JP2002308960A - Resin composition, solder resist resin composition and their cured products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which excels in photosensitivity, excels in the flexibility and soldering heat resistance, resistance to heat deterioration, and electroless gold plating resistance of cured products, can be developed with a dilute alkali solution, and is suited in use for solider resists and interlaminar insulating layers. SOLUTION: The resin composition comprises (A) a maleimide group- containing polycarboxylic acid urethane resin obtained by reacting (c) a reaction product of (a) an epoxy resin having two epoxy groups in the molecule with (b) a maleimide group-containing monocarboxylic acid, (d) an organic polyisocyanate compound, (e) a tetracarboxylic dianhydride, and (f) a hydroxyl group-containing (meth)acrylate as the optional component, and (B) a diluent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition containing a specific maleimide group-containing resin (A) and a diluent (B) and useful as a resin composition for printed wiring boards, and a cured product thereof. More specifically, it is useful as a solder resist for flexible printed wiring boards, a plating resist, a solder resist for multilayer printed wiring boards, and an interlayer electric insulating material. It has excellent developability, and its cured film has good adhesion and flexibility (bending). The present invention relates to a resin composition which gives a cured product excellent in solder heat resistance, chemical resistance, plating resistance and the like, and a cured product thereof.

[0002]

2. Description of the Related Art A wiring (circuit) pattern formed on a substrate by screen printing or the like is not required in a soldering process performed when protecting a wiring (circuit) pattern from an external environment or mounting electronic components on a printed wiring board. In order to protect solder from adhering to any part, a protective layer called a cover coat or a solder mask is coated on a printed wiring board. Conventionally, as a solder resist ink used in such applications, a polyfunctional epoxy resin-based ink has been mainly used, but the cured film obtained has good heat resistance but low flexibility (flexibility). There was a problem. Accordingly, such a solder resist ink is limited in its use for a rigid board which does not require the flexibility of a cured film, and is difficult to use for a flexible printed wiring board (FPC) which has been increasingly used in recent years. It is.

Under the circumstances described above, many proposals have recently been made as resist inks having flexibility. For example, JP-A-2-269166 discloses a thermosetting solder resist ink comprising polyparabanic acid, an epoxy resin and a polar solvent, and JP-A-6-41485 discloses a thermal drying method comprising polyparabanic acid and a phenoxy resin as essential components. Molded solder resist inks have been proposed.
However, since these solder resists form a resist pattern by screen printing, it is difficult to respond to fine image formation associated with today's high density, for example, the line width of the screen is limited. . For this reason, in recent years, there has been proposed an ultraviolet curable photo-developing type as disclosed in JP-A-2-173949, JP-A-2-173750, JP-A-2-173751, and the like, but it is still insufficient. It has not yet reached the point of imparting flexibility. In recent years, in the process of processing printed circuit boards, the number of plating steps such as nickel plating, gold plating, tin plating, and copper plating is increasing. However, when an ultraviolet-curable solder resist is used, photopolymerization is started in the solder resist ink. The agent is usually used at a concentration of 5 to 10% by weight, and a considerable amount remains in the cured film after the cured product, and is eluted from the cured film into the plating solution during the plating step, which may cause a problem.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to use a specific maleimide group-containing resin (A) so that a photopolymerization initiator is not used or the curability ( Excellent in photosensitivity), a fine image can be formed by exposure and development with a diluted alkaline aqueous solution,
The cured film obtained by heat-curing in the post-curing (post-curing) process is rich in flexibility and forms a film with excellent solder heat resistance, heat deterioration resistance, electroless gold plating resistance, acid resistance and water resistance. It is an object of the present invention to provide a resin composition suitable for an alkaline developing type resist ink particularly for a flexible printed wiring board or a high multilayer wiring board, and a cured product thereof.

[0005]

The present invention provides a resin composition containing a specific maleimide group-containing polycarboxylic acid urethane resin (A) and a diluent (B) in order to solve the above-mentioned problems. It has been found that the above problems can be achieved by using the present invention, and the present invention has been completed. That is, according to the present invention, (1) a reaction product (c) of an epoxy resin (a) having two epoxy groups in one molecule, a maleimide group-containing monocarboxylic acid (b), and an organic polyisocyanate compound (d) And a resin containing a maleimide group-containing polycarboxylic acid urethane resin (A) obtained by reacting a tetracarboxylic dianhydride (e) with a hydroxyl group-containing (meth) acrylate (f) as an optional component, and a diluent (B) The composition according to (1), comprising (2) an epoxy resin (g) having two or more epoxy groups in one molecule and an ethylenically unsaturated group-containing polycarboxylic acid resin (C), (3) An epoxy resin having an epoxy group having two or more epoxy groups in one molecule (g) is a phenol novolak epoxy resin, a cresol novolak epoxy resin, a tris Enorumetan type epoxy resin and (1)

[0006]

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(In the formula (1), X represents —CH ₂ — or —C
(CH ₃ ) ₂ —, n is an integer of 1 or more, and M represents a hydrogen atom or the following formula (G).

[0008]

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However, when n is 1, M represents the formula (G),
When n is greater than 1, at least one of M is of the formula (G)
And the rest represent hydrogen atoms. (2) The resin composition according to (2), which is at least one selected from epoxy resins represented by (4), and any one of (1) to (3), which contains a photopolymerization initiator (D). The resin composition according to the paragraph,
(5) The resin composition according to any one of (1) to (4), which contains a thermosetting component (E), (6), for a solder resist or an interlayer insulating layer of a printed wiring board. (1) The resin composition according to any one of (5), (7), a cured product of the resin composition according to any one of (1) to (6), (8), ( The present invention relates to an article having a cured product layer according to 7), (9), and an article according to (8), which is a printed wiring board.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin composition of the present invention is a mixture of a maleimide group-containing polycarboxylic urethane resin (A) and a diluent (B). The component (A) used here preferably has an acid value of 10 to 300 mgKOH / g. As described above, the epoxy resin (a) having two epoxy groups in one molecule and the maleimide group-containing monocarboxylic acid It can be obtained by reacting the reactant (c) of (b), the organic polyisocyanate compound (d), the tetracarboxylic dianhydride (e), and the hydroxyl group-containing (meth) acrylate (f) as an optional component.

Specific examples of the epoxy resin (a) having two epoxy groups in one molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, biphenol diglycidyl ether, and bi (tetramethylphenol) diglycidyl ether. Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane -1,4-dimethanol diglycidyl ether, polysulfide-modified epoxy resin (eg, product name FLEP-10, F manufactured by Toray Thiokol Co., Ltd.)
LEP-50, FLEP-60, FLEP-80, etc.).

Specific examples of the maleimide group-containing monocarboxylic acid (b) include, for example,

[0013]

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As shown in the above, from the maleic anhydride and the primary aminocarboxylic acid, a known technique [for example,
DH Rich et al.
Of medical chemistry (Journal o
f Medical Chemistry) "No. 18
(B-1), secondly, a maleimide compound having a hydroxyl group and a compound having one acid anhydride group in the molecule. (B-2) and the like.

As the maleimide compound having a hydroxyl group, for example, a reaction formula

[0016]

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## STR1 ## As shown in the above formula, maleimide and formaldehyde are used

[0018]

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As shown in the above formula, the compound can be synthesized from maleic anhydride and a primary amino alcohol using a known technique (for example, see US Pat. No. 2,526,517 and JP-A-2-268155). it can.

The primary aminocarboxylic acid used in the above reaction includes, for example, asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methyl-phenylalanine , Lysine, leucine, cycloleucine, 3-
Aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-amino Caprylic acid,
Examples include, but are not limited to, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocapric acid, 15-aminopentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid, and the like.

The primary amino alcohol used in the above reaction includes, for example, 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-
Amino-3-phenyl-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-
Amino-3-methyl-1-butanol, 2-amino-4
Methylthio-1-butanol, 2-amino-1-pentanol, (1-aminocyclopentane) methanol, 6
-Amino-1-hexanol, 7-amino-1-heptanol, 2- (2-aminoethoxy) ethanol, and the like, but are not limited thereto.

Specific examples of the compound having one acid anhydride group in the molecule include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-hexahydroanhydride. Examples thereof include phthalic acid and methyl-tetrahydrophthalic anhydride.

The half-esterified product (b-2) is
It can be obtained by reacting one chemical equivalent of a hydroxyl group in the maleimide compound having a hydroxyl group with about one chemical equivalent of an anhydride group in a compound having one acid anhydride group in the molecule. The reaction temperature is preferably from 60 to 100C, and the reaction time is preferably from 1 to 10 hours. An organic solvent can be used as required during the reaction. The reaction between the epoxy resin (a) and the maleimide group-containing monocarboxylic acid (b) is carried out without a solvent or a solvent having no alcoholic hydroxyl group, specifically, solvents such as acetone, ethyl methyl ketone, Ketones such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene, glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethylene glycol dimethyl ether Ethers,
Esters such as ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, and cyclic esters such as γ-butyrolactone , Petroleum solvents such as petroleum ether, petroleum naphtha and sorbene naphtha can be preferably used.

At the time of the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst is 0.1 to 10% by weight based on the reaction product. Specific examples of catalysts are:
Examples include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, and zirconium octoate.

Further, during the reaction, a polymerization inhibitor may be used for the purpose of preventing polymerization. Specific examples of the polymerization inhibitor include P-
Methoxyphenol, hydroquinone, methylhydroquinone, phenothiazine and the like can be mentioned. The amount of the polymerization inhibitor to be used is 0.05 to 3% by weight based on the weight of the reaction product.

During or after the reaction, one or more of the following reactive diluents (B-2) can be used. The reaction temperature is 60 to 150 ° C., particularly preferably 80.
~ 120 ° C. The reaction time is preferably 5 to 60 hours.

Next, the obtained reactant (c), the organic polyisocyanate compound (d), the tetracarboxylic dianhydride (e) and the hydroxyl group-containing (meth) acrylate (f) as an optional component are reacted. As a reaction method, (c) and (e) are reacted, and then (d) is reacted. Further, a method of reacting (f) if necessary (first method), a method of reacting (c) and (d), a reaction of (e), and a reaction of (f) as necessary ( 2nd method).

Specific examples of the organic polyisocyanate compound (d) used in synthesizing the resin (A) of the present invention include, for example, tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and 2-isocyanatoethyl-2. , 6-Diisocyanate caproate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate trimer, methylene-bis (4-
Phenylisocyanate), norbornane-diisocyanatomethyl, m-xylene diisocyanate, 1,3
Organic polyisocyanates (d-1) such as -bis (isocyanatomethyl) cyclohexane, urethane prepolymers having terminal isocyanate groups (d-2) which are reaction products of these organic polyisocyanates (d-1) and various polyol compounds, etc. Can be mentioned.

Specific examples of various polyol compounds include:
Examples thereof include an alkyl polyol, a polyester polyol, a polyether polyol, a polycaprolactone polyol, an acrylic polyol, a polybutadiene polyol, and a polysilicon polyol. The tetracarboxylic dianhydride (e) used when synthesizing the resin (A) of the present invention is, for example, a compound represented by the general formula (2)

[0030]

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(Wherein, R ₃ represents a tetravalent organic group having 2 to 30 carbon atoms), and those represented by a tetracarboxylic dianhydride or a derivative thereof. Can be.

The tetracarboxylic dianhydride represented by the general formula (2) is not particularly limited. Examples thereof include pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, and 3,3 ′. , 4,4′-biphenyltetracarboxylic acid, 2,3 ′, 3,4′-biphenyltetracarboxylic acid,

2,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3 6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid,
3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, m-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 [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 1, 1,1,3,3,3-hexafluoro-2,2
-Bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,7,8-phenanthrenetetracarboxylic Acid, dianhydride of aromatic tetracarboxylic acid such as 4,4′-bis (2,3-dicarboxyphenoxy) diphenylmethaneethylene glycol bis (anhydrotrimellitate), the following general formula (3)

[0034]

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(Wherein R ₄ and R ₅ are monovalent hydrocarbon groups,
Preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms (phenyl group, tolyl group, naphthyl group);
Each may be the same or different, and liter is an integer of 1 or more. ), Cyclobutenetetracarboxylic acid, butanetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid And the like. These are used alone or in combination of two or more. As a specific example of the hydroxyl group-containing (meth) acrylate (f), a (meth) acrylate having one or two hydroxyl groups in a molecule is preferable, and specifically, 2-hydroxyethyl (meth) acrylate, As specific examples of the hydroxypropyl (meth) acrylate and the hydroxyl group-containing (meth) acrylate (f), a (meth) acrylate having one or two hydroxyl groups in a molecule is preferable, and specifically, 2-hydroxyethyl (Meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3
-Phenylpropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, di (meth) acrylate of bisphenol A diglycidyl ether, di (meth) of hydrogenated bisphenol A diglycidyl ether
Acrylate, di (meth) acrylate of bisphenol F diglycidyl ether, di (meth) acrylate of hydrogenated bisphenol F diglycidyl ether, di (meth) acrylate of biphenol diglycidyl ether,
Examples thereof include di (meth) acrylate of a polysulfide-modified epoxy resin.

In the first method of the above-mentioned reaction method, for example, 0.5 to 0.99 equivalents of the anhydride group of the component (e) per 1 equivalent of the hydroxyl group in the component (c) is preferable, and particularly preferably 0.5 to 0.99 equivalent. 0.9 equivalent. Next, (d) was adjusted to 0.5 to 0.9 per equivalent of hydroxyl group in the reaction product of (c) and (e).
Reacting the equivalents to obtain the component (A); reacting (d) with 1.2 to 2.0 equivalents; and further reacting the isocyanate in the reaction product of (c), (e) and (d). Any of the cases where the component (A) is obtained by reacting 1 to 2 equivalents of the hydroxyl group in the component (f) per equivalent of the group. As the second method, for example, per equivalent of hydroxyl group in the component (c),
The isocyanate group of component (d) is reacted with 0.5 to 0.9 equivalent, and then 0.5 to 0.9 equivalent of (e) per equivalent of hydroxyl group in the reaction product of (c) and (d). When the component (A) is obtained by the reaction, 1.2 to 2.0 equivalents of the component (e) are reacted, and the anhydride group in the reaction product of the components (c), (d) and (e) is further reacted. One equivalent of the hydroxyl group in component (f)
Any reaction may be used in which the component (A) is obtained by reacting up to 2 equivalents.

The reaction temperature is 60 to 120 for each reaction.
° C, particularly preferably 80 to 100 ° C. The reaction time is preferably 1 to 30 hours.

In the present invention, a diluent (B) is used. Specific examples of the diluent (B) include, for example, the above-mentioned solvents, butanol, octyl alcohol, ethylene glycol,
Organic solvents (B-1) such as alcohols such as glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, and tetraethylene glycol monomethyl (or monoethyl) ether; and carbitol (meth) acrylate Of phenoxyethyl (meth) acrylate, acryloylmorpholine, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta and hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Water-soluble diluent (B-2).

The amount of the components (A) and (B) contained in the resin composition of the present invention is 10 (A) + (B) in total.
The content of (A) and (B) is preferably 10 to 90% by weight, and more preferably 20 to 80% by weight.
The content of (B) is preferably 10 to 90% by weight.

In the present invention, an ethylenically unsaturated group-containing polycarboxylic acid resin (C) may be used. The ethylenically unsaturated group-containing polycarboxylic acid resin (C) contains 2 per molecule.
It is a reaction product of an epoxy resin (g) having two or more epoxy groups, a monocarboxylic acid (h) containing an ethylenically unsaturated group, and a polybasic anhydride (i).

The epoxy resin (g) having two or more epoxy groups in one molecule includes, for example, the above-mentioned general formula (1)
Epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol
Glycidyl ethers such as novolak type epoxy resin, cresol / novolak type epoxy resin, trisphenolmethane type epoxy resin, brominated epoxy resin, bixylenol type epoxy resin and biphenol type epoxy resin; 3,4-epoxy-6-methylcyclohexyl Alicyclic epoxy resins such as methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane A heterocyclic epoxy resin such as triglycidyl isocyanurate, etc., and preferred are a phenol-novolak epoxy resin, a cresol-novolak epoxy resin, and trisphenol Epoxy resins represented by methane type epoxy resin and (1) can be exemplified.

The epoxy resin represented by the general formula (1)
In formula (1), it can be obtained by reacting an alcoholic hydroxyl group of a raw material epoxy compound in which M is a hydrogen atom with an epihalohydrin such as epichlorohydrin. Raw epoxy compounds are commercially available, for example, Epicoat series (Epicoat 1009, 1031:
Yuka Shell Epoxy Co., Ltd.), Epicron series (Epiclon N-3050, N-7050: manufactured by Dainippon Ink and Chemicals, Inc.), DER series (DER-64)
Bisphenol A epoxy resin such as 2U, DER-673MF: manufactured by Dow Chemical Co., Ltd .; and bisphenol F type epoxy resin such as YDF series (YDF-2004, 2007: manufactured by Toto Kasei Co., Ltd.).

Next, specific examples of the ethylenically unsaturated group-containing monocarboxylic acid (h) include, for example, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β
-Furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid and the like. Of these, acrylic acid is preferred.

The epoxy resin (g) is reacted with the monocarboxylic acid (h) containing an ethylenically unsaturated group,
The polybasic acid anhydride (i) is reacted. Regarding the reaction between the component (g) and the component (h), the reaction ratio between the component (g) and the component (h) is such that the equivalent ratio of the carboxyl group of the component (h) is 0.1 to 1 equivalent of the epoxy group of the component (g). It is preferable to react 3 to 1.2 equivalents, particularly preferably 0.9 to 1.
05 equivalents.

During or after the reaction, as a diluting solvent, aromatic hydrocarbons such as toluene and xylene; ethyl acetate;
Esters such as butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; cyclohexane And one or more solvents such as alicyclic hydrocarbons such as methylcyclohexane and petroleum solvents such as petroleum ether and petroleum naphtha.

During or after the reaction, one or more of the above-mentioned reactive diluents (B-2) can be used.

Further, it is preferable to use a catalyst for accelerating the reaction. Examples of the catalyst include basic compounds such as triethylamine, benzylmethylamine, methyltriethylammonium chloride, triphenylstibine, and triphenylphosphine. The amount used is preferably 0.1% with respect to the reaction raw material mixture.
10 to 10% by weight, particularly preferably 0.3 to 5% by weight.

During the reaction, it is preferable to use a polymerization inhibitor in order to prevent polymerization of the ethylenically unsaturated groups. As the polymerization inhibitor, for example, P-methoxyphenol,
Hydroquinone, methylhydroquinone, phenothiazine and the like can be mentioned. The amount used is preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on the reaction raw material mixture. The reaction temperature is 60 to 1
The temperature is 50 ° C, particularly preferably 80 to 120 ° C. The reaction time is preferably 5 to 60 hours.

Next, the polybasic acid anhydride (i) is reacted. Examples of the polybasic acid anhydride (i) include succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyl-
Examples thereof include tetrahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride. The amount used is preferably 0.05 to 1.00 equivalent of the anhydride group of the component (i) per equivalent of the hydroxyl group in the reaction product of the above (g) and (h). Let it. The reaction temperature is 60
To 150 ° C, particularly preferably 80 to 100 ° C. The reaction time is preferably 1 to 10 hours.

The amount of the component (A) + (B) component 1
20 to 300 parts by weight, preferably 3 to 100 parts by weight
A ratio of 0 to 200 parts by weight is appropriate.

In the present invention, a photopolymerization initiator (D) may be used. As the photopolymerization initiator (D), for example, 1-
Acetophenones such as hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one;
Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as benzyldimethyl ketal;
Benzophenones such as 4,4'-bisdiethylaminobenzophenone and 4-benzoyl-4'-methyldiphenylsulfide; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and the like, alone or in combination of two or more. They can be used in combination. Further, N, N-
Dimethylaminobenzoic acid isoamyl ester, N, N-
Dimethylaminobenzoic acid ethyl ester, pentyl-4
-Photopolymerization accelerators such as tertiary amines such as dimethylaminobenzoate can be used alone or in combination of two or more.

The amount of the photopolymerization initiator (D) used is from (A) to
The proportion is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the total amount of the component (C).

In the present invention, it is preferable to use a thermosetting component (E) as a curing system component in addition to the components described above.
By using this, a material for a printed wiring board having excellent solder heat resistance and electrical characteristics can be obtained. As the thermosetting component (E) used in the present invention, a maleimide group-containing polycarboxylic acid (meth) acrylate resin (A) and an ethylenically unsaturated group-containing polycarboxylic acid resin (C) are combined with a thermosetting functional group in the molecule. , But are not particularly limited. Examples thereof include an epoxy resin, a melamine compound, a urea compound, and an oxazoline compound. As the epoxy resin, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin,
Glycidyl ethers such as cresol / novolak type epoxy resin, trisphenol methane type epoxy resin, brominated epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin; 3,4-epoxy-6
-Methylcyclohexylmethyl-3,4-epoxy-6
-Methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,
Alicyclic epoxy resins such as 4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl hexahydrophthalate and glycidyl dimer; and heterocyclic epoxy resins such as triglycidyl isocyanurate. Can be Among them, an epoxy resin having a melting point of 50 ° C. or more is preferred because it can form a tack-free photopolymer film after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline,
2,4-diphenyloxazoline and the like.

Among these thermosetting components (E), epoxy resins are particularly preferred because of their excellent reactivity with carboxyl groups in components (A) and (C) and good adhesion to copper.

The preferred range of the amount of the thermosetting component (E) used is generally such that the functional group of the thermosetting component (E) is 0 per carboxyl group in the components (A) and (C). .2
It is a ratio that becomes -3.0 equivalents. Above all, from the viewpoint of excellent solder heat resistance and electrical characteristics when formed into a printed wiring board.
A ratio of 0 to 1.5 equivalents is preferred.

When an epoxy resin is used as the thermosetting component (E), a curing accelerator for the epoxy resin is used to accelerate the reaction with the carboxyl groups in the components (A) and (C). Is preferred. Specific examples of the curing accelerator for the epoxy resin include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1-methylimidazole.
Imidazole compounds such as cyanoethyl-2-ethylimidazole and 1-cyanoethyl-2-undecylimidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-diaminotriazine, 2,4-diamino-6-tolyl Triazine derivatives such as triazine; polyphenols and the like. These curing accelerators can be used alone or in combination.

Further, in the present invention, the above-mentioned maleimide group-containing polycarboxylic acid urethane resin (A), diluent (B), ethylenically unsaturated group-containing polycarboxylic acid resin (C), photopolymerization initiator (D) And the thermosetting component (E),
Further, if necessary, various additives, for example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica and clay; thixotropic agents such as Aerosil; phthalocyanine Coloring agents such as blue, phthalocyanine green, titanium oxide, etc .; silicone, fluorine-based leveling agents and defoamers; polymerization inhibitors such as hydroquinone, P-methoxyphenol, methylhydroquinone, etc. are added for the purpose of enhancing the performance of the composition You can do it.

The above-mentioned component (E) may be mixed in advance with the resin composition, but it is preferable to use the component (E) before mixing it on a printed circuit board. That is, the two-component type of the main component solution mainly composed of the components (A) and (C) and the epoxy curing accelerator and the like, and the curing agent solution mainly composed of the component (E), When used, it is preferable to mix them.

The resin composition of the present invention can be used, for example, on a polymer film (for example, a film made of polyethylene terephthalate, polypropylene, polyethylene, etc.) as a support.
1) can be evaporated and laminated to be used as a photosensitive film.

The resin composition (liquid or film form) of the present invention is useful as an insulating material between layers of electronic parts, as a resist ink such as a sonoleder resist for printed circuit boards, etc. It can also be used as a coating agent, adhesive or the like. The cured product of the present invention is obtained by curing the above-described resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. For example, when irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (such as an excimer laser) and the like are used. May be used. The cured product of the resin composition of the present invention is used for an electric / electronic component such as a printed board as a permanent resist or an interlayer insulating material for a build-up method. The thickness of the cured product layer is about 0.5 to 160 μm, preferably about 1 to 60 μm.

The printed wiring board of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention is applied to a substrate for printed wiring with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. Of the composition, the coating film is usually 60 to 110 ° C., preferably
By drying at a temperature of preferably 60 to 100 ° C., a tack-free coating film can be formed. Thereafter, a photomask on which an exposure pattern such as a negative film is formed is brought into direct contact with the coating film (or placed on the coating film in a non-contact state), and ultraviolet light is usually irradiated at an intensity of about 10 to 2000 mJ / cm ^2. Then, the unexposed part using an image liquid described below,
For example, development is performed by spraying, rocking immersion, brushing, scrubbing, or the like. After that, by further irradiating with ultraviolet rays, and then performing heat treatment at a temperature of usually 100 to 200 ° C., preferably 140 to 180 ° C., excellent flexibility, heat resistance of the resist film and solvent resistance A printed wiring board having a permanent protective film that satisfies various properties such as properties, acid resistance, adhesion, and electrical properties can be obtained.

Examples of the organic solvent used for the development include halogens such as trichloroethane, aromatic hydrocarbons such as toluene and xylene; esters such as ethynole acetate and butyl acetate; 1,4-dioxane and tetrahydrofuran. Ketones such as methyl ethyl ketone and methyl isobutyl ketone; lactones such as γ-butyrolactone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; fats such as cyclohexanone and cyclohexanol Solvents such as cyclic hydrocarbons and petroleum solvents such as petroleum ether and petroleum naphtha,
As the water and the aqueous alkali solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used. Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as the active light for exposure.

[0065]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples. In the following, “parts” means “parts by weight” unless otherwise specified.

(Synthesis Example of Reactant (C)) Synthesis Example 1 Bisphenol A diglycidyl ether (YD-8125 epoxy equivalent 173, manufactured by Toto Kasei Co., Ltd.) 346
g, maleimidocaproic acid 414 g, carbitol acetate 410.6 g, P-methoxyphenol 0.3 g
And 2.3 g of triphenylphosphine at 98 ° C.
For about 32 hours, and the acid value (mgKOH / g) is 3.
After reaching 0 or less, the reaction was terminated, and a reactant (C-1) containing a substance of the following structural formula having a solid content concentration of 65% by weight as a main component:
I got

[0067]

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(Synthesis Example of Maleimide Group-Containing Polycarboxylic Urethane Resin (A)) Synthesis Example 2 1706.2 g of the reaction product (C-1) obtained in Synthesis Example 1, 218 g of pyromellitic acid and carbitol acetate 11
After charging 7.4 g and reacting at 95 ° C. for about 10 hours, the reaction was terminated when the hydrate group disappeared, and then 84 g of hexamethylene diisocyanate and carbitol acetate 4 were added.
5.2 g was charged and reacted at 80 ° C. for 15 hours, and the reaction was terminated when the concentration of the isocyanate group became 0.3% or less.
Solid content concentration 65% by weight, acid value of solid content (mg KOH /
g) 80.0 maleimide group-containing polycarboxylic acid urethane resin (A-1) was obtained. The weight average molecular weight of the solid content was about 4500 (by GPC method).

Synthesis Example 3 2558.3 g of the reaction product (C-1) obtained in Synthesis Example 1, 436 g of pyromellitic acid and carbitol acetate 23
4.8 g was charged and reacted at 95 ° C. for about 10 hours to terminate the reaction when the anhydride group disappeared. Then, 348 g of tolylene diisocyanate and carbitol acetate 18 were added.
After charging 7.4 g and reacting at 80 ° C. for about 8 hours, when the isocyanate group concentration reached 2.23% by weight, 243.6 g of 2-hydroxyethyl acrylate and 131.2 g of carbitol acetate were charged, and the mixture was heated at 80 ° C. The reaction was carried out for about 10 hours until the isocyanate group became 0.3% by weight or less.
(gKOH / g) 83.8, a maleimide group-containing polycarboxylic acid urethane resin (A-2) was obtained. The weight average molecular weight of the solid content was about 4000 (by GPC method).

(Synthesis Example of Ethylenically Unsaturated Group-Containing Polycarboxylic Acid Resin (C)) Synthesis Example 4 In the above general formula (1), X is —CH ₂ —, M is a hydrogen atom, and the average degree of polymerization n is Bisphenol F 6.2
After dissolving 380 g of a type epoxy compound (epoxy equivalent 950 g / eq, softening point 85 ° C.) and 925 g of epichlorohydrin in 462.5 g of dimethyl sulfoxide, 60.9 g (1.5 mol) of 98.5% NaOH at 70 ° C. with stirring. Was added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the completion of the reaction, 250 parts of water was added and washed. After oil-water separation, most of dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation under reduced pressure from the oil layer, and then dimethyl sulfoxide was distilled off.The reaction product containing by-product salts was dissolved in 750 parts of methyl isobutyl ketone. Further, 10 parts of 30% NaOH was added and reacted at 70 ° C. for 1 hour. After the reaction is completed, add 200
The part was washed twice with water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer, and the epoxy equivalent was 310 g.
/ Eq, an epoxy resin (f) having a softening point of 69 ° C. was obtained. When the obtained epoxy resin (f) was calculated from the epoxy equivalent, about 5 of the 6.2 alcoholic hydroxyl groups in the starting bisphenol F type epoxy compound were epoxidized. This epoxy resin (f)
310 g and 207.1 g of carbitol acetate were charged and heated and stirred at 90 ° C. to dissolve. The obtained solution was cooled to 60 ° C., and 72.0 g of acrylic acid, 0.8 g of methylhydroquinone and 1.8 g of triphenylphosphine were obtained.
Was added and heated and dissolved at 80 ° C., and reacted at 98 ° C. for 35 hours to obtain an acrylate ester having an acid value (mg KOH / g) of 1.0 and a solid content of 65% by weight. Next, 591.7 g of this acrylic acid ester, 152 g of tetrahydrophthalic anhydride, and 81.8 of carbitol acetate were used.
g, and reacted at 90 ° C. for 10 hours.
An ethylenically unsaturated group-containing polycarboxylic acid resin (C-1) having a concentration of 05.5 mgKOH / g and a solid content of 65% was obtained. The weight average molecular weight of the solid content was about 7,500 (by GPC method).

Examples 1 to 1, Comparative Examples 1 to 1 The resist compositions of the present invention were blended, dissolved and kneaded according to the blending compositions shown in Table 1 to prepare the resist compositions. Then, the prepared resist composition is applied to a printed circuit board (a laminate of an imide film and a copper foil) by screen printing,
For 20 minutes. Then, a negative film was applied to this substrate, and the exposure was performed according to a predetermined pattern using an exposure machine at 600 mJ.
/ UV was irradiated with integrated exposure amount of cm _^2, 1wt% Na ²
The test substrate was prepared by developing with an aqueous solution of CO _{3 and} heat curing at 150 ° C. for 60 minutes. The photosensitive performance of the obtained resist composition was evaluated. With respect to the obtained test substrate, characteristics such as alkali developability, solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating resistance were evaluated. Table 2 shows the results. The evaluation method and evaluation criteria are shown below.

Table 1 Example Comparative Example 12 3 12 2 2 (A) Component Resin (A-1) obtained in Synthesis Example 2 154 77 Resin (A-2) obtained in Synthesis Example 3 107.8 77 (B) Component KAYARAD DPHA * 1 16 16 16 16 16 16 Carbitol acetate 10 10 (C) component Resin (C-1) obtained in Synthesis Example 4 46.2 154 154 154 154 (D) component Irgacure 907 * 2 4 2 2 10 10 3 Kayacure DETX-S * 3 0.48 0.24 0.24 1.2 1.2 0.36 (E) component YX-4000 * 4 30 30 30 30 DEN-438 * 5 30 30 Others Fine silica powder (filler) 10 10 10 10 10 10 Melamine (epoxy cured) Accelerator) 1.2 1.2 1.2 1.2 1.2 1.2 KS-66 (antifoaming agent) * 6 1.0 1.0 1.0 1.0 1.0 1.0

Note) * 1; KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Dipentaerythritol, penta and hexaacrylate mixtures. * 2; Irgacure 907: Ciba Specialty Chemicals, photopolymerization initiator, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one. * 3: Kayacure DETX-S: manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator, 2,4-diethylthioxanthone. * 4; YX-4000: a bisphenol-type epoxy resin manufactured by Yuka Shell Epoxy. * 5; DEN-438: Dow Chemical Co., Ltd., phenol novolak epoxy resin. * 6: KS-66: a silicone-based defoamer manufactured by Shin-Etsu Chemical Co., Ltd.

Evaluation Method and Evaluation Criteria (1) Photosensitivity: Step tablet 2 was applied to the dried coating film.
One stage (manufactured by Stoffer) is closely attached and the integrated light amount is 600 mJ.
/ Cm ² UV irradiation. Next, the number of steps of the coating film left undeveloped with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² is confirmed. The following criteria were used: …: 6 steps or more. Δ: 4 to 5 steps ×: 3 steps or less (2) Developability: The coating film was dried at 80 ° C. for 60 minutes, and
The developability by spray development with a 1% aqueous sodium carbonate solution at 0 ° C. was evaluated. …: No residue is visually observed. ×: Residues are visually observed.

(3) Solder heat resistance: A rosin-based flux was applied to a test substrate, immersed in molten solder at 260 ° C. for 10 seconds, and evaluated by the state of the cured film when peeled off with a cellophane adhesive tape. …: No abnormality. ×: Peeling occurred.

(4) Flexibility: Judgment was made in a state where the test substrate was folded at 180 degrees. ○ …… No crack. △: Some cracks. ×: Cracks were formed in the bent portion, and the cured film was separated.

(5) Heat deterioration resistance: The test substrate was left at 125 ° C. for 5 days, and then evaluated in a state of 180 ° solid bending. ○ …… No crack. △: Some cracks. ×: Cracks were formed in the bent portion, and the cured film was separated.

(6) Electroless Gold Plating Resistance: The gold plating was performed on the test substrate as described below, and the state was determined by peeling with a cellophane (registered trademark) adhesive tape. …: No abnormality. Δ: Some peeling was observed. ×: No peeling.

Electroless gold plating method: A test substrate was acidified with an acidic degreasing solution at 30 ° C.
(5 vol. L-5B aqueous solution) for 3 minutes to degrease, then dipped in running water for 3 minutes and washed with water. Next, the test substrate was placed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 hours.
The sample was immersed for 3 minutes, soft-etched, and then immersed in running water for 3 minutes and washed. Next, the test substrate was immersed in a 30 ° C. catalyst solution (10 vol% aqueous solution of a metal plate activator 350, manufactured by Meltex Co., Ltd.) for 7 minutes. . The test substrate to which the catalyst was applied was immersed in a 20 vol% aqueous solution of nickel plating solution (PH 4.6) at 85 ° C. for 20 minutes to perform electroless nickel plating. After the test substrate was immersed in a 10 Vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was subjected to a 95 ° C. gold plating solution (available from Meltex Co., Ltd., Aurolectroless UP15Vol% and potassium cyanide 3V).
immersed in running water for 3 minutes and washed with hot water at 60 ° C. for 3 minutes and washed with hot water. After sufficient washing with water, the water was drained off, dried, and a test board plated with electroless gold was obtained.

Table 2 Example Comparative example Item 1 2 3 1 2 3 Photosensitivity ○ ○ ○ ○ ○ × Developability ○ ○ ○ ○ ○ ○ Soldering heat resistance ○ ○ ○ ○ ○ ○ Flexibility ○ ○ ○ × × × Heat deterioration ○ ○ ○ × × × Electroless gold plating ○ ○ ○ ○ ○ ×

As is clear from the results shown in Table 2, the resin composition of the present invention has sufficient photosensitivity even when the amount of the photopolymerization initiator used is small, and shows good alkali developability. A cured film having excellent heat resistance, flexibility, heat deterioration resistance and electroless gold plating property is provided.

[0082]

According to the present invention, the amount of the photopolymerization initiator used is at least sufficiently curable, and the cured product is excellent in flexibility, solder heat resistance, heat resistance, deterioration, and electroless gold plating resistance.
Development was possible with a dilute alkali solution, and a resin composition suitable for a solder resist and for an interlayer insulating layer was obtained. This resin composition is suitable for a solder resist and an interlayer insulating layer of a printed wiring board, particularly a flexible printed wiring board.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 63/00 C08L 63/00 A 4J036 75/04 75/04 G03F 7/027 513 G03F 7/027 513 514 514 515 515 7/028 7/028 H05K 1/03 610 H05K 1/03 610L 3/00 3/00 FF term (reference) 2H025 AA01 AA04 AA07 AA10 AA13 AB15 AB20 AC01 AD01 BC66 BC69 BC72 BC73 BC74 BC83 BC85 BC86 CA00 CC17 FA17 4J002 CC16Y CC18Y CD02X CD02Y CD05X CD05Y CD06X CD06Y CD07X CD07Y CD09Y CD14X CD14Y CD20X CK02W EE036 EN096 ET017 EU187 EU217 EV066 EV306 EW146 FD010 FD030 FD090 FD146 FD147 G01G01 G01 G01G01 G01 G01G01 G01 SA25 SA28 SA29 SA54 SA58 SA61 SA64 TA08 TA10 UA01 UA02 VA01 WA01 WA02 WA06 4J027 AE02 AE03 AE04 AE05 AG03 AG04 AG05 AG06 AG07 AG12 AG23 AG24 AG27 AG32 AJ08 CA10 CA14 CA15 CA18 CA20 CA25 CA34 CA36 CB10 CC05 CD08 CD09 CD10 4J034 BA08 BA09 CA26 CB05 CB07 DA01 DA05 DB03 DB05 DB07 DF01 DF12 DG00 FC01 DM01 FC01 GA51 GA62 GA65 HA01 HA02 HA07 HC03 HC12 HC17 HC22 HC35 HC46 HC52 HC54 HC61 HC64 HC67 HC71 HC73 RA05 RA07 RA08 RA14 4J036 AA01 AC02 AF01 CA19 CA21 CA22 CB22 HA02 JA01 JA06 JA08 JA10

Claims (9)

[Claims] 1. A reaction product (c) of an epoxy resin (a) having two epoxy groups in one molecule and a monocarboxylic acid (b) containing a maleimide group, an organic polyisocyanate compound (d), and tetracarboxylic dianhydride A resin composition comprising a maleimide group-containing polycarboxylic urethane resin (A) obtained by reacting the product (e) with a hydroxyl group-containing (meth) acrylate (f) as an optional component, and a diluent (B). 2. A reaction product of an epoxy resin (g) having two or more epoxy groups in one molecule, a monocarboxylic acid containing an ethylenically unsaturated group (h), and a polybasic anhydride (i). The resin composition according to claim 1, which contains an ethylenically unsaturated group-containing polycarboxylic acid resin (C). 3. An epoxy resin having an epoxy group having two or more epoxy groups in one molecule (g) is a phenol.
Novolak type epoxy resin, cresol / novolak type epoxy resin, trisphenol methane type epoxy resin and formula (1) (In the formula (1), X is —CH ₂ — or —C (CH ₃ ) ₂ —, n is an integer of 1 or more, and M is a hydrogen atom or the following formula (G). 2] However, when n is 1, M represents the formula (G), and when n is greater than 1, at least one of M represents the formula (G) and the rest represents a hydrogen atom. The resin composition according to claim 2, which is at least one selected from epoxy resins represented by the formula (3). 4. The resin composition according to claim 1, further comprising a photopolymerization initiator (D). 5. The resin composition according to claim 1, further comprising a thermosetting component (E). 6. The resin composition according to claim 1, which is used for a solder resist or an interlayer insulating layer of a printed wiring board. 7. A cured product of the resin composition according to any one of claims 1 to 6. 8. An article having the cured product layer according to claim 7. 9. The article according to claim 8, which is a printed wiring board.