E) include, for example, bismuthiol, benzenedithiol, cyclohexanethiol, hexanedithiol, 2-mercapto-1-methyl- Imidazole, 5-amino-1,
Examples include 3,4-thiadiazole-2-thiol, 2-mercapto-benzimidazole, 2-mercapto-benzothiazole, 1H-1,2,4-triazole-3-thiol, and bismuthyl represented by the following formula is resistant. It is particularly preferable from the viewpoint of plating solution properties.

Embedded image

In the photosensitive resin composition of the present invention,
The amount of the component (A) used is preferably 20 to 95 parts by weight, with the total amount of the components (A) and (B) being 100 parts by weight. When the amount of the component (A) is less than 20 parts by weight, the PCT resistance tends to decrease, and when it exceeds 90 parts by weight, the sensitivity tends to decrease. The amount of the component (B) used is preferably 5 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If the amount of the component (B) is less than 5 parts by weight, the sensitivity tends to decrease, and if it exceeds 90 parts by weight, the PCT resistance tends to decrease. Also,
The amount of component (C) used is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the total of components (A) and (B). If the amount of the component (C) is less than 0.01 parts by weight, the sensitivity tends to decrease, and if it exceeds 20 parts by weight, the shape of the negative pattern formed tends to deteriorate.

The amount of the component (D) is from 0 to 40 with respect to 100 parts by weight of the total amount of the components (A) and (B).
It is preferable to use parts by weight. (C) Component usage is 4
If the amount exceeds 0 parts by weight, the light sensitivity tends to decrease. The amount of the component (E) is preferably 0 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount of the component (E) exceeds 20 parts by weight, the shape of the negative pattern formed tends to be poor, and the plating solution tends to be contaminated.

Dyes, pigments, plasticizers, stabilizers and the like may be added to the photosensitive resin composition of the present invention as needed.
Further, the photosensitive resin composition of the present invention has heat resistance, moisture resistance,
Known and commonly used thermosetting resins and cross-linking agents can be used for the purpose of improving properties such as electric corrosion resistance. Examples of the thermosetting agent include a combination of a known and commonly used epoxy resin such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolac, and cresol novolac type with an epoxy curing agent such as an amine type or an acid anhydride type, and a melamine resin. , A urea resin, an amino resin such as a guanamine resin, a derivative thereof, and a phenol resin.

The method for producing a relief pattern according to the present invention is characterized in that a layer of the above-described photosensitive resin composition of the present invention is formed on a substrate, imagewise exposed, and then developed. Hereinafter, the method for producing the relief pattern of the present invention will be described in detail.

In the method for producing a relief pattern of the present invention, a method of forming a layer of the photosensitive resin composition of the present invention on a substrate includes first dissolving the photosensitive resin composition of the present invention uniformly, After the photosensitive resin composition in the form of a solution is uniformly applied on the substrate, the solvent is removed by heating or blowing with hot air to form a dry film, whereby the composition can be formed on the substrate. The thickness of the dried film is not particularly limited, and is 5 to 10
The thickness is preferably 0 μm, more preferably 10 to 60 μm. The conditions for drying the photosensitive resin composition are not particularly limited, but the drying temperature is preferably from 60 to 130 ° C, and if necessary, drying may be performed under reduced pressure.

When the photosensitive resin composition of the present invention is used, it is not necessary to pre-heat the substrate in advance by heating as described above, but the adhesion between the substrate and the photosensitive resin layer is further improved. Pre-heat treatment of the substrate may be performed for improvement.

The layer of the photosensitive resin composition thus obtained is then imagewise exposed to actinic light using a negative or positive film. The active light is a known active light source, for example, a carbon arc, a mercury vapor arc,
Light generated from a xenon arc or the like is used. The sensitivity of the photoinitiator contained in the layer of the photosensitive resin composition is usually
Since it is greatest in the ultraviolet region, the active light source should then effectively emit ultraviolet light.

Next, after exposure, using an alkaline aqueous solution containing 0.1 to 50% by weight of an organic solvent or a surfactant, unexposed by a known method such as spraying, rocking immersion, brushing, and scraping. Remove the part and develop. The organic solvent or surfactant used in the developer may be a well-mixed one with water to form a uniform developer, or a non-uniform developer which hardly mixes with water. Examples of such an organic solvent or surfactant include butyl carbitol, N, N-dimethylformamide, methyl cellosolve, ethyl cellosolve,
3-Methyl-3-methoxybutyl acetate, heptanoic acid diethanolamide, polyoxyethylene paracumyl phenyl ether and the like are used, and polyoxyethylene paracumyl phenyl ether is particularly preferable. Further, as an alkali component used in the developer, sodium carbonate, sodium hydroxide, borax and the like are used in a range of 0.01 to 30% by weight. Further, the temperature of the developer used for development is
It is controlled by the developability of the photosensitive layer. Further, a surfactant, an antifoaming agent and the like may be mixed in the developer.

After the development is completed, UV irradiation or heating with a high-pressure mercury lamp can be performed for the purpose of improving PCT resistance, solder heat resistance, chemical resistance and the like. It is preferable that the amount of ultraviolet irradiation at the time of ultraviolet irradiation is 0.2 to 10 J / cm ^2, and the temperature at the time of irradiation is 60 to 150 ° C. The heating temperature is preferably 150 to 250 ° C., and the heating time is preferably 15 to 120 minutes. The order of the irradiation of the ultraviolet rays and the heating may be any order, but it is more preferable that the irradiation of the ultraviolet rays is performed first and the heating is performed thereafter. The thus obtained relief pattern in the present invention is suitable as a solder resist, after which components such as an LSI can be mounted.

[0051]

Next, the present invention will be described in more detail by way of examples. Parts in the following examples mean parts by weight unless otherwise specified.

Synthesis Example 1 [(A) Preparation of Solution of Ethylene Unsaturated Group-Containing Polyimide Precursor] A thermometer, a stirrer, a cooling pipe, and a nitrogen gas inlet pipe were attached.
2208 g of γ-butyrolactone and 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 528.90 g
(1.29 mol) and 2.66 g (0.02 mol) of 2-aminobenzimidazole were added, and the temperature was raised to 45 ° C.
While maintaining the temperature at 43 to 50 ° C., 322.00 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
(1.00 mol) was added in small portions. After addition, 45 ° C
And then cooled to 20 ° C., and 93.00 g of 2-methacryloyloxyethyl isocyanate
(0.60 mol) was added dropwise, and the mixture was reacted for 2 hours while maintaining the temperature at 18 to 23 ° C. to obtain a solution (A-1) of an ethylenically unsaturated group-containing polyimide precursor. The solid content of the obtained solution (A-1) of the ethylenically unsaturated group-containing polyimide precursor (A-1) is 30% by weight, and the weight average molecular weight is 25,
000.

Synthesis Example 2 [(A) Preparation of Solution of Ethylene Unsaturated Group-Containing Polyimide Precursor] A thermometer, a stirrer, a cooling pipe, and a nitrogen gas inlet pipe were attached.
2292 g of γ-butyrolactone and 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 528.90 g
(1.29 mol) and 2.66 g (0.02 mol) of 2-aminobenzimidazole were added, and the temperature was raised to 45 ° C.
While maintaining the temperature at 43 to 50 ° C., 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride 358.00
g (1.00 mol) was added in small portions. After addition, 45
After continuing the reaction at 5 ° C. for 5 hours, the mixture was cooled to 20 ° C. and 93.00 g of 2-methacryloyloxyethyl isocyanate
(0.60 mol) was added dropwise, and the mixture was reacted for 2 hours while maintaining the temperature at 18 to 23 ° C. to obtain a solution (A-2) of an ethylenically unsaturated group-containing polyimide precursor. The solid content of the obtained solution (A-2) of the ethylenically unsaturated group-containing polyimide precursor (A-2) is 30% by weight, and the weight average molecular weight is 25,
000.

Synthesis Example 3 [(A) Preparation of Solution of Ethylene Unsaturated Group-Containing Polyimide Precursor] A thermometer, a stirrer, a cooling pipe, and a nitrogen gas inlet pipe were attached.
In a reaction vessel having a capacity of 5 liters capable of heating and cooling, 2040 g of γ-butyrolactone and 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 487.90 g
(1.19 mol) and 2.66 g (0.02 mol) of 2-aminobenzimidazole were added, and the temperature was raised to 45 ° C.
While maintaining the temperature at 43 to 50 ° C., 322.00 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
(1.00 mol) was added in small portions. After addition, 45 ° C
After continuing the reaction for 5 hours, the mixture was cooled to 20 ° C., and 62.00 g of 2-methacryloyloxyethyl isocyanate was added.
(0.40 mol) was added dropwise, and the mixture was reacted for 2 hours while maintaining the temperature at 18 to 23 ° C. to obtain a solution (A-3) of an ethylenically unsaturated group-containing polyimide precursor. The solid content of the obtained solution (A-3) of the ethylenically unsaturated group-containing polyimide precursor (A-3) was 30% by weight, and the weight average molecular weight was 28,
000.

Synthesis Example 4 [Preparation of Solution of (A) Ethylenic Unsaturated Group-Containing Polyimide Precursor] A thermometer, a stirrer, a cooling pipe, and a nitrogen gas inlet pipe were attached.
2208 g of γ-butyrolactone and 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 528.90 g
(1.09 mol) and 2.66 g (0.02 mol) of 2-aminobenzimidazole were added, and the temperature was raised to 45 ° C.
While maintaining the temperature at 43 to 50 ° C., 322.00 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
(1.00 mol) was added in small portions. After addition, 45 ° C
After continuing the reaction for 5 hours, the mixture was cooled to 20 ° C and 31.00 g of 2-methacryloyloxyethyl isocyanate was added.
(0.20 mol) was added dropwise, and the mixture was reacted for 2 hours while maintaining the temperature at 18 to 23 ° C. to obtain a solution (A-4) of a polyimide precursor containing an ethylenically unsaturated group. The solid content of the obtained solution (A-4) of the ethylenically unsaturated group-containing polyimide precursor (A-4) was 30% by weight, and the weight average molecular weight was 30,
000.

Synthesis Example 5 [(B) Preparation of Solution of Photopolymerizable Unsaturated Compound] A 1-liter volume capable of heating and cooling equipped with a thermometer, a stirrer, a cooling pipe, a nitrogen gas introduction pipe and a dropper. In a reaction vessel, 137.3 g of toluene and 210 g (1.00 mol) of trimethylhexamethylene diisocyanate were added.
The temperature was raised to 70 ° C, and while maintaining the temperature at 70 to 75 ° C, 72 g (0.5 mol) of cyclohexanedimethanol and 130 g (1.0 mol) of 2-hydroxyethyl methacrylate were added dropwise little by little. After the dropwise addition, the reaction was continued at 70 ° C. for 5 hours, cooled to room temperature, and a solution of the photopolymerizable unsaturated compound (B-
1) was obtained. The solid content of the obtained (B-1) was 75% by weight.

Comparative Synthesis Example 1 A thermometer, a stirrer, a cooling pipe, and a nitrogen gas introduction pipe were attached.
2954.7 g of γ-butyrolactone and 2,2-bis [4-
(4-aminophenoxy) phenyl] propane 410.
000 g (1.00 mol), heated to 45 ° C.
While keeping the temperature at 3 to 50 ° C, 334.880 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
(1.04 mol) was added in small portions. After addition, 45 ° C
For 5 hours, and then cooled to room temperature to obtain a polyamic acid solution (a-1). The solid content of the solution (a-1) of the obtained aromatic polyamic acid compound was 20% by weight, and the weight average molecular weight was 60,000.

Comparative Synthesis Example 2 A thermometer, a stirrer, a cooling pipe, and a nitrogen gas introduction pipe were attached.
In a 5 liter reaction vessel capable of heating and cooling, 2973 g of γ-butyrolactone and 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 405.90 g
(0.99 mol) and 2.66 g (0.02 mol) of 2-aminobenzimidazole were added, and the temperature was raised to 45 ° C.
While maintaining the temperature at 43 to 50 ° C., 334.880 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
(1.04 mol) was added in small portions. After addition, 45 ° C
After continuing the reaction for 5 hours, the mixture was cooled to room temperature to obtain a polyamic acid solution (a-2). The solid content of the obtained solution (a-2) of the aromatic polyamic acid compound was 20% by weight, and the weight average molecular weight was 60,000.

Examples 1 to 6, Comparative Examples 1 to 6 Components (A) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2, component (B) obtained in Synthesis Example 5, and (C) component,
The components (D) and (E) were mixed in the proportions (parts by weight) shown in Tables 1 and 2 to obtain a solution of the photosensitive resin composition. Next, a copper-clad laminate (MCL-E-679 manufactured by Hitachi Chemical Co., Ltd.) having a copper thickness of 18 μm was supplied to Sumitomo 3M Limited.
Polished with Scotch Bright, washed with water,
Dried for 5 minutes. To this test substrate, uniformly apply a solution of the photosensitive resin composition having the above composition using an applicator,
It was dried on a hot plate at 90 ° C. for about 10 minutes. The thickness of the layer of the photosensitive resin composition after drying was 20 μm.
With respect to the test substrate on which the layer of the photosensitive resin composition thus obtained was formed, developability, storage stability, PCT resistance
Properties and gold plating resistance were tested by the following methods. The results are shown in Tables 1 and 2.

(1) Developability The test substrate on which the layer of the photosensitive resin composition obtained above was formed was subjected to an alkaline aqueous solution containing 2% by weight of polyoxyethylene paracumylphenyl ether and 0.5% by weight of sodium carbonate. And spray developed at 45 ° C. for 60 seconds.
After the development, the resin remaining after being magnified 30 times was visually evaluated for developability. The evaluation criteria are as follows. ：: Good developability (no resin left on substrate surface) ×: Poor developability (residual resin left on substrate surface)

(2) Storage stability The photosensitive resin composition obtained above was treated at room temperature (20 to 23).
C.) for one week, a test substrate was prepared in the same manner as in (1), and the developability was evaluated. The evaluation criteria are as follows. ：: Good storage stability (no resin remains on the substrate surface and good developability) ×: Poor storage stability (a little resin remains on the substrate surface and developability) Bad one)

(3) PCT resistance The copper-clad laminate (MCL-E-679 manufactured by Hitachi Chemical Co., Ltd.) having a copper thickness of 18 μm was polished with Scotch Bright manufactured by Sumitomo 3M Co., Ltd., and washed with water. Dry at 80 ° C. for 15 minutes. A solution of the photosensitive resin composition having the above composition was uniformly applied to the test substrate using an applicator in the same manner as described above, and dried on a hot plate at 90 ° C. for 10 minutes. The thickness of the layer of the photosensitive resin composition after drying was 20 μm. Next, exposure was performed at an exposure amount of 500 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Then Toshiba Denki
Ultraviolet irradiation was performed again at an amount of 1 J / cm ² using an ultraviolet irradiation apparatus manufactured by Co., Ltd., and then further heated at 175 ° C. for 60 minutes by a dryer. The test substrate thus obtained was subjected to 5 hours at 121 ° C. and 2 atm using a PCT tester manufactured by Hirayama Seisakusho.
The PCT treatment was performed until 00 hours, and the adhesion was evaluated by a tape test by a cross cut method. The evaluation results are described in the following format. A / B (indicates that A out of B did not peel)

(4) Gold plating resistance The copper-clad laminate (MCL-E-679 manufactured by Hitachi Chemical Co., Ltd.) having a copper thickness of 18 μm was polished with Scotch Bright manufactured by Sumitomo 3M Limited and washed with water. And dried at 80 ° C. for 15 minutes. A solution of the photosensitive resin composition having the above composition was uniformly applied to the test substrate using an applicator in the same manner as described above, and dried on a hot plate at 90 ° C. for 10 minutes. The thickness of the layer of the photosensitive resin composition after drying was 20 μm. Next, the negative mask shown in FIG. 1 was brought into close contact with the photosensitive resin composition layer, and exposed with an exposure amount of 500 mJ / cm ² using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Next, after removing the negative mask, the developer is treated with an alkaline aqueous solution containing 2% by weight of polyoxyethylene paracumylphenyl ether and 0.5% by weight of sodium carbonate.
Spray developed at 60 ° C for 60 seconds. After development, 10
After heating and drying for 1 minute, the film was re-irradiated with ultraviolet rays at an amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and then further heated at 175 ° C. for 60 minutes with a dryer.

The test substrate thus obtained was placed in an acidic degreasing solution (manufactured by World Metal Co., trade name: Z-200) for 6 hours.
An acidic degreasing treatment was performed by immersion at 0 ° C. for 1 minute. Next, it was immersed in a soft etching solution (100 g / liter aqueous solution of ammonium persulfate) at 23 ° C. for 3 minutes to perform a soft etching process. Next, after pickling with a 10% by weight aqueous sulfuric acid solution, the copper surface was activated by immersion in a substituted palladium plating solution (Meltex Corp., trade name: Melplate Activator 350) for 5 minutes at 23 ° C. . Next, electroless nickel plating solution (ICP-
It was immersed in Nicol U) at 85 ° C. for 30 minutes to perform electroless nickel plating. Next, it was immersed in a displacement gold plating solution (trade name: IM-GOLD, manufactured by Nippon Kojunka Kagaku) at 85 ° C. for 10 minutes to perform displacement gold plating. Next, it was immersed in an electroless gold plating solution (trade name: HGS-2000, manufactured by Hitachi Chemical Co., Ltd.) at 65 ° C. for 40 minutes to perform electroless gold plating. After performing such an operation, plating resistance was evaluated by observing the appearance of the resist. The evaluation criteria are as follows. ：: Good plating resistance (resisting and peeling of resist, and no peeling of plating occurs) ×: Poor plating resistance (thing of floating and peeling of resist and peeling of plating generated)

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

According to the first aspect of the present invention, the photosensitive resin composition according to the present invention can be applied to the production of printed wiring boards by heat curing at a temperature of 250 ° C. or less, whereby PCT resistance, low temperature curing property, solder heat resistance, plating solution resistance, Excellent chemical resistance, electrical insulation, storage stability and work environment. The photosensitive resin composition according to claim 2,
The photosensitive resin composition according to claim 1 has the effect, is more excellent in PCT resistance, and has high sensitivity. The photosensitive resin composition according to claim 3 exhibits the effect of the photosensitive resin composition according to claim 2, and is a photosensitive resin composition having more excellent PCT resistance, more excellent developability, and higher sensitivity. is there. The method for producing a relief pattern according to claim 4 is characterized in that
It has excellent CT properties, low-temperature curability, solder heat resistance, plating solution resistance, chemical resistance, electrical insulation, work environment, etc., and can produce a relief pattern suitable for an interlayer insulating film and the like.

[Brief description of the drawings]

FIG. 1 is a negative mask used in a plating resistance test in Examples and Comparative Examples.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 18/81 C08G 18/81 73/12 73/12 G03F 7/028 G03F 7/028 H01L 21/027 H01L 21/30 502R (72) Inventor Fumihiko Ota 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Hiroyuki Kawakami 4-3-1-1, Higashicho, Hitachi City, Ibaraki Hitachi Chemical Industry Co., Ltd.

Claims (4)

[Claims] (A) (a) General formula (I) (Wherein, R ¹ represents a tetravalent organic group having 2 to 30 carbon atoms) or a tetracarboxylic dianhydride or a derivative thereof, and (b) a general formula (II): (Wherein, R ² represents a divalent organic group having 1 to 30 carbon atoms) and (c) a general formula (III) (Wherein n is an integer of 1 to 4, R ³ represents a hydrogen atom, a halogen atom, a nitro group or an alkyl group having 1 to 9 carbon atoms) or a derivative thereof. (D) 1
Ethylenically unsaturated group-containing polyimide precursor obtained by reacting a compound having one isocyanate group and one or more ethylenically unsaturated groups in a molecule, (B) photopolymerization having one or more ethylenically unsaturated groups A photosensitive resin composition comprising a water-soluble unsaturated compound and (C) a photopolymerization initiator. 2. The composition further comprises (D) a blocked isocyanate resin and (E) a heterocyclic compound having at least one thiol group, in addition to the components (A), (B) and (C). 2. The photosensitive resin composition according to item 1. 3. Component (A) is 20 to 95 parts by weight based on 100 parts by weight of the total of components (A) and (B).
The component (B) has a total amount of the components (A) and (B) of 10
As 0 parts by weight, 5 to 80 parts by weight, the component (C) is
0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B), and the component (D) is used based on 100 parts by weight of the total amount of the components (A) and (B). And 0-4
The photosensitive resin composition according to claim 2, wherein 0 parts by weight and the component (E) are 0 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 4. A method for producing a relief pattern, comprising forming a layer of the photosensitive resin composition according to claim 1, 2 or 3 on a substrate, exposing it imagewise, and then developing.