JPH1192540A - Resin composition and cured material obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which gives a cured material soluble in an aqueous alkali and is suitable for an etching resist ink by blending a carboxylated copolymer, a specified compound, methacrylamide, a monofunctional (meth)acrylate monomer and a photopolymerization initiator. SOLUTION: This composition contains a carboxylated copolymer (A), a compound (B) represented by the formula (wherein R1 , R2 and R3 are each H or CH3 ), methacrylamide (C), a monofunctional (meth)acrylate monomer (D) and a photopolymerization initiator (E). The component A preferably comprises a copolymer of styrene or α-methylstyrene with (meth)acrylic acid. The component B preferably comprises a product of reaction of tetrahydrophthalic anhydride with 2-hydroxyethyl (meth)acrylate. An example of the component D is 2-hydroxyethyl (meth)acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition curable by ultraviolet rays, and more particularly to a novel resin composition suitable as an etching resist ink for manufacturing a printed wiring board and a cured product thereof. .

[0002]

2. Description of the Related Art Conventionally, an ultraviolet curable etching resist ink contains a polyester, a hydroxyalkyl acrylate, a photopolymerizable monomer, a carboxylic acid having 2 to 36 carbon atoms, and a photopolymerization initiator. Composition (see, for example, JP-A-51-2503), a hydroxyalkyl acrylate half-ester compound of a polyester and a polybasic acid (or an anhydride thereof), a vinyl monomer having an ethylenically unsaturated bond, and a photopolymerization initiator. (For example, JP-A-57-13444) and the like.

[0003]

However, in the composition according to the prior art, when the resist film is peeled off, the resist film is not completely dissolved by the aqueous alkali solution, and the swelled and peeled film is formed by a filter or a peeling liquid jet nozzle. It has the problem of causing blockage.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and as a result, the present invention is suitable for an etching resist ink which is cured by ultraviolet rays, and the obtained cured portion is an aqueous alkaline solution (for example, 5% NaOH aqueous solution) and a cured product thereof. That is, the present invention provides (1) a carboxyl group-containing copolymer (A),

[0005]

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(Wherein, R ₁ , R ₂ and R ₃ in the formula (1) are each H or CH ₃ ), methacrylamide (C), monofunctional (meth) acrylate A resin composition containing a monomer (D) and a photopolymerization initiator (E); (2) a carboxyl group-containing copolymer (A) comprising styrene or α-methylstyrene and (meth) acrylic acid; The resin composition according to (1), which is a copolymer, and (3) the compound (B) represented by the general formula (1) is a reaction product of tetrahydrophthalic anhydride and 2-hydroxyethyl (meth) acrylate ( The resin composition according to 1), (4) the resin composition according to (1) to (3), which is used for an ultraviolet-curable etching resist ink, and (5).
(1) A cured product of the resin composition according to (3).

[0007] The resin composition of the present invention is cured by irradiation with ultraviolet light, and the cured portion is soluble in an aqueous alkaline solution.
The resin composition of the present invention uses the properties of a cured film, such as acid resistance and aqueous alkali solution solubility, to perform its function as a cured film, and then to remove the film, particularly in the field of printed wiring boards as described above. It can be suitably used as an etching resist ink for production.

The resin composition of the present invention comprises a carboxyl group-containing copolymer (A), a compound (B) represented by the above general formula (1), methacrylamide (C), and a monofunctional (meth) acrylate monomer ( D) and a photopolymerization initiator (E).

The carboxyl group-containing copolymer (A) used in the present invention includes, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate. Co-polymer with monoacrylate monomers such as acrylate, phenyl (meth) acrylate, phenyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and styrene monomers such as styrene and α-methylstyrene Coalescence and the like. Preferred copolymers (A) include copolymers of (meth) acrylic acid and styrene or α-methylstyrene. The acid value (mgOH / g) is 100-300.
Is preferred. Such copolymers are readily available on the market. For example, Johnson Krill J manufactured by Johnson Co., Ltd.
-67 (weight average molecular weight 10 ⁴ , acid value (mgKOH /
g) 195, softening point 143 ° C), Joncryl J-67
8 (weight average molecular weight 7000, acid value (mgKOH / g)
200, softening point 146 ° C.), John Krill J-682
(Average molecular weight 1600, acid value (mgKOH / g) 23
5, softening point 110 ° C.).

The compound (B) represented by the general formula (1) used in the present invention is obtained as an approximately equimolar reaction product of tetrahydrophthalic anhydride or 2-methyl-tetrahydrophthalic anhydride with hydroxyalkyl (meth) acrylate. As the obtained (meth) acrylate having a hydroxyalkyl group, for example, 2-hydroxyethyl (meth)
Examples thereof include 2-hydroxy (C2 to C3) alkyl (meth) acrylates such as acrylate and 2-hydroxypropyl (meth) acrylate. Preferred compound (B)
Examples thereof include a reaction product of tetrahydrophthalic anhydride and 2-hydroxyethyl acrylate, a reaction product of tetrahydrophthalic anhydride and 2-hydroxyethyl methacrylate, or a mixture of these reaction products.

The monofunctional (meth) acrylate monomer (D) used in the present invention is an acrylate monomer having one acrylate group in a molecule, for example, carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl Oxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like can be mentioned.

The photopolymerization initiator (E) used in the present invention includes, for example, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, benzophenone, 4,4 '-Diethylaminobenzophenone, dichlorobenzophenone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,
Benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ethyl ester and the like can be mentioned. These can be used alone or in combination.

(A) to Constituting the Resin Composition of the Present Invention
The proportion of the component (E) used in the mixture of the components (A) to (E) is preferably 0.1% for the carboxyl group-containing polymer (A).
5-20% by weight, especially 1-10% by weight is preferred. or,
The use ratio of the compound (B) represented by the general formula (1) is 55 to 85% by weight in the mixture of the components (A) to (E).
, And particularly preferably 60 to 80% by weight. The use ratio of methacrylamide (C) in the mixture of the components (A) to (E) is preferably 5 to 20% by weight, and particularly preferably 7 to 15% by weight. The usage ratio of the monofunctional (meth) acrylate (D) is 5 to 20 in the mixture of the components (A) to (E).
% By weight, and particularly preferably 7 to 15% by weight. The proportion of the photopolymerization initiator (E) used is preferably 0.5 to 15% by weight, more preferably 3 to 7% by weight in the mixture of the components (A) to (E).
% By weight is preferred.

The resin composition of the present invention may further contain, if necessary, a coloring agent, a leveling agent such as a silicon compound or a fluorine-based surfactant, an antifoaming agent, an adhesion promoter such as a silane coupling agent, Aerosil, etc. And a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and phenothiazine; and an inorganic filler such as talc, silica dioxide, and barium sulfate.
When these additives and the like are used, the amounts of the additives are, for example, 0.5 to 3 parts by weight of a coloring agent, 10 to 60 parts by weight of an inorganic filler, and 100 parts by weight of the total amount of the components (A) to (E).
About 0.5 to 3 parts by weight of each of the other additives is a rough guide, but may be appropriately increased or decreased according to the purpose of use.

[0015] The resin composition of the present invention comprises the above (A)
It can be prepared by mixing, dispersing and kneading the component (E), other additives, fillers and the like. The resin composition thus obtained can be cured by irradiating ultraviolet rays after printing a pattern to a thickness of 10 to 50 μm on a printed board by screen printing, for example, as an ultraviolet-curable etching resist ink. .

[0016]

Next, the present invention will be described in detail with reference to examples. (Synthesis example of compound (B) represented by general formula (1))

Synthesis Example 1 152 g of tetrahydrophthalic anhydride, 120.3 g of 2-hydroxyethyl acrylate, and 0.1 g of hydroquinone monomethyl ether as a polymerization inhibitor were charged, and the reaction was continued at 90 ° C. while gradually increasing the temperature. The reaction was continued for about 20 hours until the anhydride group disappeared, and the acid value (mg
KOH / g) 206, a compound of the following structural formula (B-1)
Get.

[0018]

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Synthesis Example 2 152 g of tetrahydrophthalic anhydride, 134.8 g of 2-hydroxyethyl methacrylate, and 0.1 g of hydroquinone monomethyl ether as a polymerization inhibitor were charged, and the reaction was continued at 90 ° C. while gradually increasing the temperature. The reaction was continued for about 20 hours until the anhydride group disappeared, and the acid value (m
gKOH / g) 195.5 (B-
Obtain 2).

[0020]

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Example 1 John Krill 67 (Component (A): manufactured by Johnson Co., Ltd.)
Styrene and acrylic acid copolymer, weight average molecular weight 10
⁴ , acid value (mgKOH / g) 195, softening point 143 ° C)
4.00 g, compound (B-1) of Synthesis Example 1 23.60
g, 24.90 g of compound (B-2) of Synthesis Example 2, 6.60 g of methacrylamide (C), and carbitol acrylate (monofunctional (meth) acrylate monomer (D)) 7.
10 g and 3.80 g of benzyldimethyl ketal (photopolymerization initiator (E)) were mixed and dissolved. Next, 0.5 g of cyanine blue, 0.9 g of Modaflow (a leveling agent manufactured by Monsanto), and talc (filler) 2 were further added to the mixture.
After 8.5 g was uniformly mixed, the mixture was sufficiently kneaded with a three-roll mill (manufactured by Inoue Seisakusho) to obtain a resin composition of the present invention (ultraviolet curable etching resist ink).

The resin composition of the present invention is applied to a screen by 0.1, 0.15, 0.2, 0.3, 0.8, 1.0 m
Using a pattern having five m-widths each, printed on a copper foil of a printed wiring board by a screen printing method and cured with ultraviolet light, a sample having a pencil hardness of 4H was obtained. . This sample was placed in a cupric chloride etching solution at 50 ° C.
For 30 minutes, there was no abnormality in the state of all the coating films of 0.1 to 1.0 mm width. 50 coatings
When dissolved in 5% aqueous sodium hydroxide solution at
Dissolved in 3 seconds.

Example 2 Johnson J-678 (Component (A): Johnson Co., Ltd.)
Copolymer of α-methylstyrene and acrylic acid, weight average molecular weight 7000, acid value (mgKOH / g) 200,
(Softening point 146 ° C) 2.96 g, compound of Synthesis Example 1 (B-
1) 39.53 g, compound (B-2) of Synthesis Example 2
58 g, 6.92 g of methacrylamide (C), 4.94 g of 2-hydroxypropyl methacrylate (monofunctional (meth) acrylate monomer (D)), 3.95 g of benzyldimethyl ketal (photopolymerization initiator (E)), Shanin Blue 0.5g, Modaflow 0.99g and Talc 2
After uniformly mixing 9.64 g of the composition, kneading, printing, and curing were performed in the same manner as in Example 1, and a sample having a pencil hardness of 3H was obtained.

This sample was placed in a cupric chloride etching solution for 50 days.
When treated at 30 ° C. for 30 minutes, there was no abnormality in the state of all the coating films having a width of 0.1 to 1.0 mm. 5 coatings
When dissolved in a 5% aqueous sodium hydroxide solution at 0 ° C.,
Dissolved in 18 seconds.

Comparative Example 1 80 g (1.05 mol) of propylene glycol, 25 g (0.15 mol) of isophthalic acid and 99 g of maleic anhydride
(0.85 mol) in an N ₂ gas atmosphere.
Softening point 60.5 obtained by reacting at 200 ° C. for 18 hours.
C., 4.4 g of polyester having an acid value of 53, 25.61 g of the compound of Synthesis Example 1, 24.88 g of the compound of Synthesis Example 2, 7.32 g of carbitol acrylate, 2.93 g of 2-hydroxypropyl methacrylate, and benzyl methyl ketal 3. .90 g, Shanin Blue 0.5 g, Modaflow 0.99 g, and talc 29.27 g were uniformly mixed, and then kneaded, printed, and cured in the same manner as in Example 1. A sample having a hardness of 3H was obtained.

This sample was placed in a cupric chloride etching solution for 50 hours.
When treated at 30 ° C. for 30 minutes, there was no abnormality in the state of all the coating films having a width of 0.1 to 1.0 mm. 5 coatings
When dissolved in a 5% aqueous sodium hydroxide solution at 0 ° C., 3
It swelled and peeled in 0 seconds.

As is clear from the results of the above Examples and Comparative Examples, the cured product of the resin composition of the present invention is soluble in an aqueous alkaline solution and has good acid resistance.

[0028]

The resin composition of the present invention has good stability, and its cured product is soluble in an aqueous alkaline solution and has good acid resistance, and is suitable for an ultraviolet-curable etching resist ink.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 H05K 3/06 H05K 3/06 H

Claims (5)

[Claims] 1. A carboxyl group-containing copolymer (A) having the general formula (1): ## STR1 ## (Wherein R ₁ , R ₂ and R ₃ are H or CH ₃ in the formula (1)), methacrylamide (C), monofunctional (meth) acrylate monomer (D) And a photopolymerization initiator (E). 2. The resin composition according to claim 1, wherein the carboxyl group-containing copolymer (A) is a copolymer of styrene or α-methylstyrene and (meth) acrylic acid. 3. The resin composition according to claim 1, wherein the compound (B) is a reaction product of tetrahydrophthalic anhydride and 2-hydroxyethyl (meth) acrylate. 4. The resin composition according to claim 1, which is used for an ultraviolet-curable etching resist ink. 5. A cured product of the resin composition according to any one of claims 1 to 3.