JPH1195428A - Resin composition and its cured body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin comspn. useful for a permanent resist applied on a printed circuit board by incorporating a specified polymer, a (meth)acrylate compd., a diluent, a photopolymn. initiator and a compd. having a carbodiimido group. SOLUTION: The resin compsn. contains a polymer (A) contg. hydroxyl and/or carboxyl groups in one molecule, a (meth)acrylate compd. (B), a diluent (C), a photopolymn. initiator (D) and a compd. (E) having a carbodiimido group. The especially pref. amts. of the components A, B, C, D and E are 20-70 wt.%, 10-50 wt.%, 10-50 wt.%, 1-10 wt.% and 1-20 wt.%, respectively, of the amt. of the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition useful as a permanent resist provided particularly on a printed wiring board, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, printed wiring boards are manufactured by using a copper-clad laminate and by a subtractive method in which unnecessary portions of a copper foil circuit are removed by etching. It is difficult to form a wiring board, and the small diameter through hole and via hole cannot be uniformly formed by electroplating. It is.

[0003] On the other hand, recently, a full additive method of forming an adhesive layer on a laminate made of an insulating base material and forming a circuit and a through hole by electroless plating has attracted attention. In this method, the conductor pattern accuracy is determined only by the transfer accuracy of the plating resist, and since the conductor portion is formed only by electroless plating, even with a substrate having a high aspect ratio through hole, uniform through hole plating with high throwing power can be achieved. It is possible to do. Until now, the additive method, which has been considered suitable for general consumer use, has begun to be put into practical use as an industrial, high-density, high-multilayer substrate manufacturing process.

[0004]

Generally, in an additive method for manufacturing a substrate for consumer use, a plating resist pattern is transferred by a screen printing method. However, in order to manufacture a printed wiring board having high-density wiring, ,
It is necessary to form a plating resist pattern by photolithography, that is, to employ a photo-additive method using a photoresist. Photoresists suitable for photo-additive methods include sensitivity, resolution,
In addition to the inherent properties of photoresist such as developability, the following properties are required. Development is limited to 1,1,1-trichloroethane-based organic solvent or alkaline aqueous solution, so that it can be developed by any of them, it can withstand electroless plating performed for a long time under high temperature and high alkaline conditions, plating After processing, have excellent solder resist properties as permanent resist, 260 in soldering process
It has heat resistance to withstand temperatures of around ° C and solvent resistance to organic solvents for cleaning flux used at the time of soldering, and does not lower the thermal reliability of the entire substrate even when laminated. At present, photoresists that can be used in the additive method are commercially available, but their performance is not yet satisfactory.

Accordingly, an object of the present invention is to form a resist with high pattern accuracy by a photographic method by developing using a dilute alkaline aqueous solution or water and sufficiently resisting or soldering the electroless copper plating solution of the full additive method. Process 2
One-part suitable for permanent resist used without removing even the final product, with heat resistance to withstand temperatures around 60 ° C and solvent resistance to organic solvents for cleaning flux used during soldering And a cured product thereof.

[Means for Solving the Problems]

[0006] The present invention relates to (1) a method in which a hydroxyl group and / or
Or a polymer (A) containing a carboxyl group, a (meth) acrylate compound (B), a diluent (C), a photopolymerization initiator (D), and a compound (E) having a carbodiimide group. Resin composition, (2)
The resin composition according to (1), wherein the compound (E) having a carbodiimide group is a powder; (3) the resin composition according to (1) or (2), which is used for a permanent resist; (4) (1) or ( (5) The cured product of (3), wherein the cured product is a permanent resist.

In the present invention, a polymer (A) containing a hydroxyl group and / or a carboxyl group in the molecule is used.
Examples of the polymer (A) include a copolymer (A-1) of (meth) acrylic acid and a monofunctional monomer, and a reaction product (A-) of a copolymer of styrene and maleic anhydride with an alcohol.
2), a partially saponified polymer of polyvinyl acetate (A-
3) and a copolymer (A-4) of a hydroxyl group-containing mono (meth) acrylate and / or a hydroxyl group-containing monovinyl ether with a water-soluble monomer. Particularly preferred polymers include the copolymer (A-1) and the polymer (A
-2) and a copolymer (A-4).

The monofunctional monomer in the copolymer (A-1) of (meth) acrylic acid and a monofunctional monomer is a monomer having one vinyl group in the molecule. Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)
Alkyl mono (meth) such as hydroxyl group-containing mono (meth) acrylate such as acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate
Acrylic monomers such as aromatic mono (meth) acrylates such as acrylate, phenyloxyethyl (meth) acrylate, 2,4,6-tribromophenyloxyethyl (meth) acrylate and benzyl (meth) acrylate; styrene; Styrene monomers such as vinyltoluene and α-methylstyrene are exemplified.

As a reaction product (A-2) of a copolymer of styrene and maleic anhydride with an alcohol, commercially available products such as SMA-1440 and SMA manufactured by Sartomer Co. are available.
-17352, SMA-2625 and the like. As one raw material alcohol, for example, methanol,
Ethanol, butanol, benzyl alcohol and the like can be mentioned.

As the partially saponified polymer (A-3) of polyvinyl acetate, commercially available products such as Gohsenol KP-08, Gohsenol KP-06 and Gohsenol NK-05 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. And the like.

As the hydroxyl group-containing mono (meth) acrylate in the copolymer (A-4) of the hydroxyl group-containing mono (meth) acrylate and / or the hydroxyl group-containing monovinyl ether and the water-soluble monomer, for example, 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Examples of the hydroxyl group-containing monovinyl ether include 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether. Examples of the water-soluble monomer include acryloylmorpholine, (meth) acrylamide, N-vinylpyrrolidone, N-vinylformaldehyde, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, N, N-diethyl ( Data) acrylamide, acrylic water-soluble monomers such as methoxypolyethylene glycol (meth) acrylate.

The number average molecular weight (M) of these polymers (A)
n) is preferably in the range of 500 to 100,000, and 10
The range of 00 to 70000 is more preferable.

In the present invention, the (meth) acrylate compound (B) is used. (Meth) acrylate compound (B)
Examples thereof include monomers and oligomers. Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acryloylmorpholine, phenoxyethyl (meth) acrylate, and isobornyl (meth)
Mono (meth) acrylates such as acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, N-vinylcaprolactam, methoxytetraethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexane Di (meth) acrylates such as diol di (meth) acrylate, nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, bisphenol A polyethoxylate (meth) acrylate, and glycerin diglycidyl ether di (meth) acrylate; Methylolpropane, pentaerythritol,
Ditrimethylolpropane, dipentaerythritol,
Examples include polyhydric (meth) acrylates of polyhydric alcohols such as tris-hydroxyethyl isocyanurate, and polyhydric (meth) acrylates of ethylene oxide or propylene oxide adducts of these polyhydric alcohols.

Examples of the oligomer include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin and (meth) acrylic. Epoxy (meth) acrylate which is a reaction product with an acid,
Examples thereof include polyurethane (meth) acrylate and polyester (meth) acrylate.

Specific examples of the diluent (C) include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and the like. Glycol ethers, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, and organic solvents such as petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. And the like.

As the photopolymerization initiator (D), for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-propan-1-one, acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzophenone, p-chlorobenzophenone, p,
p-bisdimethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4 '
-Benzophenones such as methyldiphenyl sulfide, benzoin ethers such as benzyl, benzoin, benzoin methyl ether and benzoin butyl ether, ketals such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and 2-isopropyl Thioxanthones such as thioxanthone, anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6-tris-
S-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. These photopolymerization initiators (D) can be used alone or in combination of two or more.

In the present invention, the compound (E) having a carbodiimide group is used. The compound (E) having a carbodiimide group is used as a thermosetting component in the present invention, and the heat resistance, solvent resistance, acid resistance,
Improve various properties such as adhesion. The compound (E) having a carbodiimide group can be easily obtained from the market. Specifically, for example, Carbodilite V-03 (a polycarbodiimide-based resin having a carbodiimide group represented by "-N = C = N-" in the molecule) manufactured by Nisshinbo Co., Ltd. Resin content 40%, solvent toluene), carbodilite V-06 (resin content 40%,
Water 60%), carbodilite 10M-SP (white powder,
Average particle diameter of 10 μm, melting temperature of about 125 ° C., carbodilite 9010 (white powder, average particle diameter of 10 μm, melting temperature of about 140 ° C.), and the like.
0 μm is a compound (E) which is hardly soluble in the components (A) and (B) (for example, carbodilite 10M-SP, carbodilite 9010, etc.).

(A) to Constituting the Resin Composition of the Present Invention
As the use ratio of the component (E), the amount of the component (A) is preferably from 10 to 80% by weight in the composition, and particularly preferably from 20 to 70% by weight.
% By weight is preferred. The amount of the component (B) is 5 to 5% in the composition.
It is preferably 60% by weight, particularly preferably 10 to 50% by weight. The amount of the component (C) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight in the composition. The amount of the component (D) is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight in the composition. The amount of the component (E) in the composition is preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.

The composition of the present invention may further contain, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica dioxide, and the like for the purpose of further improving properties such as adhesion and hardness. Shaped silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide,
Inorganic fillers such as aluminum hydroxide and mica powder can be used. The amount used is from 0 to 60% by weight in the composition of the present invention.
More preferably, it is particularly preferably 5 to 40% by weight.

Further, if necessary, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; and a thickening agent such as hydroquinone and hydroquinone monomethyl ether. Agents, silicone-based, fluorine-based and polymer-based antifoaming agents and / or leveling agents, imidazole-based adhesion-imparting agents, thiazole-based adhesion-imparting agents, triazole-based adhesion-imparting agents and silane coupling agents, etc. Various additives such as a property imparting agent can be used.

The composition of the present invention can be obtained by preferably blending the above-mentioned components in the above-mentioned proportions and uniformly mixing them with a roll mill or the like.

The cured product of the resin composition of the present invention is, for example,
It can be obtained as follows. That is, 1 on the laminate
Coating with a film thickness of 0 to 160 μm,
After the drying, the negative film is brought into direct contact with the coating film, and then irradiated with ultraviolet rays, and the unexposed portions are dissolved and removed with a dilute alkaline aqueous solution (eg, a 1 to 2% Na ₂ CO ₃ aqueous solution) or water (development) ). After washing with water and drying, if necessary, further irradiate with ultraviolet rays, and then heat and cure at 150 ° C. for 30 to 60 minutes to obtain a cured product. The cured product of the resin composition of the present invention is used for electric / electronic parts such as printed wiring boards having through holes as permanent resists.

[0023]

EXAMPLES The present invention will be further described below with reference to examples.

Examples 1 and 2 Comparative Examples 1 and 2 In accordance with the composition shown in Table 1, the numerical values are parts by weight.
The respective components were mixed, dispersed and kneaded to prepare a resin composition for permanent resist. 30 μm of the obtained composition was placed on a laminate.
And dried at 80 ° C. for 60 minutes. Then, a negative mask was brought into contact with the resist, and the resist was irradiated with ultraviolet rays (about 30 mJ / cm ² ) using an ultra-high pressure mercury lamp. The unexposed portion was 2.0 kg for 60 seconds with water (Example 1 and Comparative Example 1) or a 1% aqueous solution of Na ₂ CO ₃ (Example 2 and Comparative Example 2).
/ Cm ^{2 at} a spray pressure. After washing and drying, 150
Heat curing was performed at 30 ° C. for 30 minutes. This was immersed in an electroless copper plating solution at 70 ° C. for 10 hours to form an electroless copper plating film of about 20 μm, thereby producing an additive-processed multilayer printed wiring board. Table 1 shows the results of evaluating the resist characteristics in the process of obtaining the additive multilayer printed wiring board in this manner.

Evaluation method (Developability) ・ ・ ・: At the time of development, the ink was completely removed, and complete development was possible. C: At the time of development, a small amount of residue remains and there is a part that is not developed. (Solvent resistance) The cured resist film was immersed in acetone for 20 minutes, and the state was visually observed. ○ ・ ・ ・ ・ No change at all. ×: blisters and peeling occurred. (Plating resistance) ○ ・ ・ ・ ・ No change is observed in the electroless copper plating process. C: Discoloration, blistering, and peeling occurred in the electroless copper plating step.

(Solder Heat Resistance) According to the test method of JIS C 6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds three or two times, and the change in appearance was evaluated. (Post-flux resistance) Dipping was performed twice for 10 seconds, and the change in appearance was evaluated. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling and solder dipping of the cured film Note) Post flux used (rosin type): JIS
Use flux according to C 6481.

(Flux resistance for leveler) Dipping for 10 seconds was performed three times, and after immersing in boiling water for 10 minutes, the change in appearance was evaluated. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling and solder dipping of the cured film Note) Flux for leveler used: manufactured by MEC Corporation ,
W-121

(Shelf Life of Resist Composition) The state of the resist composition after being left at 40 ° C. for one month was observed. ○ ・ ・ ・ ・ No change in viscosity and other appearances △ ・ ・ ・ ・ Slightly increased viscosity × ・ ・ ・ ・ Gelled

[0029]

Table 1 Example Comparative Example 12 12 SMA-17352 * 1 75 25 75 25 Jyoncryl J-67 * 2 50 50 KAYARAD DPHA * 3 25 25 25 25 Irgacure 907 * 4 3.0 3.0 3.0 Kayacure DETX-S * 5 0.5 0.5 0.5 0.5 Carbitol acetate 25 25 25 25 IMCIL A-108 * 6 35 35 35 35 Aerosil 380 * 7 3 3 3 3 Modaflow * 8 1.0 1.0 1.0 1.0 Phthalocyanine Green 1.8 1.8 1.8 1.8 1.8 Carbodilite 10M-SP * 9 10 Carbodilite 9010 * 10 10 EOCN-104S * 11 10 Dicyandiamide 0. 5 ───────────────────────────────シ Shell life of resist composition ○ ○ ○ × Developability ○ ○ ○ ○ Plating solution ○ ○ × × Solvent resistance ○ ○ ○ × Solder heat resistance Post flux resistance ○ ○ × △ Leveler flux resistance ○ ○ △ ○

Note) * 1: SMA-17352: manufactured by Sartomer Co., Ltd., a reaction product of a copolymer of styrene and maleic anhydride with an alcohol, average molecular weight 1700, melting point 160-17.
0 ° C, acid value (mgKOH / g) 270. * 2: Joncryl J-67: manufactured by Johnson Co., Ltd., copolymer of styrene and acrylic acid, weight average molecular weight 100
00, acid value (mgKOH / g) 195, softening point 143 ° C * 3: KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Mixture of dipentaerythritol penta and hexaacrylate. * 4: Irgacure 907: Ciba-Geigy Corporation
, Photopolymerization initiator. * 5: Kayacure DETX-S: manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator * 6: IMCIL A-108: silica dioxide, manufactured by Tatsumori Corporation.

* 7: Aerosil 380: Anhydrosilica manufactured by Nippon Aerosil Co., Ltd. * 8: Modaflow: Defoamer manufactured by Monsanto. * 9: Carbodilite 10M-SP: manufactured by Nisshinbo Co., Ltd.
Thermosetting polycarbodiimide resin, white powder, average particle size 10 μm, melting temperature about 125 ° C. * 10: Carbodilite 9010: Thermosetting polycarbodiimide resin, manufactured by Nisshinbo Co., Ltd., white powder, average particle size 1
0 μm, melting temperature about 140 ° C. * 11: EOCN-104S: Nippon Kayaku Co., Ltd. cresol novolak epoxy resin.

From the evaluation results shown in Table 1, the resin composition of the present invention has a long shelf life and good developability, and the cured product is excellent in solvent resistance, plating solution, solder heat resistance and the like. I have.

[0033]

The resin composition of the present invention is a one-part type, has a long shelf life, is easy to develop, and its cured product is isopropyl alcohol, trichloroethylene, methylene chloride,
Excellent resistance to solvents such as acetone, excellent plating solution resistance to electroless plating performed for a long time under high temperature and high alkalinity conditions, and heat resistance to withstand temperatures around 260 ° C in the soldering process. Therefore, it is particularly suitable for a permanent resist provided when manufacturing a printed wiring board.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/06 C08L 101/06 G03F 7/004 501 G03F 7/004 501 7/027 502 7/027 502 7/028 7/028 H05K 3/18 H05K 3/18 D 3/28 3/28 D // C08F 2/50 C08F 2/50 20/10 20/10

Claims (5)

[Claims] 1. A polymer having a hydroxyl group and / or a carboxyl group-containing polymer (A), a (meth) acrylate compound (B), a diluent (C), a photopolymerization initiator (D) and a carbodiimide group. A resin composition comprising the compound (E). 2. The resin composition according to claim 1, wherein the compound (E) having a carbodiimide group is a powder. 3. The resin composition according to claim 1, which is used for a permanent resist. 4. A cured product of the resin composition according to claim 1 or 2. 5. The cured product according to claim 4, wherein the cured product is a permanent resist.