JP2001209175A - Photosensitive composition and its cured body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy beam curable photosensitive composition excellent in developability, curability, stability and the resistance of the exposed part to a developing solution and capable of forming a cured coating film excellent in adhesion, electric insulating property, resistance to the heat of soldering, solvent, acid and alkali resistances and plating resistance required by a soldering resist. SOLUTION: The photosensitive composition contains a prepolymer (A) having two or more polymerizable unsaturated groups and one or more carboxyl groups in one molecule, a photopolymerization initiator (B), a reactive diluent (C) and a blocked isocyanate (D) in an A:B:C:D weight ratio of 100:(1-30):(1-100):(2-100).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition, and more particularly, to a printed wiring board excellent in various properties such as developability, curability, stability, adhesion, heat resistance and chemical resistance. The present invention relates to a photosensitive composition useful for forming a solder resist film for use and an insulating resin layer of various electronic components.

[0002]

2. Description of the Related Art In a printed wiring board, a solder resist is widely used as a permanent protective film for a circuit. Solder resist is a film formed on the entire surface of the circuit conductor except for the parts to be soldered.When wiring electronic components on printed wiring boards, it prevents solder from adhering to unnecessary parts and Is used as a protective coating to prevent direct exposure to air. As a solder resist for a printed wiring board, a liquid developable solder resist ink is used from the viewpoint of high precision, high density, and consideration of environmental issues. As a liquid solder resist, for example, JP-A-60-208337
JP-A-61-59447 proposes a solder resist ink composition containing a novolak-type epoxy resin partially reacted with acrylic acid as a main component. However, these ink compositions have problems such as insufficient curability after exposure, and tackiness after coating film formation.

[0003] Japanese Patent Publication No. 1-54390 discloses an energy ray-curable resin obtained by reacting a reaction product of a novolak type epoxy resin with an unsaturated monocarboxylic acid with a polybasic anhydride, a photopolymerization initiator, A photosensitive resin composition comprising a diluent and an epoxy compound has been proposed. However, since the reaction between the carboxyl group and the epoxy compound contained in the energy ray-curable resin proceeds even at room temperature, the photosensitive resin composition is not exposed when the ink is left for a long time or the coating film drying time is extended. There was a problem that development unevenness occurred in the portion. JP-A-2-169602 proposes a photosensitive resin composition comprising an unsaturated group-containing carboxylic acid compound, an oxazoline compound, a photopolymerization initiator, and a diluent. In this photosensitive resin composition, However, there were problems such as insufficient stability. As described above, the conventionally proposed photosensitive composition does not satisfy all the properties such as developability, curability, and stability, and a solder resist composition having these properties is desired. .

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned various problems and is excellent in developability, curability and stability, and also has resistance to a developing solution in an exposed portion. An object is to provide an energy ray-curable photosensitive composition. Furthermore, in addition to the above-mentioned excellent properties, it forms an excellent cured coating such as adhesion, electrical insulation, solder heat resistance, solvent resistance, acid resistance, alkali resistance, and plating resistance required for a solder resist. A photosensitive composition suitable for the manufacture of printed wiring boards, etc., and a cured product obtained from the composition, and a print comprising a cured film obtained by curing the composition. It is another object to provide a wiring board.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve these problems, and as a result, a specific isocyanate compound has been used instead of an epoxy resin usually used in a photosensitive composition. By using, developability,
The present inventors have found that a photosensitive composition having excellent curability, stability, adhesion, heat resistance, and chemical resistance can be produced, and have completed the present invention. That is, according to the present invention, two molecules are contained in one molecule.
A prepolymer having at least one polymerizable unsaturated group and at least one carboxyl group (A), a photopolymerization initiator (B), a reactive diluent (C), and a blocked isocyanate (D)
A photosensitive composition comprising each of the following components as essential components.

In a preferred embodiment of the photosensitive composition of the present invention, the prepolymer (A) is an epoxy compound (a)
And a compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule,
A product obtained by reacting a saturated or unsaturated polybasic acid anhydride (c), and having an acid value of 45 to 20 at a solid content.
0 mgKOH / g, wherein the blocked isocyanate (D) is a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule, a phenol, an alcohol, an acid amide, an oxime, an ester , Diketones, mercaptans, ureas, imidazoles, acid imides, amines and carbamates are reaction products with a blocking agent selected from the group consisting of, especially a compound having an isocyanurate ring. And each of the above components (A) to (D)
Of the photopolymerization initiator (B): 1 to 30, the reactive diluent (C): 1 to 100, and the blocked isocyanate (D) with respect to the prepolymer (A): 100 in weight ratio. : 2 to 100. Furthermore, according to another aspect of the present invention, a cured product obtained by curing the photosensitive composition, and a cured film obtained by curing the photosensitive composition are used. Is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component (A) to (D) of the photosensitive composition of the present invention and uses and usage thereof will be described in detail. In this specification, the notation “(meth) acrylic acid” means acrylic acid or methacrylic acid, and the notation “(meth) acrylate” means acrylate or methacrylate.

Prepolymer (A) Prepolymer (A) constituting the photosensitive composition of the present invention
Has two or more polymerizable unsaturated groups and one or more carboxyl groups in one molecule, for example, an epoxy compound (a) and one or more polymerizable unsaturated groups in one molecule. A prepolymer obtained by reacting a compound (b) having one carboxyl group in the presence of a catalyst, if necessary, with a saturated or unsaturated polybasic anhydride (c), Is mentioned.

The epoxy compound (a) used for synthesizing these prepolymers (A) can be appropriately selected from those commonly used in the production of solder resists. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, bixylenol epoxy resin, N-glycidyl epoxy resin, triglycidyl isocyanurate, phenol novolak resin, cresol novolak resin , Ethylphenol novolak resin, isopropylphenol novolak resin,
tert-butylphenol novolak resin, 3,5-
Xylenol novolak resin, bromophenol novolak resin, bisphenol A novolak resin, naphthalene novolak resin, glycidyl compound of polyvinylphenol, epoxy compound of condensate of phenols with aromatic aldehyde having phenolic hydroxyl group, alkyl acrylate and methacrylic acid Copolymers of at least one monomer selected from alkyl esters and at least one epoxy group-containing monomer selected from epoxy group-containing (meth) acrylates, and the like, may be used. These epoxy compounds can be used alone or in combination of two or more. Above all, novolak epoxy resins such as phenol novolak type, cresol novolak type and bisphenol A novolak type are particularly preferable, and these epoxy resins can be used alone or in combination of two or more thereof.

[0010] 1 used in the synthesis of the prepolymer (A)
Examples of the compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in the molecule include (meth)
Reaction products of acrylic acid, crotonic acid, cinnamic acid, pentaerythritol tri (meth) acrylate and succinic anhydride, reaction products of pentaerythritol tri (meth) acrylate and phthalic anhydride, pentaerythritol tri (meth) acrylate and tetrahydro Reaction product of phthalic anhydride, reaction product of dipentaerythritol penta (meth) acrylate and succinic anhydride, reaction product of dipentaerythritol penta (meth) acrylate and phthalic anhydride, dipentaerythritol penta (meth) And b) a reaction product of acrylate and tetrahydrophthalic anhydride.

[0011] One or more polymerizable unsaturated groups and 1
The compound (b) having two carboxyl groups was added in an amount of 0.1 to 1.0 equivalent of the epoxy group of the epoxy compound (a).
It is preferable to carry out the reaction at 8 to 1.2 equivalents. 1 in 1 molecule
When the amount of the compound (b) having at least one polymerizable unsaturated group and one carboxyl group is less than 0.8 equivalent, the stability of the photosensitive composition becomes insufficient. Content tends to be high, and the curing properties tend to be insufficient. The reaction between the epoxy compound (a) and the compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule is preferably performed at 100 to 120 ° C.

The prepolymer (A) is obtained by adding a reaction product of the above epoxy resin (a) and a compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule, and It can be obtained by reacting a saturated or unsaturated polybasic acid anhydride (c). Here, as the saturated or unsaturated polybasic anhydride (c) used, for example, maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydro Phthalic anhydride, 4-
Acid anhydrides such as ethyltetrahydrophthalic anhydride are exemplified. These acid anhydrides are suitable from the viewpoints of developability and reactivity with thermosetting components. Among these, succinic anhydride and tetrahydrophthalic anhydride are particularly preferred.

The amount of the saturated or unsaturated acid anhydride (c) to be used is preferably 0.3 to 1.0 equivalent based on 1.0 equivalent of the epoxy group of the epoxy compound (a). When the amount of the saturated or unsaturated acid anhydride (c) is less than 0.3 equivalent, the developability of the photosensitive composition becomes insufficient, and when it exceeds 1.0 equivalent, the solvent resistance tends to become insufficient. There is. The reaction with a saturated or unsaturated acid anhydride (c) is preferably from 60 to 120
Performed at ° C. The solid content acid value of the prepolymer (A) is usually 45 to 200 mgKOH / g, preferably 60 to 200 mgKOH / g.
１１０110 mgKOH / g. Acid value is 45mgKOH
If it is less than / g, the developability of the photosensitive composition tends to be insufficient, and if it exceeds 200 mgKOH / g, the solvent resistance tends to be insufficient.

In the synthesis of the prepolymer (A), for example, when the obtained prepolymer is liquid at ordinary temperature, the reaction can be carried out without a solvent. However, the viscosity of the reaction system is adjusted, and the mixing is performed. It is preferable to carry out the reaction using a solvent for the purpose of improving the heat transfer by making it sufficient. Here, examples of the solvent that can be used include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methylcellosolve;
Glycol ethers such as methyl carbitol and diethylene glycol dimethyl ether; esters such as ethyl acetate and butyl acetate; ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl Acetates of glycol ethers such as ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; polyhydric alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and nonane; petroleum naphtha and solvent naphtha Petroleum solvents such as;
Water and the like. These solvents can be used alone or in combination of two or more. The amount of solvent used is
The amount is preferably 5 to 1000 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the prepolymer (A).

Photopolymerization initiator (B) Photopolymerization initiator (B) used in the photosensitive composition of the present invention.
Can be appropriately selected and used from commonly used photopolymerization initiators. Specific examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2. -Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 1- [4-
(2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, -Anthraquinones such as amylanthraquinone.

Further, 2,4-dimethylthioxanthone,
Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone or xanthone; 2-benzyl-2- Α-aminoketones such as dimethylamino-1,1- (4-morpholinophenyl) -butanone-1;
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3)
-(1H-pyrrol-1-yl) phenyltitanium,
eta ⁵ - cyclopentadienyl eta ⁶ - click Mesnil iron (1 +) - hexafluorophosphate (1-) and the like can also be mentioned.

These photopolymerization initiators can be used alone or in combination of two or more. The photopolymerization initiator may be used in combination with one or more benzoic acid-based or tertiary amine-based photopolymerization accelerators. The amount of the photopolymerization initiator (B) to be used is preferably 1 to 30 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the prepolymer (A). When the use amount of the photopolymerization initiator (B) is less than 1 part by weight, the curing reaction by the energy beam becomes difficult to proceed. On the other hand, 3
If the amount is more than 0 parts by weight, the characteristics as a solder resist tend to decrease.

Reactive diluent (C) The reactive diluent (C) makes the photosensitive composition more sufficiently cured by energy rays, and has excellent chemical resistance, heat resistance and alkali resistance. Use to get.
The reactive diluent (C) used in the present invention is a compound having at least two double bonds in one molecule. Examples of such a compound include 1,4-butanediol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth)
Glycol di (meth) acrylates such as acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, and neopentyl glycol di (meth) acrylate hydroxypivalate are exemplified.

Examples of the reactive diluent include dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, and ethylene oxide-modified di (meth) phosphate. ) Acrylates, allylated cyclohexyl di (meth) acrylates,
Isocyanurate di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate Dipentaerythritol penta (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol tetra (Meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The above polyfunctional reactive diluent may be used alone or
It can be used in combination of more than one kind. The amount of the reactive diluent (C) to be used is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, per 100 parts by weight of the prepolymer (A). If the amount of the reactive diluent (C) used is less than 1 part by weight, the curing reaction by the energy rays becomes difficult to proceed. On the other hand, if it exceeds 100 parts by weight, the tackiness tends to be insufficient.

Blocked Isocyanate (D) In the present invention, the blocked isocyanate (D) is
It is added to improve the strength of the coating film after curing of the photosensitive composition. Examples of the blocked isocyanate (D) that can be used for this purpose include those obtained by blocking a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule with a blocking agent. Examples of the polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule include, for example, 3
Polyisocyanurate compound (D) having an isocyanurate ring introduced by isomerization (isocyanuration reaction)
1) An isocyanate group-terminated polyurethane polyisocyanate compound (D2), a polyurea polyisocyanate compound, polymeric isocyanate, or diphenylmethane diisocyanate obtained by reacting an organic diisocyanate with a polyfunctional active hydrogen compound.

The organic polyisocyanate compound used for producing the polyisocyanurate compound (D1) includes, for example, 2,4-tolylene diisocyanate, 2,2
6-tolylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4'-diphenylmethane diisocyanate, 4,
4'-diphenyl ether diisocyanate, 3,3 '
-Dimethyldiphenylmethane-4,4'-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,
3'-dimethoxydiphenyl-4,4'-diisocyanate, α, α, α ', α'-tetramethylxylylene diisocyanate, polyphenylenepolymethylene polyisocyanate, modified carbodiimide and modified uretimine of 4,4'-diphenylmethane diisocyanate Aromatic diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, aliphatic diisocyanate such as 2-methylpentane-1,5-diisocyanate, lysine diisocyanate, etc., isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, And alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate. Among these, as the organic polyisocyanate compound, those having a cyclic structure such as aromatic diisocyanates and alicyclic diisocyanates are preferable.

The polyisocyanurate compound (D1) is
It can be produced by a method known per se. The compound (D1) is usually produced by a method in which an organic diisocyanate is reacted in the presence of an isocyanuration catalyst. As the isocyanurate-forming catalyst, conventionally known ones can be used. For example, 2,4,6-tris (dimethylaminomethylphenol), triethylamine, N, N ′, N ″ -trisdimethylaminopropylhexahydrotriazine Tertiary amines such as tetraalkylalkylenediamine, diazabicyclooctane and lower alkyl-substituted products thereof; tertiary amine and ethyl alcohol, monosubstituted carbamic acid ester, aldehyde,
Co-catalyst combination system with alkylene oxide, alkylene imine, ethylene carbonate, 2,3-butanedione and the like;
Tertiary alkyl phosphines; Alkyl ammonium hydroxides and organic weak acid salts such as tetramethylammonium, tetraethylammonium and tetrabutylammonium; Hydroxyalkylammonium hydrochlorides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium and triethylhydroxypropylammonium Oxides and organic weak acid salts are exemplified.

Other specific examples of the isocyanuration catalyst include alkali metal salts of imides such as potassium phthalimide; quaternary onium hydroxy compounds of N, P, As and Sb; onium hydroxy compounds of S or Se. Onium compounds; alkyl-substituted ethyleneimines such as N-methylethyleneimine; carboxylic acids such as potassium acetate, sodium acetate, cobalt acetate, lead 2-ethylhexanoate, sodium benzoate, potassium naphthenate and magnesium naphthenate Metal salts; oxides, hydroxides, carbonates of alkali metals and alkaline earth metals, metal salts of enolic compounds and phenols, etc .; epoxy compounds, epoxy compounds and tertiary amines, aromatic secondary
Metal salt of a secondary amine, for example, a combination system with a cocatalyst such as sodium salt of diphenylamine; various organic metals such as titanium tetrabutylate and tributylantimony oxide;
Friedel Crafts catalysts such as aluminum chloride and boron trifluoride; chelate compounds of alkali metals such as sodium salicylaldehyde; and metal chelate compounds of β-diketone such as aluminum acetylacetone and lithium acetylacetone. Among the above isocyanuration catalysts, tertiary amines such as N, N ′, N ″ -trisdimethylaminopropylhexahydrotriazine, and metal carboxylate salts such as sodium acetate, cobalt acetate, potassium naphthenate and magnesium naphthenate are exemplified. preferable.

The concentration of the isocyanuration catalyst varies depending on the type of the catalyst used, the reaction temperature and the like, but is usually 0.01 to 10% by weight based on the polyisocyanate compound.
Is selected from the range. In addition to the above catalyst, as a co-catalyst,
For example, aliphatic alcohols such as methanol, ethanol, and butanol; polyhydric alcohols such as ethylene glycol, 1,3-butanediol, neopentyl glycol, and trimethylolpropane; polyethers such as polypropylene glycol, phenols; It is preferred that secondary amines, imidazoles and the like are used in combination usually at 0.05 to 10% by weight based on the polyisocyanate. Alcohols such as aliphatic alcohols, polyhydric alcohols, and phenols as co-catalysts can be added at the same time as the isocyanurate-forming catalyst, or can be reacted with an organic diisocyanate in advance to form a urethane bond, and then subjected to the isocyanurate-forming reaction. Can also be performed. The reaction temperature for the isocyanuration is generally 0 to 200 ° C, preferably 0 to 1 ° C.
It is selected from the range of 00 ° C.

A solvent may or may not be used in the isocyanuration reaction. Examples of the solvent used include inert solvents commonly used in polyurethane production, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, and acetic acid. Ester solvents such as isobutyl; glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate; tetrahydrofuran, dioxane and the like One or more aprotic polar solvents such as N-methylpyrrolidone can be used. By selecting the type and amount of the solvent to be used and the resin concentration, the viscosity of the reaction solution can be adjusted according to the use conditions.

The progress of the reaction can be monitored by measuring the NCO content of the reaction solution, measuring the infrared spectrum, measuring the refractive index, and the like. When a predetermined NCO content or isocyanuration rate is reached, the reaction is stopped with a polymerization terminator suitable for the type of catalyst used. Examples of the reaction terminator include inorganic acids such as hydrochloric acid, phosphoric acid, and phosphorous acid; and phosphate esters such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, diethyl phosphate, and dibutyl phosphate. Phosphites such as monomethyl phosphite, monoethyl phosphite, monobutyl phosphite, dimethyl phosphite, diethyl phosphite, and dibutyl phosphite;
Examples thereof include sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, methyl p-toluenesulfonate, and ethyl p-toluenesulfonate or alkyl esters thereof; and perfluorinated sulfonic acids such as nonafluorobutanesulfonic acid. The addition amount of the reaction terminator is preferably in the range of from the same amount as the added catalyst to twice the amount. The polyisocyanurate compound (D1) can be usually used for the blocking reaction without removing the unreacted monomer. However, the polyisocyanurate compound may contain a large amount of the unreacted monomer depending on the isocyanurate conversion rate. If it has an adverse effect, the unreacted monomer may be removed by thin-film distillation or the like before use in the blocking reaction.

In the production of the isocyanate group-terminated polyurethane polyisocyanate compound (D2) obtained by reacting an organic diisocyanate with a polyfunctional active hydrogen compound, the organic diisocyanate compound includes the above-mentioned organic diisocyanate compound, a modified buret thereof, and uretimine. Modified products, carbodiimide modified products and the like can also be mentioned. These organic isocyanates may be used alone or in combination of two or more.

The polyfunctional active hydrogen compound used for producing the isocyanate group-terminated polyurethane polyisocyanate compound (D2) includes a polyfunctional hydroxy compound. Polyfunctional hydroxy compounds, such as glycerin, trimethylolpropane, trimethylolethane,
Trifunctional or higher polyhydric alcohols such as 1,2,6-hexanetriol, 2-hydroxyethyl-1,6-hexanediol, 1,2,4-butanetriol, erythritol, sorbitol, pentaerythritol and dipentaerythritol Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1 , 3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, , 5-pentanediol, 3-methyl-
1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, 1,3,5-trimethyl-1, Aliphatic glycols such as 3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol; 1,4-cyclohexanediol, 1,4
Alicyclic glycols such as cyclohexanedimethanol,
Monomer glycols such as aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene are exemplified.

Further, as the polyfunctional hydroxy compound,
High molecular weight polyols, for example, polyols such as polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, and polyacryl polyols, which are reaction products of bisphenol A with ethylene oxide or propylene oxide, are also included. Examples of polyether polyols include, for example, glycols such as ethylene glycol, propylene glycol, and diethylene glycol; trifunctional or higher functional polyols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol; and polyamines such as ethylenediamine and toluenediamine. Examples thereof include hydroxyl group-containing polyether polyols obtained by addition polymerization of an alkylene oxide such as ethylene oxide and propylene oxide, and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

Examples of the polyester polyol include dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, and phthalic acid or carboxylic acids such as trimellitic acid and tri- and tetracarboxylic acid such as pyromellitic acid; ethylene glycol; Propylene glycol, 1,
4-butanediol, 1,5-pentanediol, 3-
Methyl-1,5 pentanediol, 2,2-diethylpropanediol, 2-ethyl-2-butylpropanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, And diols such as 1,4-cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, and those obtained by polycondensation with polyhydroxy compounds such as bisphenol A and bisphenol F. Examples of the polyetherester polyol include, for example, those obtained by reacting an ether group-containing diol or a mixture thereof with another glycol with the dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide. And poly (polytetramethylene ether) adipate.

Examples of the polycarbonate polyol include, for example, a dealcoholization condensation reaction of a polyhydric alcohol with a dialkyl carbonate such as dimethyl carbonate and diethyl carbonate, a phenol condensation reaction of a polyhydric alcohol with a diphenyl carbonate, and a deethylation reaction of a polyhydric alcohol with ethylene carbonate. A polycarbonate polyol obtained by a glycol condensation reaction or the like is included. Examples of the polyhydric alcohol used in the condensation reaction include, for example,
1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5
Aliphatic diols such as -pentanediol, 3-methyl-1,5-pentanediol, 2,2-diethylpropanediol, 2-ethyl-2-butylpropanediol and neopentyl glycol; 1,4-cyclohexanediol And alicyclic diols such as 1,4-cyclohexanedimethanol.

As other polyfunctional active hydrogen compounds, for example, diamines and amino alcohols can be used. Examples of the diamines include hexamethylene diamine, xylene diamine, isophorone diamine, N,
Examples include N-dimethylethylenediamine and the like, and examples of the amino alcohol include monoethanolamine and diethanolamine. The preferred molecular weight of the polyol component as these polyfunctional active hydrogen compounds is 35 to 5,000 in number average molecular weight. When a polyol having a molecular weight of more than 5000 is used, the crosslinking density tends to decrease, and the strength of the coating film tends to decrease.

The temperature in the production (urethane-forming reaction) of the isocyanate group-terminated polyurethane polyisocyanate compound (D2) in the present invention is usually selected from the range of 10 to 90 ° C. Although a reaction catalyst is not particularly necessary, in some cases, an organic tin catalyst such as dibutyltin dilaurate or dibutyltin dioctoate; an organic lead catalyst such as lead octanoate; a triethylamine, dimethyloctylamine, diazabicycloundecene, or the like; It is also effective to use a catalyst of a tertiary amine compound or the like. The progress of the urethanization reaction can be monitored by measuring the NCO content during the reaction. The reaction is stopped when the target NCO content is reached. These reactions can be carried out without solvent or in a solvent. As the solvent to be used, one or more of the inert solvents exemplified in the above-described isocyanuration reaction can be used. By selecting the type and amount of the solvent to be used and the resin concentration, the viscosity can be adjusted according to the use conditions.

As described above, the blocked isocyanate (D) used in the present invention can be obtained by blocking a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule with a blocking agent. Examples of the blocking agent include oximes such as formamide oxime, methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, p-tert-butylphenol, Thymol, p-naphthol, p-nitrophenol, p-
Phenols such as chlorophenol; methanol, ethanol, butanol, tert-butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, butylcellosolve, methylene carbitol,
Alcohols such as benzyl alcohol, phenylcellosolve, and furfuryl alcohol; acid amides such as ε-caprolactam, acetanilide, acetanisidide, acetate amide, benzamide, δ-valerolactam, and γ-butyrolactam.

Further, esters such as dimethyl malonate and diethyl malonate; diketones such as methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercaptans such as butyl mercaptan, thiophenol and tert-dodecyl mercaptan; urea and thiourea , Ureas such as ethylene urea; imidazole, 2-methylimidazole, 2-
Imidazoles such as ethylimidazole; acid imides such as succinimide and maleic imide; amines such as diphenylamine, phenylnaphthylamine, aniline and carbazole; imines such as ethyleneimine, propyleneimine and polyethyleneimine; phenyl phenylcarbamate And blocking agents such as carbamates such as 2-oxazolidine; sulfites such as sodium bisulfite and potassium bisulfite. Among these, acid amides, diketones, esters, alcohols and carbamates are preferred as the blocking agent.

The blocking reaction of the polyisocyanate compound with the above-mentioned blocking agent is carried out by a conventionally known method. The amount of the blocking agent used in the reaction is usually 1 equivalent or more and 2 equivalents or less relative to 1 equivalent of the active isocyanate group.
Preferably it is 1.05-1.5 equivalent. If it is less than 1 equivalent, active isocyanate groups remain, and if it is more than 2 equivalents, an unreacted blocking agent remains, which may have an adverse effect. The reaction temperature for blocking is usually 10 to 15
It is selected from the range of 0 ° C. Although a reaction catalyst is not particularly required, in some cases, dibutyltin dilaurate,
It is also effective to use an organotin-based catalyst such as dibutyltin dioctoate; an organic lead-based catalyst such as lead octanoate; a urethanization catalyst of a tertiary amine-based compound such as triethylamine, dimethyloctylamine, and diazabicycloundecene. It is a target.

Although the molecular weight of the blocked polyisocyanate (D) used in the present invention is not particularly limited, it is usually 300 to 100,000, preferably 500 in number average molecular weight.
~ 20,000. If the number average molecular weight exceeds 100,000, the molecular weight between crosslinks becomes longer and the coating strength decreases,
The viscosity may be too high and the workability may be reduced. In the composition of the present invention, the above-mentioned blocked isocyanates (D) can be used alone or in combination of two or more. The amount of the blocked isocyanate (D) to be used is preferably 2 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the prepolymer (A). If the amount of the blocked isocyanate (D) is less than 2 parts by weight, the hardness of the coating film tends to decrease.
If the amount exceeds 0 parts by weight, curability by energy rays tends to decrease.

Other Additives The composition of the present invention may be used by adding a solvent in order to adjust viscosity and improve coating properties and handling properties. As such a solvent, the solvent used at the time of synthesizing the prepolymer (A), which is a component of the present invention, may be used as it is, or after removing these once and adding a solvent according to the intended use. Is also good. The solvent to be used can be appropriately selected from those exemplified as the solvent that can be used for the synthesis of the prepolymer (A). Also,
Additives can be added to the composition of the present invention as needed. Specifically, for example, inorganic fillers such as silica, alumina, talc, clay, calcium carbonate, and barium sulfate; organic pigments such as phthalocyanine-based and azo-based; tackiness improvers; rosin; Agents; paint additives such as defoamers, coupling agents and leveling agents;
Curing accelerators such as urea derivatives; and polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, N-nitrosophenylhydroxylamine aluminum salt, and N-nitrosophenylhydroxylamine ammonium salt.

Applications and Usage As described above, the composition of the present invention is used for a solder resist film for a printed wiring board and an insulating resin layer of various electronic components. When using, depending on the application, aluminum, metal plate such as stainless steel, screen mesh,
It is applied to paper, wood, synthetic resin, semiconductor substrate, or any other substrate, dried and cured before use. For curing,
For example, various ionizing radiations such as an electron beam, an α-ray, a β-ray, a γ-ray, an X-ray, a neutron beam or an ultraviolet ray, or energy rays such as light are used. When the composition of the present invention is used as a solder resist, for example, the composition is cured as described below to obtain a cured product. First, a composition is applied on a substrate by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain flow coating method so as to have a film thickness of 10 to 100 μm. After drying at ℃, the negative film is brought into contact with the coating film and irradiated with ultraviolet rays. Next, after the unexposed portion of the coating film is dissolved and removed with a 0.5 to 5% aqueous sodium carbonate solution or a 0.5 to 2% dilute aqueous alkaline solution such as sodium hydroxide, the coating is exposed at 120 to 180 ° C. for 30 minutes to 1 minute. A cured film is obtained by heating and curing for a time.

[0041]

EXAMPLES Specific embodiments of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Synthesis Example 1 Production of Prepolymer (A-1) In a flask equipped with a thermometer, a stirrer and a reflux condenser,
Epoxy resin "Epicoat 1002" (bisphenol A type epoxy resin: Yuka Shell Epoxy Co., Ltd .: trade name,
(Epoxy equivalent = 635) 635 g and diethylene glycol monoethyl ether acetate (236 g) were added and dissolved, and then hydroquinone monomethyl ether 0.35 was added.
g, 72 g of acrylic acid and 3.5 g of triphenylphosphine.
Was reacted. Thereafter, 200 g of succinic anhydride and 152 g of a petroleum-based solvent “Solvesso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.) were added and reacted at 100 ° C. for 4 hours to produce a prepolymer (A-1). The amount of nonvolatile components (solid content) of the obtained resin solution is about 70%,
Its acid value was 120 mgKOH / g.

Synthesis Example 2: Production of Prepolymer (A-2)
02 "instead of epoxy resin" Epicoat 180S8
0 "(o-cresol novolak type: manufactured by Yuka Shell Epoxy Co., Ltd .: trade name, epoxy equivalent = 218), the amount used was 218 g, and each of diethylene glycol monoethyl ether acetate, hydroquinone monomethyl ether and triphenylphosphine was used. The reaction was carried out in the same manner except that the amounts used were changed to 78.5 g, 0.26 g and 1.8 g, respectively. After the reaction, 76.1 g of tetrahydrophthalic anhydride and 78.5 g of a petroleum-based solvent “Solvasso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.)
, And reacted at 100 ° C. for 4 hours to obtain a prepolymer (A-
2) was synthesized. The amount of nonvolatile components (solid content) of the obtained resin solution is about 70%, and its acid value is 74 mgKOH /
g.

Synthesis Example 3 Production of Prepolymer (A-3) In the above Synthesis Example 1, the epoxy resin “Epicoat 10” was used.
02 "instead of epoxy resin" Epicoat 157S7 "
0 "(bisphenol A novolak type: manufactured by Yuka Shell Epoxy Co., Ltd .: trade name, epoxy equivalent = 209), the amount used is 209 g, and each use of diethylene glycol monoethyl ether acetate, hydroquinone monomethyl ether and triphenylphosphine is used. Quantity
The reaction was carried out in the same manner except that the amounts were changed to 94 g, 0.26 g and 1.4 g, respectively. After the reaction, subsequently, 76.1 g of tetrahydrophthalic anhydride and 59 g of a petroleum-based solvent “Solvesso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.)
, And reacted at 100 ° C. for 4 hours to obtain a prepolymer (A-
3) was synthesized. The amount of nonvolatile components (solid content) of the obtained resin solution is about 70%, and its acid value is 71 mgKOH /
g.

Synthesis Example 4 Production of Prepolymer (A-4) In a flask equipped with a thermometer, a stirrer and a reflux condenser,
218 g of epoxy resin "Epicoat 180S80" (o-cresol novolak type epoxy resin: manufactured by Yuka Shell Epoxy Co., Ltd .: trade name, epoxy equivalent = 218) and 124 g of diethylene glycol monoethyl ether acetate
And 0.19 g of hydroquinone monomethyl ether, 59 g of acrylic acid, a reaction product 9 of pentaerythritol triacrylate and succinic anhydride 9
5.8 g and 2.8 g of triphenylphosphine were added and reacted at 110 ° C. until the acid value became 2 or less. Thereafter, 76.1 g of tetrahydrophthalic anhydride and 68 g of a petroleum-based solvent “Solvesso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.) were added and reacted at 100 ° C. for 4 hours to produce a prepolymer (A-4). . The amount of non-volatile components (solid content) in the obtained resin solution was about 70%, and its acid value was 57 mgKOH / g.

Synthesis Example 5: Polyisocyanurate compound
Preparation of (D-1) Tolylene diisocyanate (2,4- / 2,6) was placed in a four-necked flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel.
-Tolylene diisocyanate = 80/20 weight ratio) 36
8.99 g and 368.99 g of butyl acetate were added, and the internal temperature was adjusted to 25 ° C. Under stirring, 1.46 g of a 5% methanol solution of sodium acetate was added.
And cooled. Then, 0.45 g of a 5% butyl acetate solution of N, N ′, N ″ -trisdimethylaminopropylhexahydrotriazine was added and reacted for 2 hours. Thereafter, 1.50 g of a 5% methanol solution of potassium acetate was gradually added dropwise. Then, when the isocyanate content reached 8.2%, 0.28 g of phosphoric acid was added as a reaction terminator to stop the isocyanuration reaction, and a polyisocyanurate resin solution (D-1) was obtained.

Synthesis Example 6: Blocked isocyanate (D
In a four-necked flask equipped with the production thermometer, reflux condenser, stirrer and dropping funnel of -2), 678.70 g of the polyisocyanurate resin solution (D-1) obtained in Synthesis Example 5 was added, and the internal temperature was adjusted. 8
After the temperature was raised to 0 ° C., 160.65 g of ε-caprolactam was added, and after reacting for 8 hours, 160.65 g of butyl acetate was added to synthesize blocked isocyanate (D-2).

Synthesis Example 7: Blocked isocyanate (D
-3) 657.64 g of the polyisocyanurate resin solution (D-1) obtained in Synthesis Example 5 above was added to a four-necked flask equipped with a thermometer, a cooler, a stirrer, and a dropping funnel. 8
After heating to 0 ° C, 2-ethylhexanol 171.18
g, and after reacting for 8 hours, 171.18 g of butyl acetate
Was added to obtain a blocked isocyanate (D-3).

Examples 1 to 7 and Comparative Examples 1 to 4 The prepolymers (A-1), (A
-2), (A-3) and (A-4), the polyisocyanurate compound (D-1) obtained in Synthesis Example 4, Synthesis Example 6
And the blocked isocyanate (D-
Using (2) and (D-3), the respective resist inks were prepared by compounding them to have the compositions (parts by weight) shown in Table 1 and kneading them by a roll mill. After applying each of these inks to a copper-clad laminate, 30
After drying for 30 minutes, a coating film having a thickness of 30 μm was formed. The formed coating film was evaluated for developability, curability, adhesion, solvent resistance, acid resistance, and alkali resistance according to the following procedure. Table 2 shows the results. From the results in Table 2, it can be seen that the composition (resist ink) of the present invention is particularly excellent in stability as compared with the ink of the comparative example.

Evaluation method (1) Developability After the ink was applied to the copper-clad laminate, it was dried in hot air at 80 ° C. for 30 minutes to form a coating film having a thickness of 30 μm. 1.0 kg / cm ^{2 in} aqueous solution
Developing at a spray pressure of 60 seconds, and visually determining the dissolution state of the coating film based on the following criteria. ○: Almost no coating film left △: Some coating film left ×: Coating left

(2) The curable coating film on the copper-clad laminate was passed through Kodak Step Tablet No. 2 (21 steps) and irradiated with ultraviolet rays at 200 mJ / cm ² using a high-pressure mercury lamp.
Irradiation and then using 1% aqueous sodium carbonate
The development was carried out at a spray pressure of 0 kg / cm ² for 60 seconds, and the portion where the coating film was not removed was observed. The larger the number of steps, the better the photocurability.

(3) Stability The ink was stored in a thermo-hygrostat at 50 ° C. for one week, and the viscosity of the ink after storage was checked for any increase in the viscosity of the ink before storage. The viscosity was measured using a B-type viscometer (B8H rotational viscometer, manufactured by Tokimec Co., Ltd.). ：: Thickening is 130% or less Δ: Thickening is 130% or more and 200% or less ×: Gelation or thickening is 200% or more

(4) Solvent Resistance The formed coating film on the copper-clad laminate was irradiated with ultraviolet rays at 200 mJ / cm ² using a high-pressure mercury lamp, and further irradiated for 150 minutes.
A test piece obtained by post-curing in an oven at 30 ° C. for 30 minutes was immersed in dichloromethane at 25 ° C. for 1 hour, and the state and adhesion of the coating film were comprehensively evaluated. ：: No change is observed at all △: Very slight change ×: Notable change

(5) Acid resistance Using a test piece prepared in the same manner as in the evaluation of the solvent resistance, immersing it in a 10% by volume aqueous hydrochloric acid solution at 25 ° C. for 1 hour, and then checking the state of the coating film and the adhesion Were comprehensively evaluated. ：: No change is observed at all △: Very slight change ×: Notable change

(6) Alkali Resistance A test piece prepared in the same manner as in the evaluation of the solvent resistance was immersed in a 10% by weight aqueous solution of potassium hydroxide at 25 ° C. for 1 hour. The adhesiveness was comprehensively evaluated. ：: No change is observed at all △: Very slight change ×: Notable change

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

The composition of the present invention described above has excellent developability, curability and stability, and is extremely useful for forming a solder resist film for a printed wiring board and an insulating resin layer of various electronic components. .

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08G 59/16 C08G 59/16 G03F 7/004 501 G03F 7/004 501 7/028 7/028 H05K 3/28 H05K 3 / 28 D

Claims (12)

[Claims] 1. A prepolymer having two or more polymerizable unsaturated groups and one or more carboxyl groups in one molecule (A), a photopolymerization initiator (B), a reactive diluent (C) and a block. A photosensitive composition containing each component of the isocyanated isocyanate (D). 2. The prepolymer (A) comprises an epoxy compound (a) and one or more polymerizable unsaturated groups in one molecule.
A product obtained by reacting a saturated or unsaturated polybasic acid anhydride (c) with a reaction product of the compound (b) having two carboxyl groups and having a solid content acid value of 45
The photosensitive composition according to claim 1, wherein the amount is from 200 to 200 mgKOH / g. 3. A compound (b) in which the prepolymer (A) has one or more polymerizable unsaturated groups and one carboxyl group in one molecule per one equivalent of the epoxy group of the epoxy compound (a). Is a product obtained by reacting 0.8 to 1.2 equivalents of the compound and 0.3 to 1.0 equivalent of the saturated or unsaturated polybasic acid anhydride (c), respectively. Photosensitive composition. 4. The method according to claim 1, wherein the blocked isocyanate (D) is 1
A polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in the molecule and a phenol,
Alcohols, acid amides, oximes, esters,
4. A reaction product with a blocking agent selected from the group consisting of diketones, mercaptans, ureas, imidazoles, acid imides, amines and carbamates. The photosensitive composition as described in the above. 5. The photosensitive composition according to claim 4, wherein the blocking agent is a blocking agent selected from the group consisting of acid amides, diketones, esters, alcohols and carbamates. 6. The photosensitive composition according to claim 4, wherein the polyisocyanate compound is a polyisocyanurate compound obtained by an isocyanuration reaction of a diisocyanate compound. 7. The photosensitive composition according to claim 4, wherein the polyisocyanate compound is an isocyanate group-terminated polyurethane polyisocyanate compound obtained by reacting a diisocyanate compound with a polyfunctional active hydrogen compound. . 8. The photosensitive composition according to claim 4, wherein the polyisocyanate compound is a polyurea polyisocyanate compound, polymeric isocyanate or diphenylmethane diisocyanate. 9. The photosensitive composition according to claim 1, wherein the blocked isocyanate (D) is a compound having an isocyanurate ring. 10. The content of each of the components (A) to (D) is, by weight ratio, prepolymer (A): 100, photopolymerization initiator (B): 1 to 30, reactive diluent. (C): 1 to 1
The photosensitive composition according to any one of claims 1 to 9, wherein the ratio is 00, blocked isocyanate (D): 2 to 100. 11. A cured product obtained by curing the photosensitive composition according to claim 1. Description: 12. A printed wiring board, wherein a cured film obtained by curing the photosensitive composition according to claim 1 is used.