JPH11223946A - Photosensitive resin composition and production of photosensitive solder resist by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. which can be cured by heating at <=250 deg.C applicable for the production of a printed circuit board, which has excellent PCT resistance and heat resistance such as soldering heat resistance, and various characteristics required for a solder resist such as plating liquid resistance, chemical resistance and electric insulating property, and which can be developed with an aq. developer good for working environment, and to provide a producing method of a solder resist from this compsn. SOLUTION: This photosensitive resin compsn. contains (A) a polyimide precursor, (B) a photopolymerizable unsatd. compd., (C) a photopolymn. initiator, (D) a blocked isocyanate resin, and (E) a heterocyclic compd. having at least one thiol group. The compsn. is used to prepare a photosensitive solder resist.

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, 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, in a conventional photosensitive solder resist using a polyimide precursor,
The heat curing temperature after image formation by a photographic method is as high as 350 ° C. or more, and there is a problem that it cannot be used for a printed wiring board from the viewpoint of heat resistance of a substrate or the like. 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) The present invention further provides a photosensitive resin composition which exhibits the effect of the photosensitive resin composition of (1) and has more excellent plating solution resistance. (4) 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. (5) Further, the present invention provides a photosensitive resin composition which exhibits the effects of the photosensitive resin composition of (1) and has further excellent compatibility. (6) Further, the present invention provides a photosensitive resin composition exhibiting the effects of the photosensitive resin composition of (1) and having more excellent storage stability. (7) 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 aqueous alkaline solution having a good working environment. It provides a manufacturing method.

[0004]

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

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 each independently represent OH or a carbon atom. Represents a monovalent organic group having the number of 1 to 30, R ₃ represents hydrogen, halogen, a nitro group or an alkyl group having 1 to 9 carbon atoms, n ′ is an integer of 1 to 4,

Embedded image Represents a repeating unit), (B) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal, and (C) photopolymerization which generates free radicals upon irradiation with actinic light. The present invention relates to a photosensitive resin composition comprising: an initiator; (D) a blocked isocyanate resin; and (E) a heterocyclic compound containing at least one thiol group.

Further, according to the present invention, the polyimide precursor of the component (A) has a solid content of 20 to 95%.
5 parts by weight The photopolymerizable unsaturated compound of the component (B) is 5 to 80 parts by weight (provided that the total amount of the solid content of the component (A) and the component (B) is 1).
The photopolymerization initiator of the component (C) is used in an amount of 0.01 to 20 parts by weight (provided that the solid content of the component (A) and the total amount of the component (B) are 1).
(Based on 100 parts by weight) The blocked isocyanate resin of the component (D) is 1 to 4
0 parts by weight (based on 100 parts by weight of the total of the solid content of the component (A) and the component (B)) The heterocyclic compound containing at least one thiol group of the component (E) is 0.01 to 20 parts by weight. Parts by weight ((A)
(Based on 100 parts by weight of the total amount of the solid component and the component (B)).

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

[0008]

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).

Further, the present invention provides the photosensitive composition, wherein the component (B) is a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal and having at least one urethane bond in a molecular structure. The present invention relates to a water-soluble resin composition. The present invention also relates to the photosensitive resin composition, wherein the component (C) is a photopolymerization initiator that has no amine structure in the molecular structure and generates free radicals upon irradiation with active light.

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.

[0011]

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 component (A) may be a polyimide precursor represented by the general formula (I), or may be a polyimide precursor represented by the general formula (II)
May be a polyimide precursor comprising a repeating unit represented by The component (A) includes, for example, (a) a compound represented by the general formula (I)
II)

[0012]

Embedded image

(Wherein, R ₁ is 4 of 2-30 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 from 1 to 240, preferably 2
To 60, more preferably 2 to 30 divalent organic groups) and, if necessary, (c) a general formula (V)

[0014]

Embedded image

[0015] (wherein, n 'is an integer from 1 to 4, R ₃
Represents hydrogen, a halogen, a nitro group or an alkyl group having 1 to 9 carbon atoms) or an aminobenzimidazole or a derivative thereof in a solvent.

The tetracarboxylic dianhydride represented by the general formula (III) 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)

[0017]

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 l 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.

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, 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, Jeffamine D-230, D-400, D-200 manufactured by San Techno Chemical Co., Ltd.
0, D-4000, ED-600, ED-900, ED
An aliphatic diamine component such as polyoxyalkylenediamine such as -2001 and EDR-148 may be used. In the present invention, aminobenzimidazole or a derivative thereof represented by the general formula (V) may be used when producing a polyimide precursor. For example, 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.

When synthesizing the polyimide precursor of the component (A), the amount of the aminobenzimidazole represented by the general formula (V) or a derivative thereof is determined by the above formula (IV)
It is preferable that it is 0.1 to 10 mol% with respect to the total amount of the diamine compound represented by the formula and the aminobenzimidazole represented by the general formula (V) and its derivatives. 0.1
If it is less than mol%, the PCT resistance tends to be insufficient,
If it exceeds 10 mol%, the developability and storage stability tend to decrease. Further, the total used amount of the diamine compound represented by the general formula (IV) and the aminobenzimidazole and the derivative thereof represented by the general formula (V), and the tetracarboxylic acid represented by the general formula (III) The ratio of the amount of dianhydride used is 1.1 / 1.0 to 1.0 / 1.
It is preferred to be in the range of 1 (mol). If it exceeds this range, the molecular weight of the polyimide precursor will not be improved, so that the heat resistance and the like tend to decrease.

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), the tetracarboxylic dianhydride of the component (a), the diamine of the component (b) and, if necessary, the aminobenzimidazole or the derivative thereof of the component (c) are required. The reaction can be carried out in an organic solvent used according to the above. 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. X
Is a monovalent organic group, and in the case of via -NH-, a tetracarboxylic dianhydride and a diamine and optionally aminobenzimidazole or a derivative thereof are reacted in an organic solvent used as required. And then reacting with an isocyanate compound.

The weight average molecular weight of the polyimide precursor used in the present invention is preferably from 3,000 to 200,000, because it is excellent in low-temperature curability, heat resistance, mechanical properties and workability. .

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, 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 (by weight) 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. Further, the polyimide precursor as the component (A) may be, for example, a polymer solution thereof using a non-nitrogen-containing solvent as a solvent. Examples of the non-nitrogen-containing solvent include lactones, alicyclic ketones and the like. Ethers.

The photopolymerizable unsaturated compound having at least one terminal ethylenically unsaturated group as the component (B) is not particularly limited, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, and the like. Ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, pentenyl methacrylate, benzyl acrylate, benzyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, polyethylene glycol (meth ) Acrylates (with a total of 2 to 14 ethylene groups), polypropylene glycol di (meth) acrylate (with a total of 2 to 14 propylene groups), trimethylolpropanediac Rate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate,
Trimethylolpropaneethoxytriacrylate, trimethylolpropaneethoxytrimethacrylate, trimethylolpropanepropoxytrimethacrylate, trimethylolpropanepropoxytrimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate,
Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4 -Vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,
3-acryloyloxy-2-hydroxypropane,
1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, triacrylate of tris (β-hydroxyethyl) isocyanurate, the following general formula (X)

[0030]

Embedded image

(Wherein, R ₁₅ represents hydrogen or a methyl group;
q and r are integers of 1 or more),
Compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound, for example, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth)
Esterified products of polyvalent carboxylic acids such as acrylates, for example, phthalic anhydride and the like, and compounds having a hydroxyl group and an ethylenically unsaturated group, for example, β-hydroxyethyl (meth) acrylate, tolylene diisocyanate and 2-hydroxyethyl Urethane (meth) acrylates such as a reaction product of (meth) acrylate and a reaction product of trimethylhexamethylene diisocyanate, cyclohexane dimethanol and 2-hydroxyethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

As a result of intensive studies, the present inventors have found that the photopolymerizable unsaturated compounds used include organic isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, and trimethylhexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate. Is a photopolymerizable unsaturated compound having at least one urethane bond in its molecular structure, such as a urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a chain extender such as cyclohexane dimethanol if necessary. Is more preferable from the viewpoint of compatibility with other resist components such as a polyimide precursor and PCT resistance. Further, from the viewpoint of photosensitivity, a reaction product of trimethylhexamethylene diisocyanate, cyclohexanedimethanol, and 2-hydroxyethyl (meth) acrylate is particularly 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 which is the component (C) has no amine structure in the molecular structure, and the storage stability of the photosensitive resin composition is particularly excellent. 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,
Xanthones such as 2,4-diisopropylthioxanthone, hydroxycyclohexyl phenyl ketone (Ciba.
Geigy Corp., Irgacure 184), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck Corp., Darocure 1116),
2-hydroxy-2-methyl-1-phenylpropane-
1-one (manufactured by Merck, Darocure 1173) is preferred, and benzyldimethyl ketal is particularly preferred in terms of sensitivity, resolution, and resist shape.

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 room temperature. It is used as a resin for the thermosetting reaction, and examples of the blocked isocyanate resin include, for example, tolylene diisocyanate, hexamethylene diisocyanate, triisocyanurate composed of hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. Compounds (blocks) having an active hydrogen such as phenol, alcohol, oxime, β-dicarbonyl compound, lactam, amine imide, nitrile carbonate, isocyanate dimer, etc. ) It can be mentioned those obtained by reacting,
These are used alone or in combination of two or more. From the viewpoint of compatibility and PCT resistance, a hexamethylene diisocyanate or a triisocyanurate of hexamethylene diisocyanate is preferably used as a blocking agent, and a blocked isocyanate obtained by reacting methylethylketoxime as a blocking agent is preferable.A triisocyanurate of hexamethylene diisocyanate is preferable. A blocked isocyanate obtained by reacting methyl ethyl ketoxime as a blocking agent is particularly preferred.

Examples of the heterocyclic compound containing at least one thiol group as the component (E) include, for example,
2,5-dimercapto-1,3,4-thiadiazole,
2-mercapto-1-methyl-imidazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2-
Mercapto-benzimidazole, 2-mercapto-benzothiazole, 1H-1,2,4-triazole-3
-Thiol and the like, and 2,5-dimercapto-1,
3,4-thiadiazole is particularly preferred from the viewpoint of plating solution resistance.

In the thus obtained photosensitive resin composition of the present study, the amount of the solid component (A) used was 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. The amount of the component (D) is preferably 1 to 40 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 (C) is less than 1 part by weight, the PCT resistance decreases, and if it exceeds 40 parts by weight, the photosensitivity decreases. The amount of the component (E) is preferably 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 (E) is less than 0.01 part by weight, the plating solution resistance is reduced. When the amount exceeds 20 parts by weight, the negative pattern formed has a poor resist shape or contaminates the plating solution.

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. Further, the photosensitive resin composition of the present invention has heat resistance,
Known and commonly used thermosetting resins and bridging agents can be used for the purpose of improving properties such as moisture resistance and electric 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 novolak, cresol novolac type and an epoxy curing agent such as an amine type or an acid anhydride type is used. , Melamine resin,
Amino resins such as urea resins and guanamine resins, derivatives thereof, and phenol resins can be used. The addition amount of the thermosetting agent is preferably 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight, based on 100 parts by weight of the total of the solid content of the component (A) and the component (B). Is more preferable. If the amount is less than 0.1 part by weight, the curability may not be sufficiently improved, and if it exceeds 50 parts by weight, the viscosity stability tends to be poor.

In producing a photosensitive solder resist, first, a photosensitive resin composition containing the components (A) to (E) 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 containing preferably 0.1 to 50% by weight of an organic solvent or a surfactant. Remove 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, and polyoxyethylene paracta. Mill phenyl ether or the like is used, and polyoxyethylene paracumyl phenyl ether is particularly preferable. Further, as the alkali component used in the developer, sodium carbonate, sodium hydroxide, borax and the like are preferably 0.01%.
It is used in a range of ３０30 wt%. 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, for the purpose of improving PCT resistance, solder heat resistance, chemical resistance and the like, ultraviolet (active light) irradiation with a high-pressure mercury lamp or heating (post-heating) may be performed. The amount of UV irradiation during UV irradiation is 0.2 to 1
The irradiation temperature is preferably 0 J / cm ^2, and the irradiation temperature 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.

[0044]

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) Thermometer, stirrer, cooling pipe,
Approximately 5 heating and cooling volumes with nitrogen gas inlet
Γ-butyrolactone 2955.3 in a liter reaction vessel
g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane 405.900 g (0.99 mol)
And 2.663 g of 2-aminobenzimidazole (0.
02 mol), raise the temperature to 45 ° C, and maintain the temperature at 43 to 50 ° C, 334.880 g (1.04 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride.
Was added in small portions. After the addition, the reaction was continued at 45 ° C. for about 5 hours, then cooled to room temperature and the polyimide precursor solution (A
-1) was obtained. The solution of the obtained polyimide precursor (A-
The solid content of 1) was 20% by weight, and the weight average molecular weight was 70,000.

(Synthesis Example 2) Thermometer, stirrer, cooling pipe,
Approximately 5 heating and cooling volumes with nitrogen gas inlet
Γ-butyrolactone 3104.
1 g and 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane 405.900 g (0.99 mol)
And 2.663 g of 2-aminobenzimidazole (0.
02 mol), raise the temperature to 45 ° C., and, while maintaining the temperature at 43-50 ° C., add a small amount of 372.32 g (1.04 mol) of 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride. Were added one by one. 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-2). The solid content of the obtained polyimide precursor solution (A-2) was 20% by weight, and the weight average molecular weight was 70,000.

(Synthesis Example 3) Thermometer, stirrer, cooling pipe,
Approximately 5 heating and cooling volumes with nitrogen gas inlet
Γ-butyrolactone 2936.8 in a 1 liter reaction vessel.
g and 2,2-bis [4- (4-aminophenoxy) phenyl] propane 401.800 g (0.98 mol)
And 5.326 g of 2-aminobenzimidazole (0.
04 mol), raise the temperature to 45 ° C., and maintain the temperature at 43 to 50 ° C., and 331.660 g (1.03 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
Was added in small portions. After the addition, the reaction was continued at 45 ° C. for about 5 hours, then cooled to room temperature and the polyimide precursor solution (A
-3) was obtained. The solution of the obtained polyimide precursor (A-
The solid content of 3) was 20% by weight, and the weight average molecular weight was 65,000.

(Synthesis Example 4) Thermometer, stirrer, cooling pipe,
Approximately 5 heating and cooling volumes with nitrogen gas inlet
Γ-butyrolactone 2918.3 in a liter reaction vessel
g and 2,97.700 g (0.97 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane
And 7.989 g of 2-aminobenzimidazole (0.
06 mol), heated to 45 ° C, and kept at 43 to 50 ° C, 328.440 g (1.02 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
Was added in small portions. After the addition, the reaction was continued at 45 ° C. for about 5 hours, then cooled to room temperature and the polyimide precursor solution (A
-4) was obtained. The solid content of the obtained solution (A-4) of the polyimide precursor (A-4) was 20% by weight, and the weight average molecular weight was 60,000.

(Synthesis Example 5, Synthesis of Photopolymerizable Monomer) Toluene was placed in a reaction vessel having 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. 137.3 g and trimethylhexamethylene diisocyanate 210 g (1.00 mol) were added.
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-1). The solid content of the obtained (B-1) was 75% by weight.

(Comparative Synthesis Example) γ-butyrolactone 295 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.
4.7 g and 410,000 g (1.00 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane are added, and the temperature is raised to 45 ° C, and while maintaining the temperature at 43 to 50 ° C, 3 334.880 g (1.04 mol) of 3,3,4,4'-benzophenonetetracarboxylic 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-1).
I got The solid content of the obtained polyimide precursor solution (a-1) was 20% by weight, and the weight average molecular weight was 70,
000.

Examples 1 to 6, Comparative Examples 1 to 5 The component (A) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1,
Including the photopolymerizable monomer obtained in Synthesis Example 5 (B)
The components, component (C), component (D), component (E), and the dye were mixed in the proportions shown in Table 1 and in the proportions (parts by weight) shown in Table 2, respectively, to give a solution of the photosensitive resin composition. Obtained.

[0052]

[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 photosensitive resin composition layer thus obtained was formed was tested for developability, storage stability, PCT resistance and gold plating 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 by 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 above-mentioned 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 rays were re-irradiated at a dose of 1 J / cm ² using an ultraviolet ray irradiator manufactured by Toshiba Electric Materials Co., Ltd., and then further heated at 175 ° 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) Gold plating resistance A 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
After heating and drying for 1 minute, the film was re-irradiated with ultraviolet rays at a dose of 1 J / cm ² using an ultraviolet irradiation apparatus 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 immersed in an acidic degreasing solution (trade name: Z-200, manufactured by World Metal) at 60 ° C. for 1 minute to perform an acidic degreasing treatment. Then, it was immersed in a soft etching solution (100 g / l aqueous solution of ammonium persulfate) at 23 ° C. for 3 minutes to perform a soft etching treatment. Then, after pickling with a 10 wt% sulfuric acid aqueous solution, the solution was added to a substituted palladium plating solution (Meltex Co., trade name: Melplate Activator 350).
Palladium was plated by immersion at 3 ° C. for 5 minutes to activate the copper surface. Next, it was immersed in an electroless nickel plating solution (ICP-Nicolon U, manufactured by Okuno Pharmaceutical Co., Ltd.) 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, electroless gold plating solution (HGS-2000, manufactured by Hitachi Chemical Co., Ltd.)
The substrate was immersed 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 occurred) ×: Poor plating resistance (thing of floating and peeling of resist and peeling of plating generated)

[0059]

[Table 2]

[0060]

(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 more excellent in plating solution resistance. (4) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and is more excellent in solder heat resistance. (5) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and is further excellent in compatibility. (6) The photosensitive resin composition of the present invention exhibits the effect of the photosensitive resin composition of (1), and is more excellent in storage stability. (7) The method for producing a solder resist according to the present invention uses an alkaline aqueous solution having a good working environment, and has a PCT resistance, a low-temperature curing property, a solder heat resistance, a plating solution resistance, a chemical resistance, an electric insulation property, and the like. Excellent.

[Brief description of the drawings]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/028 G03F 7/028 H05K 3/18 H05K 3/18 D 3/28 3/28 D

Claims (7)

[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 a carbon atom. R ₃ represents a hydrogen, halogen, nitro group or an alkyl group having 1 to 9 carbon atoms, n ′ is an integer of 1 to 4, Represents a repeating unit), (B) a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal, and (C) photopolymerization which generates free radicals upon irradiation with actinic light. A photosensitive resin composition comprising an initiator, (D) a blocked isocyanate resin, and (E) a heterocyclic compound containing at least one thiol group. 2. The polyimide precursor of the component (A) has a solid content of 20 to 95 parts by weight. The photopolymerizable unsaturated compound of the component (B) has a solid content of 5 to 80 parts by weight. And the total amount of component (B) 1
The photopolymerization initiator of the component (C) is used in an amount of 0.01 to 20 parts by weight (provided that the solid content of the component (A) and the total amount of the component (B) are 1).
(Based on 100 parts by weight) The blocked isocyanate resin of the component (D) is 1 to 4
0 parts by weight (based on 100 parts by weight of the total of the solid content of the component (A) and the component (B)) The heterocyclic compound containing at least one thiol group of the component (E) is 0.01 to 20 parts by weight. Parts by weight ((A)
The photosensitive resin composition according to claim 1, wherein the mixing ratio of the solid content of the component and the total amount of the component (B) is 100 parts by weight). (3) R ₁ in the general formula (I) is represented by the following general formula (VI): (In the formula, Y is a single bond or _{-CO -, - SO 2 -,} -
_{O -, - C (CF 3} ) 2 - photosensitive resin composition according to claim 1 or 2 a tetravalent organic group represented by any one shows a) the. 4. R ₂ in the general formula (I) is the following general formula (VII): (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 each independently represents an integer of 0 to 4.) The photosensitive resin composition according to any one of claims 1 to 3. 5. The composition according to claim 1, wherein the component (B) is a photopolymerizable unsaturated compound having at least one ethylenically unsaturated group at a terminal and having at least one urethane bond in a molecular structure. The photosensitive resin composition according to claim 1. 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. A solution of the photosensitive resin composition according to any one of claims 1 to 6, which is applied to a substrate, dried, and imagewise exposed, and then a surfactant or an organic solvent is added to the substrate. .1-5
A method for producing a solder resist, wherein development is performed using an alkaline aqueous solution containing 0% by weight and 0.01 to 30% by weight of an inorganic alkaline compound as a developer.