JPH11218917A - Photosensitive resin composition and production of photosensitive solder resist using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. which can be used for the production of a printed circuit board, which can be hardened by heating at <=250 deg.C, which has excellent PCT resistance and heat resistance such as soldering heat resistance, and excellent characteristics required as a solder resist such as resistance to a plating liquid, chemical resistance and electric insulating property, which can be developed with an aq. developer preferable for the working environment and which has excellent storage stability, and to provide a producing method of a solder resist using this compsn. SOLUTION: This resin compsn. contains (A) a polyimide precursor, (B) a photopolymerizable unsatd. compd. which is the urethane reaction product of trimethylhexamethylene diisocyanate. aliphatic or aromatic alcohol and a compd. having at least one (meth)acrylate group and alcohol groups, and (C) a photopolymn. initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition used for producing a printed wiring board and the like, and a method for producing a solder resist using the same.

[0002]

2. Description of the Related Art In recent years, printed wiring boards have been developed in response to miniaturization, weight reduction, multifunctionality, high reliability, and low price of electronic devices.
A component mounting method for electrically connecting a component and a substrate on the surface of a conductor pattern without using a component hole called a surface mounting method is rapidly expanding. For the manufacture of printed wiring boards,
Using a photosensitive resin composition for higher precision and higher reliability than before, the photosensitive solder resist used for the purpose of limiting the soldering position of the printed wiring board on which the wiring is formed by photographic method and protecting the wiring is Used. However, the photosensitive solder resist used for printed wiring boards using the surface mounting method requires high heat resistance and long-term reliability, and the conventional photosensitive solder resist mainly composed of epoxy acrylate requires pressure cooker. Performing a test (hereinafter abbreviated as PCT) causes blistering and peeling of the resist, and has a problem that the heat and humidity resistance is 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. Further, in the case of a conventional photosensitive solder resist using an aromatic polyamic acid, the heat curing temperature after forming an image by a photographic method is as high as 350 ° C. or more, and it cannot be used for a printed wiring board due to the heat resistance of a substrate or the like. There is. 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.

[0003]

(1) The present invention provides a PCT resistance, a low-temperature curing property, a solder heat resistance, a plating solution resistance, and a heat resistance of 250 ° C. or less which can be applied to the manufacture of a printed wiring board. An object of the present invention is to provide a photosensitive resin composition which is excellent in various properties required for a solder resist such as chemical property and electrical insulation property, is excellent in storage stability, and can be developed using an aqueous developer having a good working environment. (2) Further, the present invention provides the photosensitive resin composition which exhibits the effect of the photosensitive resin composition of (1), is more excellent in developability, and has high sensitivity. (3) Further, the present invention provides a photosensitive resin composition which exhibits the effect of the photosensitive resin composition of (1) and has more excellent low-temperature curability. (4) Further, the present invention provides a photosensitive resin composition which exhibits the effect of the photosensitive resin composition of (1) and has more excellent plating solution resistance. (5) Further, the present invention provides a photosensitive resin composition exhibiting the effect of the photosensitive resin composition of (1) and having more excellent solder heat resistance. (6) Further, the present invention provides the photosensitive resin composition which exhibits the effect of the photosensitive resin composition of (1), has more excellent storage stability, and has higher sensitivity. (7) Further, the present invention provides a photosensitive resin composition exhibiting the effects of the photosensitive resin composition of (3), and particularly having excellent low-temperature curability. (8) Further, the present invention provides a photosensitive resin composition exhibiting the effects of the photosensitive resin composition of (1), further having excellent compatibility, and particularly having excellent PCT resistance. (9) Further, the present invention provides the photosensitive resin composition having the effect of the photosensitive resin composition of (6), particularly having excellent storage stability and particularly high sensitivity. (10) The present invention further provides a solder resist having excellent PCT resistance, low-temperature curability, solder heat resistance, plating solution resistance, chemical resistance, electrical insulation, etc., using an alkaline aqueous solution having a good working environment. It provides a manufacturing method. (11) Further, the present invention provides a method for producing a solder resist which exhibits the effects of the method for producing a solder resist of (10) and is more excellent in PCT resistance, solder heat resistance, electrical insulation and the like.

[0004]

According to the present invention, there is provided (A) a compound represented by the following general formula (I):

[0005]

Embedded image

(Wherein, R ₁ represents a tetravalent organic group having 2 to 30 carbon atoms, R ₂ represents a divalent organic group having 2 to 240 carbon atoms, and Xs independently represent OH or A polyimide precursor having a repeating unit represented by a monovalent organic group having 1 to 30 carbon atoms), (B) trimethylhexamethylene diisocyanate, an aliphatic or aromatic dialcohol, and at least one (meth) A) a photopolymerizable unsaturated compound which is a urethanization reaction product of a compound having an acrylate group and an alcohol group, and (C) a photopolymerization initiator which generates free radicals upon irradiation with actinic light; And a photosensitive resin composition characterized by the following.

In the present invention, the polyimide precursor of the component (A) is 20 to 95 parts by weight in solids, and the photopolymerizable unsaturated compound of the component (B) is 5 to 80 parts by weight (where (A) )
The solid content of the component and the total amount of the component (B) are 100 parts by weight), and the photopolymerization initiator of the component (C) is 0.01 to 20 parts by mass.
The photosensitive resin composition having a mixing ratio of 100 parts by weight (with respect to 100 parts by weight of the total of the solid content of the component (A) and the component (B)). The present invention also relates to the photosensitive resin composition, wherein the solvent is a non-nitrogen-containing solvent in the polyimide precursor of the component (A) or a polymer solution thereof.

In the present invention, R _{1 in} the general formula (I) of the component (A) is represented by the following general formula (VI)

Embedded image (In the formula, Y is a single bond or _{-CO -, - SO 2 -,} -
O-, -C (CF ₃ ) _2- ) or the photosensitive resin composition, which is a tetravalent organic group.

In the present invention, R _{2 in} the general formula (I) of the component (A) is represented by the following general formula (VII):

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

[0010]

Embedded image Wherein R _{11 to} R ₁₄ each independently represent a group having 1 to 1 carbon atoms.
6 represents a hydrocarbon group, and n independently represents an integer of 0 to 4).

[0011] The present invention also relates to the photosensitive resin composition, wherein the component (C) is a photopolymerization initiator which has no amine structure in the molecular structure and generates free radicals upon irradiation with active light. The present invention also relates to the photosensitive resin composition, wherein the non-nitrogen-containing solvent as the component (A) is a lactone, an alicyclic ketone or an ether. Also, the present invention
The present invention relates to the photosensitive resin composition, wherein the photopolymerizable unsaturated compound as the component (B) is a reaction product of trimethylhexamethylene diisocyanate, cyclohexane dimethanol, and 2-hydroxyethyl (meth) acrylate.

[0012] The present invention also relates to the photosensitive resin composition, wherein the photopolymerization initiator of the component (C) is benzyldimethyl ketal.

Further, the present invention provides a method for applying a solution of the photosensitive resin composition on a substrate, drying and applying imagewise exposure, and then adding a surfactant or an organic solvent in an amount of 0.1 to 50% by weight to an inorganic material. The present invention relates to a method for producing a solder resist, wherein development is performed using an alkaline aqueous solution containing 0.01 to 30% by weight of an alkaline compound as a developer. In addition, the present invention relates to a method for manufacturing a solder resist including a step of irradiating active light after development and a step of post-heating.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive resin composition of the present invention will be described in detail. In the photosensitive resin composition of the present invention, the polyimide precursor as the component (A) can be represented by the above general formula (I). The component (A) includes, for example, (a) a compound represented by the general formula (III):

[0015]

Embedded image

(Wherein, R ₁ is a group of 4 having 2 to 30 carbon atoms)
And (b) a general formula (IV) H ₂ N—R ₂ —NH ₂ (IV) wherein R ₂ is a carbon atom The number is 2 to 240, preferably 2
To 60, more preferably 2 to 30 divalent organic groups) in an organic solvent.

The tetracarboxylic dianhydride represented by the general formula (I) includes, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid represented by the general formula (VI): , 3 ', 4,4'-biphenyltetracarboxylic acid, 2,3', 3,4'-biphenyltetracarboxylic acid, 2,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4 And tetracarboxylic dianhydrides such as 4,4'-diphenylethertetracarboxylic acid and 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid. 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,
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]
Aromatics such as propane, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic acid, and 4,4′-bis (2,3-dicarboxyphenoxy) diphenylmethane Tetracarboxylic acid dianhydride, the following general formula (VIII)

[0018]

Embedded image

(Wherein, R ₅ and R ₆ are monovalent hydrocarbon groups, preferably C 1-10 hydrocarbon groups, more preferably C 1-5 alkyl groups or C 6-10 alkyl groups. An aromatic tetracarboxylic dianhydride represented by an aryl group (phenyl group, tolyl group, naphthyl group), which may be the same or different, and 1 is an integer of 1 or more); , 5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid,
Aliphatic tetracarboxylic dianhydrides such as cyclobutenetetracarboxylic acid and butanetetracarboxylic acid can also be used.

The diamine represented by the general formula (IV) is not particularly limited. For example, the diamine represented by the general formula (VII)
2,2-bis- [4- (4-aminophenoxy) phenyl] propane and 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. In the formula (VII), R _{11 to} R ₁₄ are each independently preferably an alkyl group or an alkoxy group having 1 to 6 carbon atoms. As other aromatic diamines, 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, a part of the diamine component, for example, ethylene diamine,
Tetramethylene diamine, hexamethylene diamine,
1,2-diaminocyclohexane, the following general formula (IX)

[0021]

Embedded image

(Wherein R ₇ and R _{8 each} have 1 to 1 carbon atoms)
0 represents a divalent hydrocarbon group, which may be the same or different; R ₉ and R _{10 each} represent a monovalent hydrocarbon group (preferably having 1 to 10 carbon atoms); And m is an integer of 1 or more), 1,3-bis (aminomethyl) cyclohexane, manufactured by San Techno Chemical Co., Ltd.
Jeffamine D-230, D-400, D-200
0, D-4000, ED-600, ED-900, ED
An aliphatic diamine component such as polyoxyalkylenediamine such as -2001 and EDR-148 may be used.

The polyimide precursor used in the present invention comprises:
It can be produced by various known methods. When X is OH in the general formula (I), it can be obtained by reacting a tetracarboxylic anhydride and a diamine in an organic solvent used as required. In the case where X contains a monovalent organic group, and in the case of via -O-, tetracarboxylic dianhydride and a hydroxyl group-containing compound are mixed and reacted to produce a half ester of tetracarboxylic acid. The acid can be chlorided with thionyl chloride and then reacted with a diamine, or the tetracarboxylic acid half ester can be synthesized with a diamine using a carbodiimide as a condensing agent. In the case where X is a monovalent organic group, and in the case of via -NH-, by reacting tetracarboxylic anhydride and a diamine in an organic solvent used as required, and then reacting with an isocyanate compound, Can be manufactured.

The ratio of the amount of the tetracarboxylic dianhydride represented by the general formula (III) to the diamine represented by the general formula (IV) is 1.1 / 1.0 to 1.0 / 1.0.
It is preferred to be in the range of 1.1 (mol). If it exceeds this range, the molecular weight of the polyimide precursor does not grow, so that heat resistance and the like tend to decrease. The weight average molecular weight of the polyimide precursor used in the present invention is 5,0
It is preferable that it is 00 to 200,000 because it is excellent in low-temperature curability, heat resistance, mechanical properties and workability.

Further, the solvent used in the reaction for producing the polyimide precursor as the component (A) must be inert to the polyimide precursor. For example, "Solvent Handbook" (Kodansha, published in 1976)
Solvents described on pages 143 to 852 of the above are used. For example, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,
Nitrogen-containing compounds such as 4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, sulfur compounds such as sulfolane and dimethylsulfoxide, γ-butyrolactone, γ-valerolactone; γ
Lactones such as caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl,
Ethers such as dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether and tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether; carbonates such as ethylene carbonate and propylene carbonate; methyl ethyl ketone; methyl isobutyl Ketone,
Ketones such as cyclohexanone and acetophenone, butanol, octyl alcohol, alcohols such as ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, and tetraethylene glycol monomethyl (or monoethyl) ether; Phenols such as phenol, cresol and xylenol, esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate, hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane, halogens such as trichloroethane, tetrachloroethane and monochlorobenzene Hydrocarbons and the like are used. These are used alone or in combination.

It is preferable to use a non-nitrogen-containing solvent from the viewpoints of PCT resistance and low-temperature curability, for example, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl. Lactones such as -γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, tetraethylene Ethers such as glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, carbonates such as ethylene carbonate and propylene carbonate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc. It is preferred to use a ketone.

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, and if it exceeds 10 times, the reaction rate tends to decrease.

Photopolymerization which is a urethanization reaction product of component (B), trimethylhexamethylene diisocyanate, an aliphatic or aromatic dialcohol, and a compound having at least one (meth) acrylate group and an alcohol group. The unsaturated compound is produced by reacting trimethylhexamethylene diisocyanate, an aliphatic or aromatic dialcohol, and a compound having at least one (meth) acrylate group and an alcohol group in a soluble solvent, and subjecting the compound to a urethanation reaction. can do. Examples of the aliphatic or aromatic dialcohol used herein include, for example, an aliphatic dialcohol such as ethylene glycol, propylene glycol, hexamethylene glycol, and cyclohexane dimethanol, or an aromatic dialcohol such as benzene dimethanol and benzene diethanol. Cyclohexanedimethanol is preferred from the viewpoint of PCT resistance. Also, at least one of the
Examples of the compound having two (meth) acrylate groups and an alcohol group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, and a monoepoxy compound. Esterification reaction products with (meth) acrylate are used, and 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of photosensitivity.

The soluble solvent used in the urethanization reaction needs to be inert to the urethanization reaction product and the raw material for the urethanization reaction. For example, the solvent is described in "Solvent Handbook" (Kodansha, 1976). Solvents described on pages 143 to 852 of Jpn. For example, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-
Nitrogen-containing compounds such as 3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and 1,3-dimethyl-2-imidazolidinone; sulfur compounds such as sulfolane and dimethyl sulfoxide; γ-butyrolactone; γ-valero Lactone,
lactones such as γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, dioxane, 1,2-dimethoxyethane, ethylene carbonate, carbonates such as propylene carbonate, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone and acetophenone,
Esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate, hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane, and halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene are used. These are used alone or in combination.
Further, it is preferably a non-nitrogen-containing solvent from the viewpoint of PCT resistance and low-temperature curability, and toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone are preferable.

Examples of the photopolymerization initiator which generates free radicals upon irradiation with actinic light as the component (C) include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin phenyl ether and the like. Benzoin ethers, benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), benzophenones such as N, N'-tetraethyl-4,4'-diaminobenzophenone, benzyldimethylketal (Ciba・ Geigy, Irgacure 65
1), benzyl ketals such as benzyl diethyl ketal, 2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloroacetophenone, p
Acetophenones such as dimethylaminoacetophenone, xanthones such as 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone, or hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 1- (4-isopropylphenyl ) -2-Hydroxy-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,
These are used alone or in combination of two or more.

The photopolymerization initiator which can be used as the component (C) includes, for example, 2,4,5-triallylimidazole dimer and 2-mercaptobenzoxazole,
Combinations with leuco crystal violet, tris (4-diethylamino-2-methylphenyl) methane and the like are also included. Additives which do not have photoinitiating property by themselves, but provide a sensitizer system having better photopolymerization initiating performance as a whole when used in combination with the above substances, such as triethanolamine for benzophenone. Can be used.

The present inventors have conducted intensive studies and found that the photoinitiator as the component (C), which does not have an amine structure in the molecular structure, has particularly good storage stability of the photosensitive resin composition. I found to do. Examples of the photopolymerization initiator which has no amine structure in the molecular structure and generates free radicals upon irradiation with actinic light include benzophenone or a benzophenone derivative having no amine structure, benzyl dimethyl ketal (manufactured by Ciba Geigy) , Irgacure 65
1), benzyl ketals such as benzyl diethyl ketal, acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloroacetophenone, 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone Xanthones, hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (manufactured by Merck, Darocure 111)
6), 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Merck, Darocure 1173) and the like are preferable, and benzyldimethyl ketal is particularly preferable in terms of sensitivity, resolution, and resist shape.

In the photosensitive resin composition of the present invention thus obtained, the amount of the solid component (A) used is 20
It is preferable that the amount be from 95 to 95 parts by weight (provided that the total amount of the solid content of the component (A) and the component (B) is 100 parts by weight).
If the amount of the solid component (A) used is less than 20 parts by weight, the PCT resistance is reduced, and if it exceeds 95 parts by weight, the sensitivity is reduced. The amount of the component (B) is preferably 5 to 80 parts by weight (provided that the total amount of the solid content of the component (A) and the component (B) is 100 parts by weight). If the amount of the component (B) is less than 5 parts by weight, the sensitivity is lowered, and if it is more than 80 parts by weight, the PCT resistance is lowered. The amount of the component (C) used is 0.
The content is preferably from 0.01 to 20 parts by weight (provided that the total amount of the solid content of the component (A) and the component (B) is 100 parts by weight). When the amount of the component (C) is less than 0.01 part by weight, the sensitivity is lowered. When the amount exceeds 20 parts by weight, the negative pattern formed has a poor resist shape.

[0034] Additives such as dyes, pigments, plasticizers and stabilizers may be added to the photosensitive resin composition of the present invention as needed. The amount of these additives is 100
It is preferably 0.001 to 10 parts by weight based on parts by weight. In addition, a known and commonly used thermosetting resin and a bridging agent can be used in the photosensitive resin composition of the present invention for the purpose of improving properties such as heat resistance, moisture resistance, and corrosion resistance.

As the thermosetting agent, for example, a combination of a commonly used epoxy resin such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolac, cresol novolac type and an epoxy curing agent of amine type, acid anhydride type or the like can be used. , Melamine resin,
Amino resins such as urea resins and guanamine resins and derivatives thereof, phenol resins, blocked isocyanate resins, and maleimide resins composed of maleic anhydride and a diamine compound or a diisocyanate compound can be used. Blocked isocyanate resin from the viewpoint of PCT resistance,
Or a maleimide resin composed of maleic anhydride and a diamine compound or a diisocyanate compound is preferable,
Further, a blocked isocyanate resin is particularly preferred from the viewpoint of light sensitivity.

The amount of the thermosetting agent added is 0.1 parts by weight based on 100 parts by weight of the total amount of the solid content of the component (A) and the component (B).
The amount is preferably from 50 to 50 parts by weight, more preferably from 0.5 to 40 parts by weight. If the addition amount is less than 0.1 part by weight, the curability may be insufficiently improved,
If it exceeds 50 parts by weight, viscosity stability tends to be poor.

In producing a photosensitive solder resist, first, a photosensitive resin composition containing the components (A) to (C) is uniformly dissolved. Next, the photosensitive resin composition in the form of a solution was added to a silicon wafer, metal, ceramic,
After uniformly coated on a substrate such as a copper-clad laminate, the solvent is removed by heating or blowing with hot air to form a dry film. The thickness of the dried film is not particularly limited, and is preferably 5 to 100 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,
If necessary, drying may be performed under reduced pressure.

In the case of using the photosensitive resin composition of the present invention, it is not necessary to preheat 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 photosensitive layer thus obtained is then imagewise exposed to actinic light using a negative or positive film. As the active light, light generated from a known active light source, for example, a carbon arc, a mercury vapor arc, a xenon arc, or the like is used. Since the sensitivity of the photoinitiator contained in the photosensitive layer is usually maximum in the ultraviolet region,
In that case, the active light source should emit ultraviolet light effectively. Next, after the exposure, the unexposed portion is removed by a known method such as spraying, rocking immersion, brushing, and scraping using an alkaline aqueous solution preferably containing 0.1 to 50% by weight of a surfactant or an organic solvent. Remove and develop. Surfactants or organic solvents used in the developer include heptanoic acid diethanolamide, polyoxyethylene paracumylphenyl ether, polydimethylsiloxane, and the like, and heptanoic acid diethanolamide or polyoxyethylene paracumylphenyl ether is preferable. Oxyethylene paracumyl phenyl ether is particularly preferred. Further, as the alkali component used in the developer, sodium carbonate, sodium hydroxide, borax and the like are preferably used in the range of 0.01 to 30% by weight. As the alkali component, an inorganic alkaline compound is preferably used. Further, the temperature of the developer used for development is adjusted by the developability of the photosensitive layer. Further, another surfactant, an antifoaming agent, and the like may be mixed in the developer.

Further, after the development, irradiation with ultraviolet rays by a high-pressure mercury lamp or heating is performed for the purpose of improving PCT resistance, solder heat resistance, chemical resistance and the like. The irradiation amount of the ultraviolet rays during the irradiation of the ultraviolet rays is preferably 0.2 to 10 J / cm ^2, and the temperature during the irradiation is preferably 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. Thus, the photosensitive resin composition of the present invention can be used for various protective films, insulating films, and the like.

[0040]

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 Synthesis of Polyimide Precursor 2954.7 g of γ-butyrolactone was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen gas introduction pipe and capable of heating and cooling and having a capacity of about 5 liters. , 2,2-bis [4-
(4-aminophenoxy) phenyl] propane 410.
00 g (1.00 mol), and the temperature was raised to 45 ° C.
While keeping the temperature at ５０50 ° C., 334.88 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (1.
04 mol) was added in small portions. After the addition, about 5
After continuing the reaction for an hour, the mixture was cooled to room temperature to obtain a polyimide precursor solution (A-1).

(Synthesis Example 2 Synthesis of Polyimide Precursor) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, and a nitrogen gas introduction pipe and capable of heating and cooling and having a volume of about 5 liters, γ-
3109.3 g of butyrolactone and 2,2-bis [4-
(4-aminophenoxy) phenyl] propane 410.
0 g (1.00 mol), and the temperature was raised to 45 ° C.
While maintaining the temperature at 50 ° C., 372.32 g of 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride
(1.04 mol) was added in small portions. After addition, 45 ° C
The reaction was continued for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (A-2).

Synthesis Example 3 Synthesis of Polyimide Precursor 2857.6 g of γ-butyrolactone was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, and a nitrogen gas introduction pipe and capable of heating and cooling and having a capacity of about 5 liters. , 2,2-bis [4-
(4-aminophenoxy) phenyl] ether 384.
00 g (1.00 mol), and the temperature was raised to 45 ° C.
While keeping the temperature at ５０50 ° C., 334.88 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (1.
04 mol) was added in small portions. After the addition, about 5
After the reaction was continued for an hour, the solution was cooled to room temperature to obtain a polyimide precursor solution (A-3).

Synthesis Example 4 Synthesis of Polyimide Precursor 2808.0 g of γ-butyrolactone was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, and a nitrogen gas introduction pipe and capable of heating and cooling and having a volume of about 5 liters. , 2-bis [4- (4-
Aminophenoxy) phenyl] ether 384.00 g
(1.00 mol), and the temperature was raised to 45 ° C.
C., while maintaining 3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride in 322.40 g (1.0%).
4 mol) was added in small portions. After the addition, the reaction was continued at 45 ° C. for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (A-4).

(Synthesis Example 5 Synthesis of Photopolymerizable Unsaturated Compound) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, a nitrogen gas introduction pipe, and a dropper and capable of heating and cooling and having a volume of about 1 liter, 137 g of toluene and 210.0 g (1.0 mol) of trimethylhexamethylene diisocyanate were added, and the temperature was raised to 70 ° C., and while maintaining the temperature at 70 to 75 ° C., 72.0 g (0.5 mol) of cyclohexanedimethanol and 2 mol
130.0 g of hydroxyethyl methacrylate (1.
0 mol) was added dropwise little by little. After the dropwise addition, the reaction was continued at 70 ° C. for about 5 hours, and then cooled to room temperature to obtain a photopolymerizable monomer solution (B-1).

(Comparative Synthesis Example 1 Synthesis of Polyimide Precursor) N-methylpyrrolidone 1696.N was placed in a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, and a nitrogen gas introduction pipe and capable of heating and cooling and having a capacity of about 5 liters. 3 g and 4,4-diaminodiphenyl ether 200.0 g (1.00 mol)
And raise the temperature to 45 ° C, while keeping it at 43-50 ° C,
226.72 g (1.04 mol) of pyromellitic dianhydride were added in small portions. After the addition, the reaction was continued at 45 ° C. for about 5 hours, and then cooled to room temperature to obtain a polyimide precursor solution (A-5).

(Comparative Synthesis Example 2 Synthesis of Photopolymerizable Unsaturated Compound) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, a nitrogen gas introducing pipe and a dropper, and capable of heating and cooling and having a capacity of about 1 liter. , 174 g of toluene and 174.0 g (1.0 mol) of tolylene diisocyanate were added, and the temperature was raised to 70 ° C, and while maintaining the temperature at 70 to 75 ° C, 232.0 g (2.0 mol) of 2-hydroxyethyl acrylate was added. It was dripped little by little. After the dropwise addition, the reaction was continued at 70 ° C. for about 5 hours, and then cooled to room temperature to obtain a photopolymerizable monomer solution (B-3).

(Comparative Synthesis Example 3 Synthesis of Photopolymerizable Unsaturated Compound) In a reaction vessel equipped with a thermometer, a stirrer, a cooling pipe, a nitrogen gas introduction pipe, and a dropper and capable of heating and cooling and having a capacity of about 1 liter. And 193 g of toluene and 250.0 g (1.0 mol) of diphenylmethane diisocyanate.
The temperature was raised to 0 ° 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 about 5 hours, and then cooled to room temperature to obtain a photopolymerizable monomer solution (B-4).

Examples 1 to 6, Comparative Examples 1 to 4 Component (A) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1
The component (B) such as the photopolymerizable unsaturated compound obtained in Synthesis Example 5 and Comparative Synthesis Examples 2 and 3, the component (C), and the dye were mixed in Table 1 and in the mixing ratio shown in Table 2, respectively. Parts by weight) to obtain a solution of the photosensitive resin composition.

[0050]

[Table 1]

Next, a copper-clad laminate having a copper thickness of 18 μm (MCL-E-679 manufactured by Hitachi Chemical Co., Ltd.) was polished with Scotch Bright manufactured by Sumitomo 3M, 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.
Dried on a hot plate at about 10 minutes. The dried thickness of the layer of the photosensitive resin composition was about 20 μm.

The test substrate on which the layer of the photosensitive resin composition thus obtained was formed was tested for developability, storage stability, PCT resistance and solder heat resistance by the following methods. The results are shown in Table 2.

(1) Developability The test substrate on which the layer of the photosensitive resin composition obtained above was formed was prepared using an alkaline aqueous solution containing 2 wt% of polyoxyethylene paracumyl phenyl ether and 0.5 wt% of sodium carbonate. 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 having a copper thickness of 18 μm (M, manufactured by Hitachi Chemical Co., Ltd.)
CL-E-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes. The test substrate was uniformly coated with the photosensitive resin composition solution having the above composition using an applicator in the same manner as described above.
Dried on a hot plate at about 10 minutes. The dried thickness of the layer of the photosensitive resin composition was about 20 μm. Next, using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd.
Exposure was performed at an exposure of 00 mJ / cm ² . Next, ultraviolet light was re-irradiated at a dose of ³ J / cm ² using an ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and then further heated at 200 ° C. for 60 minutes by a dryer. The test substrate thus obtained was subjected to a PCT treatment for up to 300 hours at 121 ° C. and 2 atm using a PCT test apparatus manufactured by Hirayama Seisakusho, and a tape test by a cross cut method was performed according to the evaluation method described below. The adhesion was evaluated. A / B (indicates that A out of B did not peel)

(4) Solder heat resistance The copper-clad laminate having a copper thickness of 18 μm (M, manufactured by Hitachi Chemical Co., Ltd.)
CL-E-679) was polished with Scotch Bright manufactured by Sumitomo 3M Limited, washed with water, and dried at 80 ° C. for 15 minutes. The test substrate was uniformly coated with the photosensitive resin composition solution having the above composition using an applicator in the same manner as described above.
Dried on a hot plate at about 10 minutes. The dried thickness of the layer of the photosensitive resin composition was about 20 μm. Next, the negative mask shown in FIG. 1 was brought into close contact with the photosensitive resin composition layer, and exposed using an HMW-590 type exposure machine manufactured by Oak Manufacturing Co., Ltd. at an exposure dose of 500 mJ / cm ² . Next, after the negative mask is peeled off, an alkaline aqueous solution containing 2 wt% of polyoxyethylene paracumyl phenyl ether and 0.5 wt% of sodium carbonate is used as a developing solution.
Spray developed at 60 ° C for 60 seconds. After development, 10
Then, the film was heated and dried again for 3 minutes, and was again irradiated with ultraviolet rays at a dose of ³ J / cm ² using an ultraviolet irradiation device manufactured by Toshiba Electric Materials Co., Ltd., and then further heated at 200 ° C. for 60 minutes by a dryer. A rosin-based flux A-226 (manufactured by Tamura Kaken) is applied to the surface of the test substrate thus obtained, immersed in a 260 ° C. solder bath for 180 seconds, and then immersed in 25 ° C. trichlene for 20 seconds. To remove the flux. After performing such an operation, the appearance of the resist was evaluated. The evaluation criteria are as follows. ：: Good solder heat resistance (no crack, floating or peeling of resist) ×: Poor solder heat resistance (Crack, floating or peeling of resist)

[0057]

[Table 2]

[0058]

(1) The photosensitive resin composition of the present invention has a PCT resistance, a low-temperature curing property, a solder heat resistance, and a plating solution resistance by heating and curing at 250 ° C. or less which can be applied to the production of printed wiring boards. It is excellent in various properties required for a solder resist, such as chemical resistance and electrical insulation, is excellent in storage stability, and can be developed using an aqueous developer having a good working environment. (2) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and has excellent developability and high sensitivity. (3) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and is excellent in low-temperature curability. (4) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and is more excellent in plating solution resistance. (5) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and has more excellent solder heat resistance. (6) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), is more excellent in storage stability, and has higher sensitivity. (7) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (3), and is particularly excellent in low-temperature curability. (8) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), further has excellent compatibility, and particularly has a P resistance.
Excellent CT properties. (9) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (6), has particularly excellent storage stability, and has particularly high sensitivity. (10) The method for producing a solder resist according to the present invention uses an alkaline aqueous solution having a good working environment to improve the PCT resistance, low-temperature curing property, solder heat resistance, plating solution resistance, chemical resistance, electrical insulation property, etc. Excellent. (11) The method for producing a solder resist of the present invention comprises the steps of (1)
The effect of the method 0) for producing a solder resist is exhibited, and the PCT resistance, solder heat resistance, electrical insulation, and the like are further improved.

[Brief description of the drawings]

FIG. 1 is a schematic view of a negative mask used for evaluating solder heat resistance in the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H05K 3/18 H05K 3/18 D 3/28 3/28 D (72) Inventor Fumihiko Ota 4--13 Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical Co., Ltd. Ibaraki Research Laboratory

Claims (11)

[Claims] (A) General formula (I) (Wherein, R ₁ represents a tetravalent organic group having 2 to 30 carbon atoms, R ₂ represents a divalent organic group having 2 to 240 carbon atoms, and Xs each independently represent OH or carbon atoms. (B) trimethylhexamethylene diisocyanate, an aliphatic or aromatic dialcohol, and at least one (meth) acrylate group And a photopolymerizable unsaturated compound which is a urethanation reaction product of a compound having an alcohol group and a compound having an alcohol group, and (C) a photopolymerization initiator which generates free radicals upon irradiation with actinic light. Photosensitive resin composition. 2. The polyimide precursor of component (A) has a solid content of 20 to 95 parts by weight, and the photopolymerizable unsaturated compound of component (B) has 5 to 80 parts by weight (provided that the solid content of component (A) is 5 to 80 parts by weight). And the photopolymerization initiator of the component (C) is 0.01 to 20 parts by weight (provided that the solid content of the component (A) and the solid content of the component (B) are 100 parts by weight). The photosensitive resin composition according to claim 1, wherein the mixing ratio is based on the total amount of 100 parts by weight). 3. The photosensitive resin composition according to claim 1, wherein the solvent in the polyimide precursor of the component (A) or the polymer solution thereof is a non-nitrogen-containing solvent. 4. A compound represented by the following general formula (VI) wherein R ₁ in the general formula (I) is (In the formula, Y is a single bond or _{-CO -, - SO 2 -,} -
_{O -, - C (CF 3} ) 2 - photosensitive resin composition according to any one of claims 1 to 3 is a tetravalent organic group represented by any one shows a) the. 5. A compound represented by the following general formula (VII), wherein R ₂ in the general formula (I) is (Wherein X is a single bond or —O—, —S—, —CO—,
—SO ₂ —, —CONH—, —CH ₂ —, —C (C
H ₃ ) _2- , -C (CF ₃ ) ₂ -or Wherein R _{11 to} R ₁₄ each independently represent a group having 1 to 1 carbon atoms.
6 represents a hydrocarbon group, and n independently represents an integer of 0 to 4.) The photosensitive resin composition according to any one of claims 1 to 4. 6. The photosensitive resin composition according to claim 1, wherein the component (C) is a photopolymerization initiator having no amine structure in the molecular structure. 7. The method according to claim 3, wherein the non-nitrogen-containing solvent is a lactone, an alicyclic ketone or an ether.
Item 6. The photosensitive resin composition according to item 1. 8. The photopolymerizable unsaturated compound as the component (B),
The photosensitive resin composition according to any one of claims 1 to 7, which is a reaction product of trimethylhexamethylene diisocyanate, cyclohexane dimethanol, and 2-hydroxyethyl (meth) acrylate. 9. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator of the component (C) is benzyldimethyl ketal. 10. A solution of the photosensitive resin composition according to any one of claims 1 to 9, which is applied to a substrate, dried, and imagewise exposed, and then a surfactant or an organic solvent is added to the substrate. .1 to
50% by weight and 0.01 to 30 inorganic alkaline compounds
A method for producing a solder resist, wherein development is performed using an alkaline aqueous solution containing by weight as a developing solution. 11. The method for producing a solder resist according to claim 10, which comprises a step of irradiating with active light after the development and a step of post-heating.