JPH11171973A - Resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that can be readily developed with high resolution, shows excellent resistance to the electroless copper plating solution through the fully-additive process and to solvents and is useful as a permanent resist for the printed circuit boards by using a specific epoxy resin and a photo-cationic polymerization initiator. SOLUTION: This resin composition contains (A) an epoxy resin of formula I or II (n and m are each an average value of >0) and (B) a photo-cationic polymerization initiator as 7-[di(p-toluyl)sulfonyl]-2-isopropylthioxanethone hexafluoro-phosphate. In a preferred embodiment, (C) an organoaluminum compound as aluminum triacetylacetonate is additionally admixed. In the proportions of individual components, the component A is 85-98 wt.%, the component B is 1.0-7.5 wt.% and the component C is 1.0-7.5 wt.% based on 100 wt.% of the total amount of the components A, B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition, particularly to a resin composition useful as a permanent resist for a printed wiring board and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, printed wiring boards have been manufactured by using a copper-clad laminate and by a subtractive method of removing unnecessary copper foil portions by etching by a circuit. This subtractive method uses fine patterns and high-density wiring. Difficult to form plate, small diameter through hole,
At present, via holes have drawbacks such as the fact that they cannot be uniformly formed by electroplating, and are not able to cope with higher densities of electronic devices.

[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.

In general, in an additive method for producing a base plate for consumer use, a plating resist pattern is transferred by a screen printing method. However, in order to produce a printed wiring board having high-density wiring, the plating resist pattern must be transferred. It is necessary to form by photolithography, that is, to adopt a photo-additive method using a photoresist. A photoresist suitable for the photo-additive method is required to have the following characteristics in addition to the inherent characteristics of the photoresist such as sensitivity, degree of development and developability. Since the chemicals used in the development process are limited to 1,1,1-trichloroethane-based organic solvents or alkaline aqueous solutions, they can be developed with either, and electroless treatment performed for a long time under high temperature and high alkaline conditions Withstands plating, has excellent solder resist properties as a permanent resist after plating, and has 26
Having heat resistance to withstand temperatures around 0 ° C., having solvent resistance to organic solvents for cleaning flux used at the time of soldering, and furthermore, does not lower the thermal reliability of the entire substrate even when laminated. And so on. At present, photoresists that can be used in the additive method are commercially available, but their performance is not yet satisfactory.

[0005]

Accordingly, it is an object of the present invention to form a resist having high pattern accuracy by a photographic method using an organic solvent (for example, γ-butyrolactone, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, etc.). ), Heat resistance that can be developed by using a mixed solution of these organic solvents and water, etc., sufficiently withstands the electroless copper plating solution of the full additive method, or withstands the temperature of about 260 ° C. in the soldering step, and It is an object of the present invention to provide a resin composition having solvent resistance to an organic solvent for cleaning flux used at the time of soldering and suitable for a permanent resist used without removing even a final product, and a cured product thereof.

[0006]

Means for Solving the Problems In order to achieve the above object, as a result of intensive studies, it has been found that a resin composition having a specific composition solves those problems, and the present invention has been completed. Reached. That is, the present invention relates to (1) Formula (I)

[0007]

Embedded image

(Where n is 0 or a number greater than or equal to 0 and is an average value).
I)

[0009]

Embedded image

(Wherein m is 0 or a number greater than or equal to 0 and is an average value), characterized in that it contains an epoxy resin (A ') represented by the following formula: and a cationic photopolymerization initiator (B). (2) a resin composition according to (1) containing an organoaluminum compound (C), (3) a resin composition according to (1) or (2) for permanent resist, (4) A cured product of the resin composition according to any one of (1) to (3),
(5) The cured product according to (4), which is a permanent resist, (6)
(4) A printed wiring board having the cured product layer according to (5).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention uses the epoxy resin (A) represented by the general formula (I) or the epoxy resin (A ') represented by the general formula (II). I do.

The epoxy resin (A) is disclosed in JP-A-9-1698.
For example, the epoxy resin described in JP-A-34-34 can be obtained by reacting epichlorohydrin with a resin obtained by reacting di (methoxymethylphenyl) with phenol. This epoxy resin (A) can be easily obtained from the market, for example, Nippon Kayaku Co., Ltd. NC-3000P (epoxy equivalent 270-300, softening point 60-75 ° C) and the like. Note that n in the above formula (I) is back calculated from the epoxy equivalent of the epoxy resin (A), and is an average value of 0 or a number of 0 or more, preferably a number of 0.5 to 10.

The epoxy resin (A ') is disclosed in JP-A-8-30.
The epoxy resin described in Japanese Patent No. 1973 can be obtained, for example, by reacting epichlorohydrin with a resin obtained by reacting dicyclopentadiene with phenol. This epoxy resin (A ') can be easily obtained from the market. For example, Nippon Kayaku Co., Ltd.'s XD-1000 (epoxy equivalent 240-260, softening point 50-80 ° C), Dainippon Ink ( EXA-72
00 (epoxy equivalent: 257, softening point: 63 ° C.) and the like. Here, m in the general formula (II) is back calculated from the epoxy equivalent of the epoxy resin (A ′), and as an average value,
It is 0 or a number of 0 or more, preferably a number of 0.5 to 10.

Examples of the cationic photopolymerization initiator (B) include an aromatic iodonium complex salt and an aromatic sulfonium complex salt. Examples of the aromatic iodonium complex salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

Examples of the aromatic sulfonium complex salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, and 4,4'-bis [diphenylsulfonio] diphenylsulfide. -Bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide-bishexafluoroantimonate, 4,4'-
Bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide-bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-
Isopropylthioxanthone hexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropyltetrakis (pentafluorophenyl) borate, Phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-ter-butylphenylcarbonyl-4'-diphenylsulfonio- Diphenyl sulfide-hexafluorophosphate, 4-ter-butylphenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluoro Antimonate, 4-ter-
Butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-tetrakis (pentafluorophenyl) borate and the like can be mentioned. These components (B) may be used alone or in combination of two or more.

Among these components (B), 7- [di (P-tolyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate, which is an initiator having an absorption wavelength (nm) up to a range exceeding 400 nm, is particularly preferred. Thioxanthone sulfoniums such as, 7- [di (P-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (P-tolyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate Salts are preferably used.

In the present invention, it is preferable to use an organoaluminum compound (C). Examples of the organoaluminum compound (C) include alkoxyaluminums such as trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, isopropoxydiethoxyaluminum and trisbutoxyaluminum, and phenoxyaluminums such as trisphenoxyaluminum and trisparamethylphenoxyaluminum. , Aluminum trisacetoxy, aluminum tristearate, aluminum trisbutyrate, aluminum trispropionate, aluminum trisacetylacetonato, aluminum tristrifluoroacetylacenate, aluminum trisethylacetoacetate,
Diacetylacetonatodipivaloylmethanatoaluminum; diisopropoxy (ethylacetoacetato) aluminum; These components (C) alone,
Alternatively, two or more kinds can be used in combination, and they are used when it is necessary to reduce the adverse effects of the ions derived from the cationic photopolymerization initiator.

The use ratio of each component of the resin composition of the present invention is appropriate, but the components (A) to (C) or (A ') to
When the total amount of (C) is 100 parts by weight, the content of component (A) or (A ') is preferably 80 to 99% by weight, particularly preferably 85 to 98% by weight. The component (B) contains 0.1.
It is preferably from 5 to 10% by weight, particularly preferably from 1.0 to 10% by weight.
7.5% by weight. The component (C) is preferably from 0 to 10% by weight, particularly preferably from 1.0 to 7.5% by weight.

In the resin composition of the present invention, a diluent is preferably used, if necessary, for mixing and dissolving the above-mentioned components. Examples of such a diluent include ethyl methyl ketone, ketones such as cyclohexanone, toluene, xylene, aromatic hydrocarbons such as tetramethylbenzene, dipropylene glycol dimethyl ether,
Glycol ethers such as dipropylene glycol diethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent Organic solvents such as petroleum solvents such as naphtha and the like can be mentioned. The ratio of the diluent used in the resin composition of the present invention,
Preferably it is 0 to 70% by weight.

In the present invention, (A)
Alternatively, an epoxy resin other than the component (A ') or a (meth) acrylate compound may be used. Examples of the epoxy resin include bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and trisphenol methane type epoxy resin. Examples of the (meth) acrylate compound include pentaerythritol tetra ( (Meth) acrylate monomers such as (meth) acrylate, dipentaerythritol penta and hexa (meth) acrylate, epoxy (meth) acrylate, urethane (meth)
(Meth) acrylate oligomers such as acrylate and polyester poly (meth) acrylate; and the like.
The use amount thereof is preferably about 0 to 50 parts by weight based on 100 parts by weight of the component (A) or (A ').

In the present invention, inorganic fillers such as barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica powder are used. It can be used, and its compounding ratio is 0 to 60% by weight in the composition.

Further, in the present invention, various additives such as a cross-linking agent, a thermoplastic resin, a coloring agent, a thickener, and an adhesion-imparting agent can be used, if necessary. Examples of the crosslinking agent include methoxylated melamine, butoxylated melamine, and the like, and examples of the thermoplastic resin include polyether sulfone, polystyrene, and polycarbonate.
Examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of the thickening agent include asbestos, olben, benton, montmorillonite, and the like. Examples of the defoaming agent include silicone-based, fluorine-based and polymer-based defoaming agents, and examples of the adhesion-imparting agent include various leveling agents and silane coupling agents. When these additives and the like are used, the amount of the additives used in the composition of the present invention is, for example, about 0.5 to 30% by weight as a rough guide, but can be appropriately increased or decreased according to the purpose of use.

The resin composition of the present invention comprises the component (A) or (A '), the component (B), or the component (C) if necessary.
Diluents, inorganic fillers and other additives are preferably blended in the proportions described above and uniformly mixed and dissolved with a roll mill or the like.
It can be prepared by dispersion or the like.

The resin composition of the present invention is used for a permanent resist, and is preferably used in a liquid form. In order to use the resin composition of the present invention, for example, 20 to 60
It is applied with a thickness of μm, heat-treated at 60 to 100 ° C. for about 10 to 60 minutes to remove the solvent, and a mask having a predetermined pattern is placed thereon and irradiated with ultraviolet rays. After that, the unexposed portion is developed with a developing solution to form a pattern, if necessary, irradiated with ultraviolet rays, and then heat-treated at 100 to 200 ° C., and a permanent protective film satisfying various characteristics may be obtained. Is obtained. As the developer, for example, an organic solvent such as γ-butyrolactone, triethylene glycol dimethyl ether, and methyl cellosolve, or a mixed solution of the organic solvent and water can be used.

[0025] The resin composition of the present invention comprises a base film (release film), a roll coater, a doctor bar,
After applying the composition using a wire bar method, a dipping method, a spin coating method, a gravure method, a doctor blade method, or the like, drying in a drying furnace set at 60 to 100 ° C. to remove a predetermined amount of solvent. And, if necessary, a dry film can be obtained by attaching a release film or the like. At this time, the thickness of the resist on the base film is adjusted to 15 to 150 μm. As the base film, for example, a film such as polyethylene terephthalate or polypropylene is preferably used. In order to use this dry film, for example, the release film may be peeled off, transferred to a substrate, and exposed, developed, and heated in the same manner as described above.

The cured product of the resin composition of the present invention obtained by the above method is used for an electric / electronic component such as a printed wiring board having a through hole as a permanent resist. The thickness of the cured layer of the printed wiring board having the cured layer of the resin composition of the present invention is preferably about 20 to 60 μm.

[0027]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Examples 1 to 4 The components were mixed, dispersed and kneaded in accordance with the composition shown in Table 1 (the numerical values are parts by weight) to obtain the resin composition of the present invention. The obtained resin composition was applied on a laminate at a thickness of 30 μm, dried at 80 ° C. for 60 minutes, brought into contact with a negative mask, and irradiated with ultraviolet rays using an ultra-high pressure mercury lamp. Next, after a heat treatment at 80 ° C. for 5 minutes, the unexposed portion was treated with triethylene glycol dimethyl ether for 120 seconds.
Development was performed with a spray pressure of 0 kg / cm ² . After washing and drying,
The entire surface was irradiated with ultraviolet rays, and then heat-treated at 150 ° C. for 30 minutes. This is added to the electroless plating solution at 70 ° C for 10
After immersion for about 20 μm, an electroless copper plating film having a thickness of about 20 μm was formed, and an additive method multilayer printed wiring board was produced. In this way, the resist characteristics in the process of obtaining the additive multilayer printed wiring board were evaluated. Table 1 shows the results.

Evaluation method (Developability) ・ ・ ・: At the time of development, ink was completely removed, and complete development was possible. ×: At the time of development, a little 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. Δ: Discoloration is slightly 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. In the table, the state of change in the appearance when immersion for 10 seconds was performed three times is described. ○ ・ ・ ・ ・ No change in appearance. Δ: Discoloration of the cured film is observed. ×: Floating, peeling, and solder dipping of the cured film. (Note) Post flux used (rosin type): JIS
C 6481. Uses flux.

(Flux resistance for leveler) The immersion was performed three times for 10 seconds, and after immersion 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 (Electrical characteristics)
Under the condition of 90% RH, DC 100 V is applied, and 500
Measure the insulation resistance after time.

[0031]

Table 1 Table 1 Formulation composition and properties test Formulation composition Example 1 2 3 4 NC-3000P * 1 75 50 XD-1000 * 2 75 75 EOCN-102S * 3 20 Carbitol acetate 25 25 25 25 B-1 * 4 1.5 1.5 B-2 * 5 0.5 2 0.5 2 Triacetylacetonatoaluminum 1 11 1 Aerosil 380 * 6 3 3 3 3 ──────────── Developability ○ ○ ○ ○ Dissolution resistance ○ ○ ○ ○ Plating solution resistance ○ ○ ○ ○ Soldering heat resistance ○ ○ ○ ○ Insulation resistance (Ω) 100 × 10 ¹¹ 80 × 10 ¹¹ 200 × 10 ¹¹ 9 × 10 ¹¹

Note) * 1 NC-3000P: manufactured by Nippon Kayaku Co., Ltd., epoxy resin represented by the general formula (I), epoxy equivalent 286, softening point 67 ° C., average of n is 2.24
It is. * 2 XD-1000: manufactured by Nippon Kayaku Co., Ltd., epoxy resin represented by the general formula (II), epoxy equivalent 25
4. The softening point is 73.3 ° C, and the average of m is 2.71. * 3 EOCN-102S: Nippon Kayaku Co., Ltd., cresol novolak type epoxy resin, epoxy equivalent 21
0, softening point 70 ° C. * 4 B-1: 4,4'-bis [diphenylsulfonio] phenylsulfide-bishexafluorophosphate. * 5 B-2: 7- [di (P-toluyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate. * 6 Aerosil 380: manufactured by Nippon Aerosil Co., Ltd.
Anhydrous silica.

As is clear from the evaluation results in Table 1, the resin composition of the present invention is excellent in developability, and the cured product is excellent in solvent resistance, plating solution resistance, solder heat resistance, and electrical properties. .

[0032]

The resin composition of the present invention and the cured product thereof are:
Despite high resolution and easy development, 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 that can withstand temperatures around 260 ° C in the soldering process. Particularly suitable as a resist for the manufacture of printed wiring boards.

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

Claims (6)

[Claims] 1. A compound of the formula (I) (Wherein, n is 0 or a number greater than or equal to 0, and is an average value). (Wherein m is 0 or a number greater than or equal to 0 and is an average value) A resin composition comprising an epoxy resin (A ′) represented by the formula (I) and a cationic photopolymerization initiator (B): . 2. The resin composition according to claim 1, which contains an organoaluminum compound (C). 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 any one of claims 1 to 3. 5. The cured product according to claim 4, which is a permanent resist. 6. A printed wiring board having a cured product layer according to claim 4.