TWI504663B - Resin composition - Google Patents

Description

Resin composition

The present invention relates to a specific resin composition, and further contains a solder resist of the specific resin composition.

A solder resist is applied to both sides of the printed circuit board to prevent adhesion of the solder to unnecessary portions and to prevent permanent corrosion of the circuit substrate. In the past, a solder resist material was generally used as a photosensitive resin composition.

However, by using a solder resist forming method in the lithography step of the photosensitive resin composition, it is not possible to sufficiently reduce the thickness, fine wiring, and lead-free of the circuit board in recent years. The problem of temperature rise in solder reflow. Therefore, the photosensitivity and developability required for the photosensitive solder resist are limited, and it is difficult to obtain a cured product which can satisfy heat resistance and mechanical properties.

In addition, when a thermosetting type solder resist is used, the formation of the opening is performed using a carbon dioxide laser (refer to Patent Document 1), and since the slag is generated at the bottom of the opening, the so-called desmear removal is performed. Glue operation is necessary. Specifically, the desmear treatment in the formation of an interlayer insulating layer such as a multilayer wiring board is a dry method using a plasma and a wet method using an alkaline oxidizing agent solution, etc., from the viewpoint of productivity or production cost. For general use. Further, the slag at the bottom of the opening of the solder resist is also examined by the same wet method. However, when the wet method is used to treat the entire substrate and is applied to the state of the solder resist, not only the opening but also the prevention The surface of the welding consumable is also treated to damage the surface of the welding consumable. Therefore, when a treatment such as nickel plating in the opening portion is performed, the deposition of the solder resist component and the contamination of the plating bath in the plating bath cause a change in the deposition rate of the plating, and thus it is necessary to increase the frequency to establish a high price. And the problem of a highly toxic plating bath.

Further, in comparison with the conventional photosensitive solder resist using the photosensitive resin composition, the thermosetting type solder resist has high heat resistance or mechanical properties, but is preferably blended to lower the coefficient of thermal expansion to blend inorganic Filling material. However, when the inorganic filler is blended, the adhesion between the solder resist and the copper wiring tends to be lowered, and further, the elution of the inorganic filler is accompanied by the problem of contamination of the plating bath by the above-described desmear treatment. Significant.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-244125

The object of the present invention is to provide a resin composition suitable for a solder resist material which has excellent adhesion to copper wiring and high desmear resistance.

The inventors focused on the results of the discussion by including a specific (A) epoxy resin and (B) containing three The novolac type phenol resin having a structure of (triazine) and (C) an imidazole derivative and/or a cyclic anthracene derivative have been found to solve the above problems, and the present invention has been completed.

That is, the present invention is as follows.

(1) A resin composition characterized by containing (A) an epoxy resin and (B) containing three a structure of a novolac type phenolic resin, and (C) an imidazole derivative and/or a cyclic anthracene derivative.

(2) The resin composition according to (1), further comprising (D) an inorganic filler.

(3) The resin composition according to (1) or (2), which contains (A) an epoxy resin, an epoxy resin having 2 or more epoxy groups in one molecule, and a liquid epoxy resin at a temperature of 20 ° C. And/or an aromatic epoxy resin which has 3 or more epoxy groups in one molecule, has an epoxy equivalent of 250 or less, and is solid at a temperature of 20 °C.

(4) The resin composition according to (1) or (2), which contains (A) an epoxy resin, an epoxy resin having 2 or more epoxy groups in one molecule, and a liquid epoxy resin at a temperature of 20 ° C. And an aromatic epoxy resin having 3 or more epoxy groups in one molecule and having an epoxy equivalent of 250 or less and a solid content at a temperature of 20 ° C, and a blending mass ratio of 20:1 to 1:10.

(5) A solder resist material characterized in that the resin composition layer formed of the resin composition according to any one of (1) to (4) is formed on a support film.

(6) The solder resist according to the above (5), wherein the cured layer after the cured resin composition layer is adhered to the copper foil at a thickness of 0.50 kgf/cm or more and 5.00 kgf/cm or less. The surface roughness (Ra value) is formed by an alkaline permanganic acid solution to have a roughened surface of 100 nm or more and 300 nm or less.

By containing a specific (A) epoxy resin, (B) containing three The structure of the novolac type phenolic resin, and (C) the imidazole derivative and/or the cyclic anthracene derivative, can provide a good adhesion to the copper wiring and high desmear resistance for the solder resist. Resin composition.

[Best form of implementing the invention]

The following is a detailed description of the preferred embodiment of the invention.

The resin composition of the present invention is characterized by containing (A) an epoxy resin and (B) containing three a structure of a novolac type phenolic resin, and (C) an imidazole derivative and/or a cyclic anthracene derivative.

[(A) Epoxy Resin]

The epoxy resin to be used in the resin composition of the present invention is not particularly limited, and examples thereof include an epoxy resin having 2 or more epoxy groups in one molecule and a liquid epoxy resin at a temperature of 20 ° C (hereinafter referred to as the first one). "Epoxy resin", "an aromatic epoxy resin which has a cyclooxy group of 3 or more in one molecule, has an epoxy equivalent of 250 or less, and is solid at a temperature of 20 ° C" (hereinafter referred to as a second epoxy resin). The term "liquid" as used herein means a state of a liquid, and "solid" means a state of a solid, and the "aromatic epoxy resin" means an epoxy resin having an aromatic ring skeleton in its molecule. Further, the number of epoxy groups in one molecule is an average.

Specific examples of the first epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, and glycidylamine type. Epoxy resin, hydrogen-added epoxy resin, etc. Any one or two or more of these may be used alone. Further, the epoxy equivalent is preferably 250 or less, more preferably 220 or less, more preferably 200 or less, or more, from the viewpoint of workability in the case of a dry film and good fluidity at the time of lamination. It should be 180 or less. Further, from the viewpoint of flexibility, the lower limit of the epoxy equivalent is preferably 50 or more, more preferably 80 or more, more preferably 120 or more, still more preferably 150 or more. A commercially available product can be used as the first epoxy resin, and specific examples thereof include "Jeppel 825" (bisphenol A type epoxy resin), and the number of epoxy groups in one molecule. : 2, epoxy equivalent: 175), "E.p. 807" made by Japan Epoxy Resin Co., Ltd. (bisphenol F type epoxy resin, number of epoxy groups in one molecule: 2, epoxy equivalent: 169) "E.p. 152" (Phenolic novolac type epoxy resin, number of epoxy groups in one molecule: 2 or more, epoxy equivalent: 175), and DIC (share) "EPICLON" HP-4032" (naphthalene epoxy resin, number of epoxy groups in one molecule: 2, epoxy equivalent: 150), and "E.p. 604" (glycidylamine epoxy) made by Japan Epoxy Resin Co., Ltd. Resin, number of epoxy groups in one molecule: 3, epoxy equivalent: 120), "Yepit YX8000" manufactured by Japan Epoxy Resin Co., Ltd. (addition of hydrogen type epoxy resin, number of epoxy groups in one molecule: 2. Epoxy equivalent: 205).

The suitable physical properties of the cured product of the resin composition include, for example, heat resistance and low expansion ratio. From the viewpoint of physical properties, the epoxy resin is preferably an aromatic epoxy resin. Therefore, the first epoxy resin in the present invention is preferably an aromatic epoxy resin. Further, the first epoxy resin may be liquid when the temperature is less than 20 °C.

Further, examples of the second epoxy resin include a phenol novolak type epoxy resin, a Phenol Novolac type epoxy resin, a naphthalene type epoxy resin, a phenol, and a phenolic hydroxyl group. An epoxide of an aldehyde of a aldehyde (triphenylmethane type epoxy resin) or the like. Any one or two or more of these may be used alone. For the second epoxy resin, a commercially available product can be used. Specific examples thereof include "N-740" (a phenol novolak type epoxy resin), and the number of epoxy groups in one molecule: 3 or more, epoxy equivalent: 180), DIC (share) "N-690" (cresol novolac type epoxy resin, number of epoxy groups in one molecule: 3 or more, epoxy equivalent: 220), DIC (share) "EXA4700" ( 4-functional naphthalene type epoxy resin, number of epoxy groups in one molecule: 4, epoxy equivalent: 162), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol epoxy resin, epoxy in one molecule) Base: 3 or more, epoxy equivalent: 168), and the like.

In the second epoxy resin, the upper limit of the epoxy equivalent is preferably 220 or less, more preferably 200 or less, and still more preferably 180 or less from the viewpoint of adhesion and chemical resistance. Further, from the viewpoint of flexibility, the lower limit of the epoxy equivalent is preferably 50 or more, more preferably 80 or more, more preferably 120 or more, still more preferably 150 or more.

In addition, even if it is an aromatic epoxy resin having an epoxy equivalent of 250 or less, it is difficult to obtain heat resistance or chemical resistance of the cured product when the epoxy resin having less than 3 epoxy groups in one molecule is used.

In particular, when the resin composition of the present invention is formed into a resin composition sheet, the epoxy resin preferably contains both the first epoxy resin and the second epoxy resin. Further, other epoxy resins than the two types of epoxy resins may be contained.

The first epoxy resin mainly serves to exhibit a good fluidity when the resin composition sheet is laminated; the second epoxy resin is mainly used after the resin composition sheet is thermally cured. The role of hardening physical properties.

In the resin composition of the present invention, the upper limit of the content ratio of the (A) epoxy resin to the total nonvolatile content in the resin composition is preferably 60% by mass or less, and more preferably 45% by mass or less. In addition, the lower limit of the content ratio of the (A) epoxy resin to the total nonvolatile content in the resin composition is preferably 5% by mass or more, and more preferably 15% by mass or more.

When the first epoxy resin and the second epoxy resin are used in combination, the upper limit of the content ratio of the first non-volatile first epoxy resin in the resin composition is preferably 30% by mass or less, more preferably 20% by mass. %the following. This is based on the viewpoint that the resin composition sheet is likely to have a tack and maintain the handleability of the resin composition sheet at a normal temperature of about 20 to 30 ° C of the resin composition sheet. In addition, the lower limit of the content ratio of the first non-volatile first epoxy resin in the resin composition is preferably 5% by mass or more, and more preferably 10% by mass or more. This is based on the viewpoint of obtaining sufficient flexibility of the resin composition sheet and maintaining the handleability of the resin composition sheet at a normal temperature of about 20 to 30 ° C of the resin composition sheet, and performing a resin composition on the circuit board. In the case of laminating the sheets, a sufficient fluidity to fill only the via holes or through holes is obtained, in order to prevent lamination of the resin composition sheets to the circuit substrate. In addition, the circuit substrate is oozing out from a large amount of the resin composition in the field covered by the resin composition, thereby causing defects in the product and contamination of the machine.

The upper limit of the content ratio of the second epoxy resin to the total non-volatile content in the resin composition is preferably 15% by mass or less, and more preferably 10% by mass or less. This is based on the viewpoint of obtaining sufficient flexibility of the resin composition sheet and maintaining the handleability of the resin composition sheet at a normal temperature of about 20 to 30 ° C of the resin composition sheet, and performing a resin composition sheet on the circuit board. At the time of lamination, a sufficient fluidity viewpoint or the like which is filled only in a via hole or a through hole is obtained. In addition, when the cured product is used in the form of a sheet of the resin composition, the cured product reflects the characteristics of the second epoxy resin, and the non-volatile portion of the resin composition is obtained from the viewpoint of exhibiting heat resistance and chemical resistance. The lower limit of the content ratio of the second epoxy resin is preferably 0.01% by mass or more, and more preferably 1% by mass or more.

The blending ratio of the first epoxy resin to the second epoxy resin is preferably 20:1 to 1:10 by mass ratio (first epoxy resin: second epoxy resin), preferably 10:1 to 1:2. When the blend ratio is within this range, the first epoxy resin and the second epoxy resin are used in combination to exert a more remarkable effect.

[(B) contains three Constructed novolac type phenolic resin]

Contains three The structure of the novolac type phenolic resin acts as a hardener for the epoxy resin. Contains three Constructed novolac type phenolic resin for making three A condensate composition obtained by reacting a phenol with an aldehyde. three Classes, phenols and aldehydes are not particularly limited; as three In general, one or more selected from the group consisting of melamine, benzoguanamine, and methyl decylamine are preferred. Further, as the phenol, it is selected from the group consisting of phenol, or cresol, ethyl phenol, n-propoxy phenol, isobutyl phenol, t-butyl phenol, octyl phenol, nonyl phenol, nonyl phenol, methyl butyl phenol, and the like. Various o-, m-, p-isomers of alkylphenols such as -t-butanol, or various o-, m-, p- of vinylphenol, allylphenol, propenylphenol, ethynylphenol One or two or more kinds of a cycloalkyl phenol such as cyclopentyl phenol, cyclohexyl phenol or cyclohexyl cresol or a substituted phenol such as phenylphenol are preferable. Further, in terms of aldehydes, fumarin and/or paraformaldehyde is preferred.

Contains three The upper limit of the nitrogen atom content (ratio of the ratio of the number of nitrogen atoms to the total number of atoms) of the novolak-type phenol resin of the structure is preferably 25% or less, and more preferably 14% from the viewpoint of solvent solubility at the time of synthesis. the following. In addition, contains three The lower limit of the nitrogen atom content (ratio of the ratio of the number of nitrogen atoms to the total number of atoms) of the novolac type phenol resin of the structure is preferably 4% or more, and more preferably 8 from the viewpoint of maintaining the adhesion of the copper wiring. %the above.

In three In the reaction between the phenol and the aldehyde, the use and type of the catalyst are not particularly limited, and the reaction proceeds even without a catalyst. In the case of the solder resist material, it is not preferable to have a residue of an inorganic substance such as a metal in the form of a residual catalyst. Therefore, when a catalyst is used, an amine-based catalyst such as trimethylamine, triethylamine, diethylamine or aniline is preferably used.

Contains three used in the present invention Commercially available products can be used as the novolac type phenol resin. Specific examples thereof include "PHENOLITE LA-7052" (nitrogen atom content: 8%) and "PHENOLITE LA-7751" (nitrogen atom content: 14%) manufactured by DIC Corporation.

In the present invention, (B) contains three a novolac type phenol resin having a structure in which the total number of epoxy groups present in the resin composition and the phenolic hydroxyl group of the phenol resin are combined (the total number of epoxy groups: the total number of phenolic hydroxyl groups) to become Blending was carried out at 1:0.5 to 1.5. If the blending ratio of the phenol resin is out of this range, the heat resistance of the cured product of the resin composition may be insufficient.

[(C) Imidazole derivatives and/or cyclic anthracene derivatives]

The imidazole derivative and/or cyclic anthracene derivative in the present invention acts as a hardening accelerator. The imidazole derivative is a compound which contains an imidazole group and which is a compound having a hardening promoting effect on an epoxy resin. That is, there is no limitation as long as it has a hardening promoting effect, and specific examples thereof include imidazole ("1,3-dioxan-2,4-cyclopentadiene"); 2-methylimidazole, 2-ethylimidazole, 2-substituted imidazole derivatives of 2-pyridazole, 2-undecylimid, 2-phenylimidazole, etc.; 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, a cyanoimidazole derivative containing 1-cyanoethyl-2-ethyl-4-methylimidazole or 1-cyanoethyl-2-phenylimidazole; 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-(2'-undecazolyl)-ethyl-S-III 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-three Containing three Imidazole derivative; isomeric cyanuric acid addition of 2-phenylimidazole, isomeric cyanuric acid addition of 2-ethylimidazole, 2,4-diamine-6-[2'-methyl Imidazolyl-(1')]-ethyl-s-three Isomeric cyanide adduct imidazole derivatives such as isomeric cyanuric acid adducts, 2-phenyl-4,5-dihydroxyethylimidazole, 2-phenyl-4-methyl-5-hydroxyl a 4,5-substituted imidazole derivative such as dimethylimidazole; 2,3-hydroxy-1H-pyrrole[1,2-a]benzylimidazole; an epoxy imidazole or the like.

The imidazole derivatives may be used alone or in combination of two or more. Among these compounds, a 4,5-substituted imidazole derivative or an epoxy-imidazole is preferable from the viewpoint of the compromise between the copper wiring adhesion and the storage stability of the resin composition.

The cyclic anthracene derivative is a compound containing a cyclic anthracene skeleton and having a hardening promoting action. That is, there is no particular limitation as long as it has a hardening promoting effect, and specific examples thereof include diindole bicycloundecene (DBU) and derivatives thereof, and such salts, or diterpene bicyclononene (DBN) and derivatives thereof. Things, and the salt of these. The term "derivative" as used herein means a compound in which a nitrogen atom bonded to an imine bond in a cyclic anthracene skeleton is bonded with a substituent, and examples of the substituent include a benzyl group and the like. Further, the so-called "salt" is specifically a phenol salt, a carboxylate, an octylate, a p-toluenesulfonate, a formate, a phthalate, a phenol novolac resin salt, a tetraphenyl borate. Wait.

Among the cyclic anthracene derivatives, DBU or a derivative thereof or a salt thereof is preferably used as a DBU salt in terms of copper wiring adhesion and storage stability of the resin composition. A salt of a DBU derivative. Specific examples thereof include DBU-phenolate (specifically, "U-CAT SAl" manufactured by San-Apro Co., Ltd.), and DBU-octanoate (specifically, San-Apro Co., Ltd., "U-CAT SA102", etc.) , DBU-p-toluenesulfonate (specifically, manufactured by San-Apro Co., Ltd., "U-CAT SA506", etc.), DBU-formate (specifically, San-Apro), "U-CAT" SA603", etc.), DBU-phthalic acid salt (specifically, San-Apro Co., Ltd., "U-CAT SA810", etc.), DBU-phenol novolak resin salt (specifically, San-Apro (manufactured by the company), "U-CAT SA841", etc.), a salt of a DBU derivative (specifically, San-Apro Co., Ltd., "U-CAT 5002", etc.).

The cyclic anthracene derivative in the present invention may be used alone or in combination of two or more.

In the case of the present invention, when an imidazole derivative and a cyclic anthracene derivative are used in combination, each of them may be composed of one type of compound or two or more types of compounds.

The imidazole derivative and the cyclic anthracene derivative in the present invention are preferably dissolved as a soluble substance in a solvent. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, propyl acetate, 2-ethyloxyethyl acetate (Cellosolve acetate), and propylene glycol methyl ether acetate (Propylene). Glycol Monomethyl Ether Acetate), acetate such as Carbitol acetate, carbitol such as 2-ethoxyethyl ester (Cellosolve) or butyl carbitol, toluene, xylene, etc. Aromatic carbonized water, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. These may be used in combination of one type or two or more types.

Further, a substance which does not dissolve in a solvent and has extremely low solubility in a solvent is preferably dispersed in the resin composition as it is. When a resin composition for the purpose of blending a powdery imidazole derivative and/or a cyclic anthracene derivative is used as a solder resist material, the primary particle is improved from the viewpoint of improving the insulation reliability of the conductor layer of the fine pattern. The upper limit of the average particle diameter is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. Further, from the viewpoint of preventing secondary aggregation, the lower limit of the average particle diameter of the primary particles is preferably 0.01 μm or more. The average particle diameter referred to herein is based on the Mie scattering theory and can be measured by the refraction ‧ scattering method of laser light. Specifically, the particle size distribution of the compound to be measured is measured on a volume basis by a laser refractive particle size distribution measuring apparatus, and the average particle diameter is determined by the median diameter. The measurement sample is preferably one in which the compound to be measured is dispersed in water by ultrasonic waves. For the laser refracting type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. is used.

The resin composition of the present invention is caused to contain three by containing (C) an imidazole derivative and/or a cyclic anthracene derivative The hardening reaction of the epoxy resin of the phenol novolak type phenolic resin is structured to improve the desmear resistance of the cured product, so that the cured product retains a beautiful and high-grade appearance even after the desmear. In addition, the adhesion of the cured product to the copper wiring is greatly enhanced.

In the present invention, the upper limit of the content ratio of the (C) imidazole derivative and/or the cyclic anthracene derivative which is not volatile with respect to the entire resin composition, preserves stability and does not cause excessive hardening in the drying step. In view of the above, it is preferably 5% by mass or less, more preferably 3% by mass or less. In addition, the lower limit of the content ratio is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more from the viewpoint of copper foil adhesion and chemical resistance.

The resin composition of the present invention is particularly suitably used as a solder resist, and a solder resist containing a resin composition containing the component (A), the component (B) and the component (C) of the present invention is used as described later. It also has the so-called excellent adhesion to copper wiring and high desmear resistance.

The solder resist containing the resin composition of the component (A), the component (B), and the component (C) of the present invention has excellent adhesion to the copper wiring, and can be used as follows [copper wiring adhesion] The measurement method described in the measurement is measured, and the peeling strength of the copper foil can be grasped. The upper limit of the copper wiring adhesion (copper foil peeling strength) of the solder resist of the resin composition of the present invention is preferably 5.00 kgf/cm or less, and more preferably 2.00 kgf from the viewpoint of practical use. /cm or less, more preferably 1.00 kgf/cm or less, still more preferably 0.95 kgf/cm or less, still more preferably 0.90 kgf/cm or less. In addition, the lower limit of the copper wiring adhesion (copper foil peeling strength) of the solder resist of the resin composition of the present invention is 0.50 kgf/cm or more from the viewpoint that the higher the adhesion is, the better. Preferably, it is preferably 0.55 kgf/cm or more, more preferably 0.60 kgf/cm or more, still more preferably 0.65 kgf/cm or more, still more preferably 0.70 kgf/cm or more, and particularly preferably 0.75 kgf/cm or more. It is very suitable for 0.80kgf/cm or more.

The desmear resistance of the solder resist containing the resin composition containing the component (A), the component (B), and the component (C) of the present invention can be evaluated by the [degelation resistance measurement] described later. The method (surface roughness (Ra value) after treatment with an alkaline permanganic acid solution) was mastered. The upper limit of the desmear resistance (surface roughness (Ra value)) of the solder resist of the resin composition of the present invention is 500 nm or less from the viewpoint of elution of the solder resist component in the plating bath. Preferably, it is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, and still more preferably 280 nm or less. In addition, the lower limit of the desmear resistance (surface roughness (Ra value)) of the solder resist of the resin composition of the present invention is preferably 50 nm or more, and more preferably 100 nm from the viewpoint of practical use. The above is more preferably 150 nm or more, and still more preferably 200 nm or more.

[(D) Inorganic filler]

In the resin composition of the present invention, an inorganic filler may be blended to lower the coefficient of thermal expansion of the resin composition. As the inorganic filler, for example, barium, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, or titanic acid can be used. Barium, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. It is better to use it.

When the inorganic filler is used, the upper limit of the average particle diameter of the primary particles is preferably 20 μm or less, more preferably 10 μm or less, and more preferably 5 μm or less from the viewpoint of improving the insulation reliability of the conductor layer of the so-called fine pattern. Further, from the viewpoint of preventing secondary aggregation, the lower limit of the average particle diameter of the primary particles is preferably 0.01 μm or more. Further, in order to improve the moisture resistance of the inorganic filler, it is preferred to apply a surface treatment agent such as a decane coupling agent to the surface treatment. The average particle diameter of the inorganic filler is based on the Mie scattering theory and can be measured by a laser refraction ‧ scattering method.

The upper limit of the content ratio of the inorganic filler to the total non-volatile content in the resin composition is preferably 85% by mass or less from the viewpoint of the meltability at the time of lamination or the adhesion to the copper wiring. It is preferably 60% by mass or less. In addition, the lower limit of the content ratio of the inorganic filler in the resin composition is preferably 30% by mass or more, and more preferably 35% by mass or more from the viewpoint of the coefficient of thermal expansion.

Further, in the cured product of the resin composition of the present invention, the coefficient of thermal expansion is preferably 80 × 10 ^-6 /K or less in the range of 30 ° C to 150 ° C, preferably 60 × 10 ^-6 /K or less. The term "thermal expansion coefficient" as used herein refers to a value measured by a deformation of a substance as a function of temperature by a non-vibrating load that is stretched while changing the temperature, and "EXSTAR TMA" manufactured by SII NanoTechnology Co., Ltd. can be used. /SS6000", etc. were measured.

The resin composition of the present invention may be blended with "(E) polymer compound" for the purpose of imparting appropriate flexibility to the solder resist after heat curing. Specific examples of the polymer compound include a phenoxy resin, a polyvinyl acetal resin, a polyamidene, a polyamidoximine, a polyether oxime, a polyfluorene, and an aliphatic polyester. Polyol, polyether polyol, polycarbonate polyol, polyethylene terephthalate polyol, acrylic resin, and the like. Any one of these may be used alone or in combination of two or more.

Specific examples of the phenoxy resin include FX280, FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YL6954, YL6974, YL7482, YL7553, YL6794, YL7213, and YL7290 manufactured by Nippon Epoxy Resin Co., Ltd., and the like.

In the case of the polyvinyl acetal resin, a polyvinyl butyral resin is preferred, and specific examples of the polyvinyl acetal resin include, for example, the electric chemical industry, DENKA BUTYRAL 4000-2, 5000-A, 6000-C. , 6000-EP, Sekisui Chemical Industry Co., Ltd. S-LEC BH series, BX series, KS series, BL series, BM series, etc.

Specific examples of the polyimine are, for example, poly-imine "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. In addition, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-37083) contains poly A modified polyimine such as a polyimine of a fluorinated alkane skeleton, which is described in JP-A-2002-12667, JP-A-2000-319386, and the like.

Specific examples of the polyamidoximine are, for example, polyamine amidoxime "VYLOMAXHR11NN" and "VYLOMAXHR16NN" manufactured by Toyobo Co., Ltd. In addition, modified polyamidoquinone imines such as polyacrylamide skeleton-containing polyamine amidoxime "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyether oxime include, for example, polyether oxime "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of the polyfluorene include, for example, "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

The polymer compound is preferably blended at a ratio of less than 30% by mass based on 100% by mass of the total nonvolatile content of the resin composition. When the amount is 30% by mass or more, the viscosity of the resin composition becomes too high, and the wiring pattern on the circuit tends to be difficult to embed. In addition, when the blending amount is too small, the effect achieved by blending the polymer compound cannot be sufficiently obtained, so the lower limit of the blending amount is preferably 1% by mass or more.

In addition to the above components, the resin composition of the present invention may be blended with other components such as an additive, an organic filler, and a hardening accelerator other than the above, insofar as the effects of the present invention are not inhibited.

The additive is not particularly limited, and specific examples thereof include an organic phosphorus-based flame retardant, an organic-based nitrogen-phosphorus compound, a nitrogen compound, a polyoxyalkylene-based flame retardant, and a metal hydroxide. a filler such as an alkane powder, a nylon powder or a fluorinated powder; a tackifier such as an organic benton or a benton; a polyoxyalkylene-based, a fluorine-based or a polymer-based antifoaming agent; Leveling agent; adhesion imparting agent such as imidazole, thiazole, triazole or decane coupling agent; phthalocyanine blue, phthalocyanine ‧ green, iodine green, bisazo yellow , pigments such as carbon black.

Examples of the organic filler include acrylic rubber particles, polyamide fine particles, and polyoxyalkylene particles. In a specific example of the acrylic rubber particles, a resin exhibiting rubber elasticity such as acrylonitrile-butadiene rubber, butadiene rubber or acrylic rubber is subjected to chemical crosslinking treatment as long as it has a resin which is insoluble and insoluble to the organic solvent. For example, XER-91 (made by Nippon Synthetic Rubber Co., Ltd.), Taffei Roydo (AC3355), AC3816, AC3832, AC4030, AC3364, IM101 (above is GANZ CHEMICAL ( Shares), 啪啦罗依多 EXL2655, EXL2602 (above is Wu Yu Chemical Industry Co., Ltd.). Specific examples of the polyamide fine particles include an aliphatic polyamine such as nylon or an aromatic polyamine such as Kevlar Fiber, and even a polyamidimide having a particle size of 50 μm or less. The resin having a guanamine bond may be specifically VESTOSINT 2070 (manufactured by DAICEL ‧ HUELS Co., Ltd.) or SP500 (manufactured by TORAY Co., Ltd.).

The average particle diameter of the primary particles of the organic filler is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the average particle diameter exceeds 20 μm, when the underlying copper wiring is in a fine pattern, there is a fear that the insulation reliability cannot be maintained. When the average particle diameter of the organic filler is too small, secondary aggregation tends to occur, and the average particle diameter is preferably 0.01 μm or more. Further, the average particle diameter of the organic filler was also measured in the same manner as the above-mentioned inorganic filler.

In the resin composition of the present invention, it is possible to further blend the imidazole derivative and the cyclic anthracene derivative from the viewpoint of further improving the copper wiring adhesion or adjusting the balance between the storage stability and the curing acceleration effect. Hardening accelerator. As such a hardening accelerator, in addition to a tertiary amine, a hydrazine or an epoxy adduct or a microencapsulated one, triphenylphosphine, tetraphenylphosphine, tetraphenylboronic acid or the like can be used. A phosphine-based compound or the like can be used singly or in combination of two or more kinds. Further, the curing accelerator is used in an amount of 0.01 to 5% by mass based on the total nonvolatile content of the resin composition.

The resin composition of the present invention can be used in various applications, particularly in the case of a solder resist, and more preferably in the form of an ink type solder resist or a dry film type solder resist. In other words, the solder resist can be formed by coating and drying the varnish of the resin composition of the present invention on the circuit board; or the resin composition layer of the present invention can be formed on the support to form a resin composition. The sheet is pressed and laminated on the circuit board to form a solder resist. In the industry, it is preferred to use a dry film type solder resist material, that is, a resin composition sheet.

The method for producing the resin composition sheet is not limited, and it may be produced by a known production method. Specifically, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, the support film may be used as a support, the resin varnish may be coated, further heated, or the organic solvent may be dried by blowing hot air to form a resin composition. Floor.

Specific examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, propyl acetate, 2-ethoxyethyl acetate, propylene glycol methyl ether acetate, and ethyl acetate. A phthalate such as diethylene glycol ester, a carbitol such as 2-ethoxyethyl or butyl carbitol, an aromatic carbonized alkane such as toluene or xylene, dimethylformamide or dimethyl Acetylamine, N-methylpyrrolidone, and the like. The organic solvent may be used in combination of two or more kinds.

The drying condition is not particularly limited, and the content ratio of the organic solvent to the resin composition layer is 10% by mass or less, and it is preferably dried to 5% by mass or less. The melt viscosity curve of the formed resin composition layer is affected by the drying conditions described later, and it is preferred that the set drying conditions satisfy the aforementioned melt viscosity characteristics. Also, depending on the amount of the organic solvent in the varnish, a varnish containing 30 to 60% by mass of an organic solvent may be dried at 50 to 150 ° C for about 3 to 10 minutes. In the technical field, suitable and optimal drying conditions can be set by simple experiments.

The thickness of the resin composition layer is not particularly limited, and is preferably larger than the thickness of the conductor layer of the circuit substrate. The thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, and the thickness of the resin composition layer is preferably 10 to 100 μm.

Further, the resin composition layer in the resin composition sheet can also be protected by a protective film described later. By the protection of the protective film, adhesion or damage of foreign matter or the like to the surface of the resin composition layer can be prevented.

In the present invention, examples of the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter referred to as "PET"), and poly 2,6 naphthalene. A plastic film such as polyester, polycarbonate or polyimine which is a polyethylene naphthalate or the like. Further, the support film and the protective film may be appropriately subjected to a matting treatment, a corona treatment, a mold release treatment, or the like.

The thickness of the support film is not particularly limited, and is preferably 10 to 150 μm, and more preferably 25 to 50 μm. Further, the thickness of the protective film is preferably from 1 to 40 μm. Further, as described later, in the production step of the resin composition sheet, the support film used as the support is heated and hardened by laminating the resin composition layer of the circuit board and laminating the resin composition layer. In the treatment, it can be used as a protective film for protecting the surface of the resin composition layer.

The support film in the resin composition sheet is peeled off after the resin composition layer is laminated on the circuit board or the resin composition layer after lamination is cured by heating to form a hardened layer. When the support film is peeled off after heat-hardening the resin composition layer, adhesion of foreign matter or the like in the hardening step can be prevented, and the smoothness of the surface of the hardened layer can be improved. In the case where the peeling is performed after the heat curing, it is preferred to apply the release treatment to the support film in advance. Further, it is preferable that the resin composition layer formed on the support film is formed such that the area of the resin composition layer is smaller than the area of the support film. Further, the resin composition sheet can be curled into a roll shape and stored and stored.

The operation of laminating the resin composition sheet on the circuit board to form the solder resist material can be carried out according to the conventional dry film type solder resist material. First, when the resin composition layer is protected by a protective film, after peeling off, the resin composition layer is laminated to the one or both sides of the circuit substrate so that the resin composition layer directly contacts the circuit substrate. . The method of laminating to a circuit substrate by vacuum lamination and heating and pressurizing under reduced pressure is an optimum method of use. The lamination process can be carried out batchwise or in a continuous roll. Further, before the lamination, the resin composition sheet and the circuit board may be preheated as needed.

A commercially available vacuum laminator can be used for vacuum lamination. Specific examples of the commercially available vacuum laminator include a Vacuum Applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum press laminator manufactured by Nihon Seiki Co., Ltd., and a Drycoater manufactured by Hitachi Plant Technologies, Hitachi. AIC (stock) vacuum laminator and the like.

The conditions of lamination, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ). The gas pressure is preferably carried out by laminating under a reduced pressure of 20 mmHg (26.7 hPa) or less.

After the laminating step, it is preferred to use a metal plate for hot pressing to planarize the laminated resin composition sheet. This flattening step is performed by heating and pressurizing the sheet with a metal plate such as a heated SUS mirror panel under normal pressure. The same conditions as those of the above lamination step can be used for the heating and pressurization conditions.

A circuit board provided with a solder resist material of the resin composition of the present invention is mainly formed on an epoxy glass, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether (Polyphenyleneether). A conductor layer (circuit) formed by patterning on one or both sides of a substrate such as a substrate. Further, the circuit board of the present invention also includes a multilayer printed circuit board in which a conductive layer (circuit) is formed by patterning on a single side or both sides of a layer formed by alternately forming a conductor layer and an insulating layer. Further, it is preferable to apply a roughening treatment such as a blackening treatment to the surface of the conductor circuit layer in view of the adhesion between the solder material and the circuit board.

After laminating the resin composition sheet to the circuit board or further performing the planarization step after lamination, the support film is peeled off when peeled off, and the film can be formed on the circuit substrate by thermal curing. Welding consumables. The heat curing conditions are selected from the range of 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably 160 ° C to 200 ° C for 30 to 120 minutes.

After the formation of the solder resist material, if the support film is not peeled off before the hardening, the peeling is performed at this time. Next, the solder resist formed on the circuit board is opened to form an opening. The opening may specifically be well-known methods such as drill, laser, plasma, etc., and if necessary, may be combined to perform the method, but a laser opening such as a carbon dioxide laser or a YAG laser is used. For the most general practice.

After the opening is formed, a desmearing treatment is applied to remove the slag generated at the bottom of the opening. The desmear treatment can be carried out by various methods known in the art, but in terms of productivity or production cost, the wet method using an alkaline permanganic acid solution is preferred. Further, when the desmear treatment is carried out with an oxidizing agent such as an alkaline permanganic acid aqueous solution, it is preferred to apply a swelling treatment to the swelling liquid before the treatment. Specific examples of the swelling liquid include Swelling Dip Securiganth P manufactured by ATOTECH JAPAN Co., Ltd., Swelling Dip Securiganth SBU, and the like. In the swelling treatment, it is preferred to immerse the circuit board in a swelling liquid heated to 60 to 80 ° C for 5 to 10 minutes. Specific examples of the alkaline permanganic acid aqueous solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. The roughening treatment of the aqueous alkaline permanganic acid solution is preferably carried out at 60 to 80 ° C for 10 to 30 minutes. An alkaline permanganic acid aqueous solution, for example, a Concentrate Compact CP or a dosing solution security P manufactured by ATOTECH JAPAN Co., Ltd., may be mentioned.

After that, after the circuit board is cleaned, the circuit board is immersed in an electroless nickel plating solution, and a nickel plating layer (having a thickness of about 1 to 10 μm) is formed in the opening of the solder resist by electroless plating. Then, the substrate is specifically immersed in an electroless gold plating solution to form a gold plating layer (having a thickness of about 0.01 to 1 μm) on the nickel plating layer, and a solder pad is formed in the opening of the solder resist material ( Solder pad). For the commercially available product, for example, "Numoku", which is a product of the above-mentioned industrial group, and the like, and "GOBRIGHT", which is a product of the electroless gold plating solution, can be exemplified.

Then, in the opening portion of the solder resist, a solder paste as a low melting point metal is printed, and specifically, a solder bump is formed by reflow at 220 to 260 ° C to form a solder bump. The bump becomes a portion to be soldered to an electronic component such as a semiconductor wafer or a capacitor, and the wiring board is completed.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited only to the examples below. In addition, the "parts" in the following description means "parts by mass".

First, the measurement methods in the physical property evaluation of the examples and comparative examples will be described.

[Measurement of adhesion of copper wiring]

The protective film of the resin composition sheet obtained in the following Examples and Comparative Examples was peeled off, and then a vacuum laminator (MVLP-500) manufactured by a machine was produced at a pressure of 5 mmHg or less and a temperature of 100 ° C. The copper foil (30 μm) treated with CZ was laminated under the conditions of a pressure of 7 kgf/cm ² . After peeling off the PET film, the resin-attached copper foil was laminated to a copper foil laminate (MVLP-500) by a machine made of COPPER CLAD LAMINATE at a gas pressure of 5 mmHg or less, a temperature of 100 ° C, and a pressure. The condition of 7 kgf/cm ² was laminated to a CZ-treated copper foil laminate. It was heat-hardened at 180 ° C for 60 minutes. In addition, the above-mentioned so-called CZ treatment is specifically a treatment in which a copper foil is immersed in a mixture of formic acid and hydrochloric acid, washed with water, and the treatment liquid is washed away to roughen the surface of the copper foil. The copper wiring adhesion was measured in accordance with the peel strength of the measured copper foil in accordance with JIS C6481.

[Degelation resistance test]

Two sheets of the resin composition sheets obtained in the following examples and comparative examples were peeled off, and two sheets of the resin composition sheets were produced by a vacuum laminator (MVLP-500) manufactured by a famous machine. The pressure was 5 mmHg or less, the temperature was 100 ° C, and the pressure was 7 kgf/cm ² , and simultaneously laminated on both faces of the FR 4 double-sided copper foil laminate. Next, hot pressing was performed using a SUS mirror panel under the conditions of a continuous temperature of 100 ° C and a pressure of 5 kgf / cm ² . Then, the PET film was peeled off and subjected to a heat hardening treatment at 180 ° C for 30 minutes. Then, a desmear treatment (Swelling Dip Securiganth P (swelling), Concentrate Compact CP (oxidation), Reduction solution Securiganth P (neutralization)) using an oxidizing agent solution is assumed. The laminate was subjected to a treatment of swelling at 60 ° C for 5 minutes, oxidation at 80 ° C for 20 minutes, and neutralization at 40 ° C for 5 minutes.

The obtained laminate was measured by a VSI contact mode, a 50-fold lens, and a measurement range of 121 μm × 92 μm using a non-contact surface roughness meter (WYKONT 3300, manufactured by Veeco Instruments Co., Ltd.) to obtain a surface roughness (Ra value). . Further, the average value of 10 points in the entire measurement range was taken as the Ra value. The desmear resistance is evaluated by the value of the surface roughness (Ra value).

[Evaluation of thermal expansion rate]

The protective film of the resin composition sheet obtained in the following Examples and Comparative Examples was peeled off, and then heat-cured by heating at 180 ° C for 90 minutes, and the support was peeled off to obtain a flaky cured product. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and subjected to thermomechanical analysis under the tensile weighting method using "EXSTAR TMA/SS6000" manufactured by SII NanoTechnology Co., Ltd., a thermomechanical analyzer. After the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. In the second measurement, the average linear thermal expansion coefficient of 25 ° C to 150 ° C was calculated.

[Example 1]

33 parts of liquid bisphenol F type epoxy resin (epoxy equivalent 170, manufactured by Nippon Epoxy Resin Co., Ltd., "Yepit 807") and cresol novolac type epoxy resin (epoxy equivalent 220, 10 parts of DIC (EPICLONN-690), which was added to a mixture of 20 parts of MEK and 10 parts of cyclohexanone, and dissolved by heating while stirring. Then add a nitrogen atom content of 8% containing three MEK varnish ("PHENOLITe LA-7052" manufactured by DIC Co., Ltd., non-volatile matter 60% by mass, non-volatile phenolic hydroxyl equivalent 120) of 30 parts of phenol novolak resin, spherical sputum as inorganic filler ( 50 parts of an average particle diameter of 1 μm, treated with an amino decane, and an imidazole-based hardening accelerator as a curing accelerator (2-phenyl-4-methyl-5-hydroxymyimid: 4P4MHZ-made by Shikoku Kasei Co., Ltd.) PW") 0.5 parts, phenoxy resin varnish (40% by mass of non-volatiles, "FX293" manufactured by Tosho Kasei Co., Ltd., glass transition temperature 163 ° C) 20 parts, and polyvinyl acetal resin varnish (nonvolatile content) 15 parts by mass, "KS1" manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 107 ° C) 15 parts were prepared into a resin varnish. The inorganic filler content was 40% by mass based on the nonvolatile content of the resin varnish.

Next, the resin varnish was coated on a polyethylene terephthalate (thickness: 38 μm, hereinafter abbreviated as PET) having a thickness of 38 μm, and coated with a coater to have a thickness of 30 μm after drying, and then the thickness of the resin composition layer was 30 μm. It was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes (the amount of residual solvent was about 1% by mass). Further, the protective film made of a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer, and curled into a roll shape. Further, the sheet-like resin composition sheet was slit into a width of 507 mm, whereby a resin composition sheet having a size of 507 mm × 336 mm was obtained. It is used for the copper foil adhesion evaluation test and the desmear resistance evaluation test, and the measurement of the thermal expansion rate. The adhesion strength was 0.89 kgf/cm, and the surface roughness was 262 nm. The cured product has a thermal expansion coefficient of 58 × 10 ^-6 /K.

[Embodiment 2]

In addition, 0.5 parts of an imidazole-based hardening accelerator ("P 2M4MZ-PW" manufactured by Shikoku Kasei Co., Ltd.) was changed to DBU salt (DBU-phenolate: "U-CAT SA 1" manufactured by San-Apro Co., Ltd.) 0.5 parts. A resin varnish was produced in the same manner as in Example 1. The inorganic filler content was 40% by mass based on the nonvolatile content of the resin varnish.

Further, a resin composition sheet was produced in the same manner as in Example 1 using this resin varnish, and a copper foil adhesion evaluation test and a desmear resistance evaluation test were performed. The adhesion strength was 0.98 kgf/cm, and the surface roughness was 299 nm. Further, the cured product has a thermal expansion coefficient of 58 × 10 ^-6 /K.

[Comparative Example 1]

A resin varnish was produced under the same conditions as in Example 1 except that an imidazole-based hardening accelerator ("2P4MHZ-PW" manufactured by Shikoku Kasei Co., Ltd.) was used. The inorganic filler content was 40% by mass based on the nonvolatile content of the resin varnish.

Further, a resin composition sheet was produced in the same manner as in Example 1 using this resin varnish, and a copper foil adhesion evaluation test and a desmear resistance evaluation test were performed. The adhesion strength was 0.75 kgf/cm, and the surface roughness was 397 nm.

[Comparative Example 2]

In addition, 0.5 part of the imidazole-based hardening accelerator ("P2SMHZ-PW" manufactured by Shikoku Kasei Co., Ltd.) was changed to 0.5 parts of a phosphorus-based hardening accelerator ("TPP-S" manufactured by Kitagawa Chemical Co., Ltd.), and Example 1 The resin varnish was also produced in the same manner. The inorganic filler content was 40% by mass based on the nonvolatile content of the resin varnish.

Further, a resin composition sheet was produced in the same manner as in Example 1 using this resin varnish, and a copper foil adhesion evaluation test and a desmear resistance evaluation test were performed. The adhesion strength was 0.89 kgf/cm, and the surface roughness was 330 nm.

[Comparative Example 3]

In addition to MEK varnish ("PHENOLITETD-2090" manufactured by DIC Co., Ltd., non-volatile content of 60% by mass, non-volatile phenolic hydroxyl equivalent of 105), 31 parts of the substitution contained three A resin was prepared in the same manner as in Example 1 except that MEK varnish ("PHENOLITELA-7052" manufactured by DIC Co., Ltd., non-volatile content: 60% by mass, non-volatile phenolic hydroxyl equivalent: 120) of 30 parts of phenol novolak resin was used. Varnish. The inorganic filler content was 40% by mass based on the nonvolatile content of the resin varnish.

Further, a resin composition sheet was produced in the same manner as in Example 1 using this resin varnish, and a copper foil adhesion evaluation test and a desmear resistance evaluation test were performed. The adhesion strength was 0.49 kgf/cm, and the surface roughness was 585 nm.

[Comparative Example 4]

In addition to the use of naphtholaralkyl resin, MEK varnish ("SN-485" manufactured by Tohto Kasei Co., Ltd., non-volatile content of 60% by mass, non-volatile phenolic hydroxyl equivalent of 215) 63 parts, substituted for three The same procedure as in Example 1 was carried out except that MEK varnish ("PHENOLITELA-7052" manufactured by DIC Co., Ltd., 60% by mass of nonvolatile matter and phenolic hydroxyl equivalent of 120% of nonvolatile matter) of the phenol novolak resin was prepared in the same manner as in Example 1. Resin varnish. The inorganic filler content was 40% by mass based on the nonvolatile content of the resin varnish.

Further, a resin composition sheet was produced in the same manner as in Example 1 using this resin varnish, and a copper foil adhesion evaluation test and a desmear resistance evaluation test were performed. The adhesion strength was 0.76 kgf/cm, and the surface roughness was 79 nm.

The above results are shown in Table 1 below.

As is clear from Table 1, the cured product of the resin composition of the example has both copper wiring adhesion and desmear resistance, and a high-performance solder resist can be realized by the resin composition of the present invention.

[Industry Utilization]

By containing a specific (A) epoxy resin, (B) containing three The structure of the novolac type phenolic resin and (C) the imidazole derivative and/or the cyclic anthracene derivative are suitable as a solder resist material having excellent adhesion to copper wiring and high desmear resistance. It is more profound to provide a solder mask containing its resin composition.

The present application is based on a Japanese patent application No. 2009-167164, the entire contents of which are incorporated herein by reference.

Claims (12)

A resin composition for a solder resist material, characterized in that it contains (A) an epoxy resin and (B) contains three a novolac type phenol resin having a structure of (triazine), and (C) an imidazole derivative and/or a cyclic anthracene derivative, wherein the (A) epoxy resin contains: an epoxy group having 2 or more in one molecule; When the temperature is 20 ° C, it is a liquid epoxy resin, and an epoxy resin having 3 or more epoxy groups in one molecule, an epoxy equivalent of 250 or less, and a solid epoxy resin at a temperature of 20 ° C. The resin composition for a solder resist according to the first aspect of the patent application, further comprising (D) an inorganic filler. The resin composition for a solder resist according to the second aspect of the invention, wherein the content of the (D) inorganic filler is 30% by mass or more based on the total non-volatile content in the resin composition. The resin composition for a solder resist according to the second aspect of the invention, wherein the content of the (D) inorganic filler is 30 to 85% by mass based on the total non-volatile content in the resin composition. The resin composition for a solder resist according to any one of claims 1 to 4, wherein the (A) epoxy resin content ratio is 5 to 60 masses with respect to the overall nonvolatile content in the resin composition. %. The resin composition for a solder resist according to any one of claims 1 to 4, wherein the (A) epoxy resin content ratio is 5 to 45 masses with respect to the overall nonvolatile content in the resin composition. %. For welding rods according to any one of claims 1 to 4 A resin composition having an epoxy group of 2 or more in one molecule, a liquid epoxy resin at a temperature of 20 ° C, and an epoxy group having 3 or more in one molecule, an epoxy equivalent of 250 or less, and a temperature. An aromatic epoxy resin which is solid at 20 ° C and has a blending mass ratio of from 20:1 to 1:10. The resin composition for a solder resist according to any one of claims 1 to 4, which has an epoxy group having 2 or more in one molecule, a liquid epoxy resin at a temperature of 20 ° C, and 1 molecule. An aromatic epoxy resin having 3 or more epoxy groups and having an epoxy equivalent of 250 or less and a solid at a temperature of 20 ° C, and a blending mass ratio of 20:1 to 1:2. The resin composition for a solder resist according to the seventh aspect of the invention, wherein the epoxy resin has 2 or more epoxy groups per molecule, and is a liquid ring at a temperature of 20 ° C with respect to the overall nonvolatile content in the resin composition. The content ratio of the oxygen resin is 30% by mass or less. The resin composition for a solder resist according to any one of claims 1 to 4, wherein the total number of epoxy groups present in the resin composition is three The combined ratio of the phenolic hydroxyl groups of the novolac type phenolic resin (the total number of epoxy groups: the total number of phenolic hydroxyl groups) is 1:0.5 to 1.5, and relative to the overall nonvolatile content in the resin composition, The content ratio of the (C) imidazole derivative and/or the cyclic anthracene derivative is 0.01 to 5% by mass. A dry film type solder resist material characterized in that a resin composition layer formed of a resin composition for a solder resist according to any one of claims 1 to 4 is applied to a support film. A circuit substrate characterized by a patent application scope The resin composition for a solder resist according to any one of items 1 to 4 is thermally hardened to form a solder resist.