JPH05289337A - Resist resin composition for chemical plating - Google Patents

Abstract

PURPOSE:To obtain a resist resin composition for chemical plating capable of forming a thick film excellent in rapid hardenability and resolution. CONSTITUTION:The resist resin composition for chemical plating mainly contains a component (A) which is an epoxy resin of >=150 poise in viscosity at 25 deg.C and having at least two glycydil ether group, bonded directly to aromatic ring, a component (B) which is an oxilane ring-containing compound of >=140 deg.C in b.p. and <=500 in molecular weight, a component (C) which is a heat latent cation polymerization initiator and a component (D) which is a sensitizer. Then, the resin composition excellent in rapid hardenability and resolution, capable of forming a resist pattern for chemical plating of thick film by a screen printing method and capable of forming reasonably a circuit pattern thick in the thickness of a conductor by the additive method is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist resin composition for chemical plating containing an epoxy resin as a main curing component, more specifically, a thick film having improved stability of viscosity with time, curing speed and printability. A cationic ink-based resist ink composition for chemical plating that can be formed. The present invention is a full-additive method including a step of forming a circuit by a chemical plating method, a part-additive method, and further a build-up method of stacking to form multiple layers (hereinafter, simply referred to as "additive method"). It is preferably used as a resist ink for chemical plating in the production of a printed wiring board, especially for thick film resists.

[0002]

2. Description of the Related Art As a method of manufacturing a printed wiring board, there is an additive method of forming a conductive circuit and through-hole conductive plating by chemical plating. In the additive method, a resist for chemical plating is used, and as the resist resin composition for chemical plating, a thermosetting epoxy resin composition (JP-A-54-013574, JP-A-58-009398) is used. Japanese Patent Laid-Open No. 59-117196, etc.) are disclosed. Further, a photocurable epoxy resin composition is disclosed in JP-A-62-
It is disclosed in Japanese Patent No. 273221 and Japanese Patent Laid-Open No. 62-273226.

[0003]

In the additive method, it is required to form a resist that can withstand severe chemical plating conditions on the substrate except the circuit forming portion. Chemical copper plating is generally adopted for circuit formation. The chemical copper plating solution used for forming this circuit has a basic composition consisting of a copper salt, a complexing agent, a reducing agent and a pH adjusting agent in order to improve the properties such as elongation and tensile strength of the deposited copper plating film. It contains a special additive (see Japanese Patent Publication No. 56-027594). Circuit formation temperature is 65 ℃
The above is performed under extremely severe conditions in which the substrate is immersed in the chemical copper plating solution having a pH value of 11 or more at 20 ° C. for 10 hours or more. Therefore, the resist for chemical plating not only withstands the above-mentioned chemical copper plating conditions, but also prevents the plating solution from being contaminated by the elution of resist constituents that cause abnormal deposition of copper and decrease in the elongation of the plating film. Liquidity is required. Further, since this resist is also used as a permanent resist, various properties required for the permanent resist such as electric insulation, solvent resistance, solder heat resistance, and moisture resistance are also required. The above-mentioned prior art has been proposed to satisfy the above characteristics, and good results in which various characteristics are well balanced have been obtained by using an epoxy resin as a basis.

However, the copper circuit may require a thickness of 70 μm or more, and in this case, the thick film of the plating resist is required to have a thickness of about 70 μm. In such a case, the film thickness cannot be formed by screen printing using the conventional resist ink, and the resist layer is formed by repeatedly applying the photoresist by repeating the photographic image forming process many times. However, low level yield and difficulty in mass production have been problems.

A resist ink based on a thermosetting epoxy resin is used in order to minimize the change in viscosity during printing.
The existing fast-curing hardener cannot be used, and for example, 12
It takes 30 minutes or more at high temperature at 0 ℃ to 180 ℃, and the printed ink flows during heat curing or penetrates into the base material, and the circuit interval becomes narrow and the resolution is likely to decrease. For this reason, the thermosetting resist ink that has been put into practical use has a basic composition that is a liquid composition obtained by diluting a solid or high-viscosity epoxy resin with a volatile organic solvent, and rapidly increases the organic content during heat curing. The solvent is volatilized to increase the viscosity and reduce the ink flow. Therefore, there is a problem that the work environment is adversely affected.

On the other hand, the UV-curable epoxy-based resist is industrially useful because the curing time is extremely short, the flow of ink is small, and the resolution is good. Although light transmission to the bottom of the applied resist layer is required, pigments and fillers are added to improve discrimination and printing characteristics, so thick film curing has a limit in terms of reliability. It was In order to improve the thick film curability, it is preferable to use a thermosetting curing agent in combination, but nitrogen such as amine, amide, imidazole and BF ₃ amine complex which are conventionally used curing agents for epoxy resins are used. Compounds having atoms are all highly basic compounds, and a good cured product cannot be obtained because of a strong inhibitory effect on cationic polymerization, and in a carboxylic acid or acid anhydride system, viscosity changes with time. No satisfactory results were obtained such as a problem that printing stability was poor because of too large a size, a curing temperature was too high for a phenol compound, a curing was too slow, or an odor of a mercapto-based compound. As described above, with conventional resist inks, the thermosetting type has a decrease in resolution due to flow and penetration during curing, or volume reduction due to volatilization of the contained organic solvent and foaming / pinholes. Due to the limit of light transmission of the mold, it was practically difficult to form a pattern having a good resolution with a film thickness of 40 μm or more.

The present invention has been made in view of the above-mentioned circumstances, and has fast plating property, little change in viscosity with time, excellent resolution, no abnormal deposition of copper between circuits, and resistance to plating solution. An object of the present invention is to provide an excellent thick film curable resist resin composition for chemical plating.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have used a curing agent system in which a thermal latent cationic polymerization initiator and a sensitizer are used in combination and A resist resin composition for chemical plating containing an epoxy compound directly bonded to an aromatic ring as a main curing component and further containing a low-molecular weight oxirane ring-containing compound has a rapid curing property of light curing and a thick film curing property of heat curing. The present invention has been completed by finding that a thick film having a thickness of 70 μm or more can be formed, excellent resolution, excellent plating solution resistance and excellent electric insulation.

The present invention is a resist resin composition for chemical plating, which contains the following components A, B, C and D. Component A: 1 whose viscosity at 25 ° C. is 150 poise or more
Epoxy resin having at least two glycidyl ether groups in the molecule and having the glycidyl ether groups directly bonded to an aromatic ring Component B: oxirane ring-containing compound having a boiling point of 140 ° C. or higher and a molecular weight of 500 or less C: Sulfonium salt-based thermal latent cationic polymerization initiator Component D: Sensitizer

In the present invention, the component A epoxy resin is the main curing component, and is, for example, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin or the like at 25 ° C.
Is a polyfunctional epoxy resin having a glycidyl ether group directly bonded to two or more aromatic rings in one molecule having a viscosity of 150 poise or more. Specifically, the following commercial products can be exemplified.

(1) Bisphenol A type epoxy resin (a) Yuka Shell Epoxy Co., Ltd. trade name: Epicoat 830, 834, 836, 8
40, same 1001, same 1002, same 1004, same 100
7, the same 1009, the same 1010 (b) Ciba-Geigy product name: Araldide YG280, the same 6010, the same 60
20, same 6030, same 6040, same 6060, same 607
1, the same 6075, the same 6084, the same 6097, the same 706
5, 7071, 7072, 7097 (c) Dow Chemical Co. product name: DER337, 557, 660, 66
1, 662, 664, 668, 669

(D) Dainippon Ink and Chemicals, Inc. product name: Epicron 860, 900, 1050, 3050, 4050, 7050 (e) Toto Kasei Co., Ltd. product name: Epotote YD-128S, YD-134,
Same YD-011, same YD-012, same YD-014, same YD-017, same YD-019 same YD-020, same YD
-7011, YD-7014, YD-7017, YD-7019, YD-7020 (f) Union Carbide Co. product name: Bakelite EKR-2002, EKR-2
003, ERR-2010, EKRB-2014,
EKRA-2018, EKRA-2053, ER
LA-2600

(G) Celanese brand name: Epilitz 515B, 520-C, 522
-C, same 530-C, same 540-C, same 550, same 56
0 (h) Richard Chemical Co. product name: Epotaf 37-141, 37-144, 3
7-300, 37-301, 37-302, 37
-304, 37-307, 37-309 (i) Mitsui Petrochemical Epoxy Co., Ltd. trade name: Epomic R-144, R-301, R-
302, R-304, R-307, R-309

(2) Novolac type epoxy resin (a) Yuka Shell Epoxy Co., Ltd. trade name: Epicoat 154 (b) Ciba Geigy trade name: EPN-1138, ECN-1235, 12
73, 1280, 1299, XU-158 (c) Dow Chemical Co. product name: DEN-438, 439

(D) Manufactured by Dainippon Ink and Chemicals, Inc. Trade name: Epicron N-673, N-680, N-
695, N-740 (e) Toto Kasei Co., Ltd. product name: Epotote YDCN-701, YDCN-7
02, YDCN-703, YDCN-704, Y
DPN-601, YDPN-602, and YDPN-6
38 (f) Union Carbide product name: EPR-0100, ERLB-0447, 0
448

(G) Celanese's product name: Epilitz 5155, 5156 (h) Richard: Chemical's product name: Epotaf 37-170 (i) Nippon Kayaku Co., Ltd. product name: EOCN-102, Same 103, same 104

In addition to the above examples, for example, an epoxy having a resin obtained by condensing resorcinol, bisphenol F, phlorogricinol and other phenolic compounds as a skeleton and having two or more glycidyl ether groups in the molecule. Resin with a viscosity of 150 at 25 ° C
More than poise can also be used. These epoxy resins may be used alone or in a mixture of two or more. In particular, the polyfunctional novolac type epoxy resin has a larger cross-linking density and better internal curability than the bisphenol A type epoxy resin, so that not only a thick film can be formed but also the curing speed is high. It is preferably used because a tough film is obtained.

The oxirane ring-containing compound of the component B is used as a reactive diluent for the purpose of adjusting the viscosity of the composition and has the oxirane ring in the molecule having a boiling point of 140 ° C. or higher and a molecular weight of 500 or lower. It is a compound that is compatible and reactive with the epoxy resin. For example, epoxy monomer and high boiling point, low molecular weight bisphenol A
Type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, alicyclic type epoxy resin and the like. These are used alone or in combination of two or more. It

In particular, an epoxy monomer having excellent compatibility and reactivity with the epoxy resin of the component A and having a low viscosity,
For example, butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, glyceryl glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 2-methyloctyl glycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether and the like are preferably used. More preferably, glycidyl ether having an aromatic ring in the molecule is used.

The sulfonium salt-based thermal latent cationic polymerization initiator of the component C is stable at the printing temperature and does not substantially generate active species. Further, cationic polymerization is performed by rapidly generating cations at a certain temperature or higher. These are various sulfonium salts that start the reaction and cure the ink-like resin composition. That is, the viscosity of the ink-like resin composition hardly changes at the printing temperature, stable printing is possible, and the subsequent heat treatment can cure the ink in a much shorter time than the conventional thermal polymerization initiator. Viscosity stability at the printing temperature is required for several hours or more, and one having a stability for several months or more at room temperature can be used as a one-pack composition, which is preferable.

Examples of the sulfonium salt-based thermal latent cationic polymerization initiator include those represented by the following general formulas [I] to [VI].

Sulfonium salt compound [I]

[Chemical 1] (In the formula, R ₁ and R ₂ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group,
Represents a vinyl group, a carbamoyl group or an alkanoyl group,
R ₃ represents a hydrogen atom, an alkyl group or an optionally substituted phenyl group, and R ₄ and R ₅ are the same or different linear or branched alkyl groups, an optionally substituted alkyl group or a benzyl group. And R ₄ and R ₅ may be bonded together, and X is SbF ₆ , AsF ₆ , PF ₆ or B.
Represents F ₄ . )

Sulfonium salt compound [II]

[Chemical 2] (In the formula, R ₆ represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, a benzyl group, a phenyl group, a benzylcarbonyl group or a benzoyl group, and R ₇ and R ₈ represent a hydrogen atom, a halogen atom or an alkyl group, respectively. R ₉ represents an optionally substituted alkyl group containing an unsaturated bond, an optionally substituted benzyl group or a phenacyl group,
R ₁₀ represents an alkyl group or an optionally substituted benzyl group, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . )

Sulfonium salt compound [III]

[Chemical 3] (In the formula, R ₁₁ represents a hydrogen atom, an alkyl group or a cyano group, R ₁₂ represents an alkyl group, an alkoxycarbonyl group or an optionally substituted phenyl group, and R ₁₃ and R ₁₄ represent
The same or different linear or branched alkyl groups, optionally substituted alkyl groups or benzyl groups, R ₁₃ and R
₁₄ may be combined together, and X is SbF ₆ , As
It represents F ₆ , PF ₆ or BF ₄ . )

Sulfonium salt compound [IV]

[Chemical 4] (In the formula, R ₁₅ and R ₁₆ each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ₁₇ and R _16
18 is the same or different linear or branched alkyl group, an optionally substituted alkyl group or a benzyl group,
R ₁₇ and R ₁₈ may be combined together, and X is SbF.
₆ , AsF ₆ , PF ₆ or BF ₄ . )

Sulfonium salt compound [V]

[Chemical 5] (In the formula, R ₁₉ represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, a benzyl group, a phenyl group, a benzylcarbonyl group or a benzoyl group, and R ₂₀ and R ₂₁ each represent a hydrogen atom, a halogen atom or an alkyl group. , R ₂₂ , R
₂₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, R ₂₄ represents an alkyl group or an optionally substituted benzyl group, and X represents SbF ₆ , AsF.
₆ represents PF ₆ or BF ₄ . )

Sulfonium salt compound [VI]

[Chemical 6] (In the formula, R ₂₅ represents a hydrogen atom or an alkyl group which may be substituted, and R ₂₆ and R ₂₇ are the same or different linear or branched alkyl groups, an alkyl group which may be substituted or benzyl. R ₂₆ and R ₂₇ may be bonded together, and X is SbF ₆ , AsF ₆ , PF ₆ or BF _4.
Represents. )

The sensitizer of the component D of the present invention is a compound which easily releases hydrogen radicals or a compound which traps radicals, and examples thereof include the following. That is, methoxyphenol, ethoxyphenol, benzyloxyphenol, t-butylcatechol, hydroquinone, 3,5-di-t-butylhydroxytoluene, 4,
Phenolic compounds such as 4'-thio-bis- (6-t-butyl-3-methylphenol) and 2,2'-methylene-bis (4-methyl-6-t-butylphenol); phenothiazine,
Amino compounds such as diphenylamine, N, N′-diphenyl-1,4-phenylenediamine, phenylmorpholine and dihydroxyethylaniline; Dialkylaminobenzoic acid alkyl esters such as isoamyl P-dimethylaminobenzoate; 4,4′-bis ( Tetraalkylaminobenzophenones such as diethylamino) benzophenone, onium salt compounds such as benzyltriethylammonium bromide and benzyltributylammonium chloride; and hydrocarbon compounds such as isopropylbenzene and triphenylmethane, and mercapto compounds. Of these, in particular, phenolic compounds such as methoxyphenol, amino compounds such as phenothiazine, and dialkylaminobenzoic acid alkyl esters such as isoamyl P-dimethylaminobenzoate are preferably used.

The compound generating an active radical which is the sensitizer of the component D of the present invention includes a compound generating an active radical upon irradiation with light. Examples thereof include commonly known photoradical initiators. Examples include benzyl-based, benzoin ether-based, benzyl ketal-based, benzophenone-based, thioxanthone-based and the like. Besides, azo compounds such as azobisisobutyronitrile, azide compounds, disulfide compounds, peroxide compounds and the like are applicable.

Of these, a ketone-based photoradical initiator is particularly preferably applied, and examples thereof include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide and 3,3 '.
-Dimethyl-4-methoxybenzophenone, tetra (t
-Butylperoxycarbonyl) benzophenone, 2-
Chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-
Dimethylthioxanthone, isopropylthioxanthone, anthraquinone, 1,8-dichloroanthraquinone, 1,2-benzanthraquinone, 9-fluorenone, benzanthrone, 9,10-phenanthrenequinone xanthone and the like are used. However, those having an amino group such as Michler's ketone cannot be used.

These compounds are sulfonium salt compounds in which a hydroxyl group is directly bonded to an aromatic ring directly bonded to an S atom, for example,
It can be preferably used when a sulfonium salt compound in which R _{6 in the} general formula [II] is a hydrogen atom or a sulfonium salt compound in which R _{19 in the} general formula [V] is a hydrogen atom is used.

In the present invention, in addition to the above components, if desired, various resins, fillers, colorants, viscosity modifiers, defoamers,
Additives such as a leveling agent and a solvent can be added. As these resins, the curability of the composition, a cationically polymerizable compound other than the above-mentioned components which can be expected to improve the printing properties and resist properties, for example, various vinyl ether compounds, various cyclic compounds such as lactones, or,
A radically polymerizable compound such as (meth) acrylate can be used, and these are used in an amount of not more than 100 parts by weight with respect to 100 parts by weight of the component A epoxy resin.
Further, in order to improve the compatibility of the component C and the component D with other components, acetonitrile, propylene carbonate, cellosolves and the like can be used as the solvent of the component C and the component D.

Examples of the filler include silica, lipophilic silica, bentonite, zirconium silicate, powdered glass and the like.

As the colorant, for example, extender pigments such as alumina white, clay, barium carbonate, barium sulfate; zinc white, lead white, yellow lead, red lead, ultramarine blue, navy blue, titanium oxide, zinc chromate, red iron oxide, carbon Inorganic pigments such as black;
Brilliant Carmine 6B, Permanent Red R, Benzidine Yellow, Phthalocyanine Blue, Phthalocyanine Green, and other organic pigments; Basic dyes such as magenta and rhodamine; Direct dyes such as direct scarlet and direct orange; Acid dyes such as roselin and metanil yellow Is mentioned.

Bentonite, silica gel, aluminum oxide powder, etc. are used as viscosity modifiers, silicone oil is used as an antifoaming agent, and fluorine-based surfactants, silicone-based surfactants, non-aqueous acrylic co-agents are used as leveling agents. Examples thereof include polymers.

These additives are added and used within a range that does not impair the essential characteristics of the composition, preferably within 200 parts by weight, more preferably within 100 parts by weight based on 100 parts by weight of the total resin content. be able to.

In the present invention, the mixing ratio of the components A, B, C and D is 100 parts by weight in total of the components A and B,
The component A is 90 to 40 parts by weight, and the component C is 0.1 to 10 parts by weight and the component D is 0.1 to 10 parts by weight based on 100 parts by weight of the total resin content including the total of the components A and B or other resin content. Parts by weight.

The composition of the present invention is cured by photo-curing by irradiation with ultraviolet rays, etc. to particularly harden the surface to prevent flow and maintain the accuracy of the printed pattern. By heating to a suitable temperature, it cures to the deep part of the resist layer to obtain the desired cured film.

[0039]

As described above, the present invention is basically composed of a polyfunctional epoxy resin (component A), a reactive diluent (component B), a thermal latent cationic polymerization initiator (component C) and a sensitizer (component D). A thick film resist ink composition for chemical copper plating used in the production of a printed wiring board by an additive method characterized by its composition.

In the present invention, the polyfunctional epoxy resin of the component A forms a tough cured film (resist film) which is excellent in cationic polymerizability and has a large crosslinking density. This cured film is extremely stable against the chemical copper plating solution under the conditions of use. Furthermore, since it is generally a high-viscosity liquid or solid at room temperature, and the temperature dependence of the viscosity at room temperature is small, the composition is adjusted to a viscosity suitable for a screen printing ink by using an appropriate diluent. It's easy to do.

Use of only a low molecular weight epoxy resin having a viscosity at 25 ° C. of less than 150 poises, that is, a low epoxy equivalent makes it possible to obtain a tough cured film, but defects such as cissing tend to occur during coating, and a smooth cured film is obtained. Is not suitable for forming. Further, when the ink for screen printing is used, since the viscosity is low and the temperature dependence of the viscosity is large, the resolution is deteriorated due to bleeding, cissing and sagging during printing. Therefore, by using the low molecular weight epoxy resin alone, it is not possible to obtain a cured film that satisfies the intended performance as a resist for chemical plating.

The oxirane ring-containing compound of the component B is a reactive diluent compatible with the component A, and adjusts the viscosity of the resin composition with a minimum amount of use. Therefore, the viscosity of the resin composition can be adjusted without deteriorating the characteristics of the polyfunctional epoxy resin of the component A.

As the reactive diluent, a low boiling point oxirane ring-containing compound is easily vaporized during the preparation of the resin composition and its composition is likely to change, so that it is difficult to form a desired resin composition. Further, an oxirane ring-containing compound having an excessive viscosity has a large viscosity itself and is not suitable for adjusting the viscosity of a resin composition. Therefore, the boiling point of the component B is 140
An oxirane ring-containing compound having a molecular weight of 500 ° C. or more and 500 or less is suitable.

The thermal latent cationic polymerization initiator of component C is
It is stable at room temperature and rapidly generates cations when heated above a certain temperature, opening the oxirane rings of components A and B,
It is a fast-curing thermo-cationic polymerization initiator that initiates polymerization.

The sensitizer of the component D generates a cation from the heat-latent cationic polymerization initiator of the component C as a result of the reaction initiated by irradiation with light such as ultraviolet rays, and opens the oxirane ring of the components A and B. Then, the polymerization is started.

In the present invention, the combination of the selected polyfunctional epoxy resin of component A, the oxirane ring-containing compound of component B, the thermal latent cationic polymerization initiator of component C and the sensitizer of component D at room temperature. A composition which is stable and has almost no change in viscosity can be obtained. Then, this composition can be rapidly cured while maintaining its shape by irradiation with light such as ultraviolet rays, and then by heating above a specific temperature,
Even under the thick film where the light cannot reach sufficiently, it is possible to rapidly initiate the cationic polymerization and cure it, and it is possible to prevent the deterioration of the resolution due to the flow and permeation of the ink, and at the same time it is possible to cure the thick film. Becomes Furthermore, an extremely stable hardened film can be obtained with respect to a chemical copper plating solution under severe conditions, and it is possible to industrially form a circuit of a thick and thick conductor by the additive method.

[0047]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the following examples.

[1] Preparation of Resist Resin Composition for Chemical Plating A polyfunctional epoxy resin corresponding to component A, an oxirane ring-containing compound corresponding to component B, and a thermal latent cationic polymerization initiator of component C, and an addition of component D are added. Samples (A-1) to (A-) of the present invention of a resist resin composition for chemical plating in a form of use as an ink for screen printing by adding a sensitizer and various additives.
6) and comparative samples (C-1) to (C-5) were prepared.
Table 1 shows each component and formulation used for the preparation of the resin composition.
Each sample was added with a predetermined amount of the components A to D shown in Table 1, dissolved by stirring, and then the other components were added and mixed, and then kneaded with a three-roll to prepare samples.

[0049]

[Table 101]

[0050]

[Table 102]

[2] Curability test and formation of cured film Screen printing and curing Chemical plating paper Phenolic base material (Hitachi Chemical Co., Ltd. ACL-
141), circuit width and circuit spacing are both 200 μm, emulsion thickness 70
Printing was performed using 250 mesh stainless clean with a pattern of μm, and this was printed using a high pressure mercury lamp (80 W / cm).
Irradiate for 10 seconds (about 2100 mJ) using 2 x lamps,
Then, it was heated and cured in a hot air circulation type oven at 150 ° C. for 30 minutes. Curing of the amine-curing type thermosetting ink of Comparative Example
It was cured by heating in the same oven at 150 ° C. for 50 minutes. Also, C
UV curable ink of -5 is a high pressure mercury lamp (80W / cm
It was cured by irradiating it with an actinic ray for 10 seconds using (x2 lamps).

[3] Roughening The resist-coated substrate of [2] above was treated under the following roughening solution composition and immersion conditions. (Roughening liquid composition) Chromium trioxide: 30 g / l Concentrated sulfuric acid: 300 ml / l Sodium fluoride: 30 g / l (immersion condition) Roughening liquid temperature: 40 ° C. Immersion time: 15 minutes Stirring: Air blowing

[4] Preparation of Chemical Copper Plating Specimen Each sample treated in the above [3] was subjected to chemical copper plating under the following conditions to prepare a chemical copper plating specimen. (a) Chemical copper plating solution composition Copper sulfate: 8 g / l Ethylenediaminetetraacetic acid: 30 g / l 37% formalin solution: 3 ml / l Polyethylene glycol: 15 ml / l α-α'dipyridyl: 20 ml / l Sodium hydroxide: Amount to be adjusted to pH 12.8 (25 ° C) Water: Amount to be adjusted to 1 liter (b) Immersion condition Chemical copper plating solution temperature: 70 ° C Immersion time: 20 hours Stirring: Air blowing

[5] Test of Specimen The cured film formed in the above item [2] and the cured film after the chemical copper plating treatment in the item [4] were subjected to the following evaluation test, and the results are shown in Table 2. It was (a) Viscosity A sample kneaded with three rolls was sealed in a glass bottle, kept at 25 ° C. in a constant temperature water bath, and its viscosity was measured with a Viscotester VT-04 type (manufactured by Lion Corporation) No. 2 rotor. Then, on the next day, the viscosity after one day was measured in the same manner.

(B) Appearance and Thickness of Printed and Cured Film 1) The printed and cured film was visually observed for smoothness, glossiness and cissing. did. 2) Further, the bleeding, the resolution and the linearity of the edge portion of the printed pattern were observed with a microscope. 3) Next, the thickness of the substrate and the resist coating portion was measured with a dial gauge, and the maximum value of the resist film thickness was determined from the difference. 4) For resolution, the circuit width is 0.18
Those in the range of 0.20 mm to 0.20 mm and the circuit interval of 0.20 to 0.22 mm were accepted. Next, the following evaluation was performed on the test body prepared in the item [4].

(C) Copper plating solution resistance 1) Surface insulation resistance Using a conductive paste on the surface of the cured film, JIS Z-31
97, a comb-shaped circuit pattern is formed according to FIG.
Initial surface insulation resistance value and 4 under the condition of 500V x 1 minute application
The surface insulation resistance value after a moisture absorption test of 0 ° C. × 95% RH × 24 hours was actually measured.

2) Adhesion property After the test body was flowed in a solder bath at 260 ° C. for 10 seconds, a 1 mm square cross cut was put in the cured film, and a peeling test with a cellophane tape was conducted. 100/100 in the column of adhesion in Table 2
Means that out of 100 sheets, 100 sheets did not peel. Further, 20/100 means that 20 sheets did not peel.

3) Solvent resistance After immersing the test piece in methyl ethyl ketone for 3 hours, the appearance was visually observed for discoloration and deterioration. The case where no discoloration or deterioration was observed was marked with ◯, and the case where it was observed was marked with x.

(D) Plating Deposition State 1) Abnormal Deposition between Circuits Using a microscope, the presence or absence of copper particles deposited between the circuits was observed.

2) Linearity of Pattern Edge The edge of a copper circuit deposited by chemical copper plating was observed under a microscope to evaluate its linearity. When the linearity was observed, it was marked with ◯, and when it was not, it was marked with x.

[0061]

[Table 2]

[0062]

As shown in Table 2, in the printed wiring board produced by using the resist resin composition for chemical plating of the present invention, as shown in Table 2, the polyfunctional epoxy resin of component A, the oxirane ring-containing compound of component B, the component By using the basic composition comprising the thermal latent cationic polymerization initiator of C and the sensitizer of component D as a screen printing ink, a printed wiring board with a high conductor thickness by an additive method can be easily manufactured. That is, by using the resist resin composition for chemical plating of the present invention, it is possible to form a thick film, a rapid-curing, high-resolution resist pattern for chemical plating by a screen printing method, and printing such as resolution. It is possible to form a circuit pattern having a large conductor thickness, which is extremely excellent in characteristics. In addition, this product also has various properties such as resistance to plating solution and stain resistance to plating solution.

The present invention provides a resist resin composition for chemical plating, which contributes to new development in the field of printed wiring boards having a large conductor thickness, which has been difficult and mass-producible in the industrial production of printed wiring boards by the additive method. It is provided, and its industrial significance is extremely large.

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Claims (2)

[Claims] 1. A resist resin composition for chemical plating, which comprises the following components A, B, C and D: Component A: 1 whose viscosity at 25 ° C. is 150 poise or more
Epoxy resin having at least two glycidyl ether groups in the molecule and having the glycidyl ether groups directly bonded to an aromatic ring Component B: oxirane ring-containing compound component having a boiling point of 140 ° C. or higher and a molecular weight of 500 or less C: Sulfonium salt-based thermal latent cationic polymerization initiator Component D: Sensitizer 2. A total of 100 parts by weight of component A and component B,
The component A is 90 to 40 parts by weight, and the component C is 0.1 to 10 parts by weight, and the component C is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total resin content obtained by adding the other resins to the total of the components A and B. The resist resin composition for chemical plating according to claim 1, wherein D is 0.1 to 10 parts by weight.