JP2005114826A - Photosensitive resin composition and method for manufacturing its hardened product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has excellent photosensitivity to active energy rays for enabling to draw a fine pattern required for a printed circuit wiring board, which can be patterned by development with an organic solvent, and which produces a hardened film having satisfying characteristics required for a solder mask, and to provide its hardened product. <P>SOLUTION: The photosensitive resin composition comprises: (A) an epoxy resin containing an ethylenically unsaturated group as a reaction product of (a) an epoxy compound having 100 to 130°C softening point (measured according to JIS K7234) and two or more glycidyl groups in the molecule, (b) a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule, and as an optional component, (c) a monocarboxylic acid compound having at least two hydroxyl groups in the molecule; (B) a photopolymerization initiator; and (C) a crosslinking agent. The photosensitive resin composition has excellent photosensitivity and its hardened product obtained by irradiation with active energy rays has excellent adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance or the like and no tackiness. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention can be used for solder masks and electroless gold plating resists in the production of printed circuit boards, and can be developed with an organic solvent. The cured product obtained by irradiation with active energy rays has adhesiveness, solder heat resistance, and the like. In particular, the present invention relates to a photosensitive resin composition exhibiting properties such as excellent properties and electroless gold plating resistance, a method for producing the cured product, and a substrate having the cured product.

Solder mask is used for the purpose of avoiding the adhesion of solder to places other than the target part when soldering parts to the printed circuit board and protecting the circuit on the printed circuit board. Various characteristics such as heat resistance, adhesion, and chemical resistance are required. Initially, melamine-based heat-curable solder resist inks were used, but later, epoxy-based heat-curable solder resist inks with excellent heat resistance, hardness, adhesion, and chemical resistance were developed. Therefore, epoxy-based heat-curing solder resist ink has become the mainstream in printed circuit boards for industrial equipment such as computers related to high reliability.
On the other hand, in the printed circuit board for consumer use, UV curable solder resist ink obtained by acrylated epoxy resin is the mainstream from the viewpoint of workability and productivity.
Recently, the demand for improving the accuracy of circuit pattern density in industrial printed wiring circuit boards has increased due to the downsizing, high functionality, resource saving, and cost reduction of electronic devices. Solder masks are being developed.

  Patent Documents 1 and 2 disclose a composition comprising a resin obtained by reacting a phenol novolac epoxy resin or a cresol novolac epoxy resin with an unsaturated monobasic acid, a photopolymerization initiator, and an amine curing agent. Is described. However, the cresol novolac type epoxy resin conventionally used in these compositions is an ortho cresol novolak type epoxy resin having a softening point of less than 100 ° C., and the composition tends to show tack, and the mask film used for circuit pattern printing is a substrate. There was a problem such as sticking to.

Japanese Patent Publication No. 6-89284 Japanese Patent Publication No. 6-89285

The printed circuit wiring board is required to have higher precision and higher density in order to reduce the size and weight of mobile devices such as mobile phones and increase the communication speed. Higher performance is required in terms of adhesion, solder heat resistance, electroless gold plating resistance, and the like. However, currently used solder masks cannot sufficiently meet these requirements.
The object of the present invention is excellent in photosensitivity to active energy rays capable of drawing a fine pattern required for today's printed circuit wiring boards, can be formed by development with an organic solvent, and the resulting cured film can be used as a solder mask. An object of the present invention is to provide a resin composition satisfying various required properties, a cured product thereof, and the like.

In order to solve the above problems, the present inventors have completed the present invention as a result of intensive studies.
That is, the present invention
(1) Epoxy compound (a) having a softening point (measured according to JIS K7234) of 100 to 130 ° C. and having two or more glycidyl groups in the molecule, monocarboxylic acid compound having an ethylenically unsaturated group in the molecule ( b) and an ethylenically unsaturated group-containing epoxy resin (A) which is a reaction product of a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule as an optional component, a photopolymerization initiator (B), and a crosslinking agent A photosensitive resin composition comprising (C);

(2) The photosensitive resin composition according to the above (1), wherein the epoxy compound (a) is a cresol novolac type epoxy resin;
(3) The photosensitive resin composition according to the above (2), wherein the cresol novolac type epoxy resin is a novolac type epoxy resin obtained from metacresol and / or paracresol;
(4) The cresol novolac type epoxy resin is a novolak type epoxy resin obtained from a cresol mixture having a molar ratio of metacresol: paracresol of 7: 3 to 3: 7, as described in (2) or (3) above A photosensitive resin composition;

(5) A method for producing a cured product of the photosensitive resin composition, wherein the photosensitive resin composition according to any one of (1) to (4) above is irradiated with active energy rays;
(6) A substrate having a layer of a cured product obtained by the production method described in (5) above;
(7) An article having the substrate according to (6) above;
About.

  Epoxy compound (a) having an epoxy resin having a softening point (measured according to JIS K7234) of 100 to 130 ° C. and having two or more glycidyl groups in the molecule, and a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule ( b) and an ethylenically unsaturated group-containing epoxy resin (A) which is a reaction product of a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule as optional components, a photopolymerization initiator (B) and a crosslinking agent The photosensitive resin composition containing (C) has no tackiness, is excellent in photosensitivity, can be patterned by development with an organic solvent, and a cured product obtained by irradiation with an active energy ray adheres closely. Performance, solder heat resistance, electroless gold plating resistance, etc., and is particularly suitable as a photosensitive resin composition for printed circuit boards.

  The photosensitive resin composition of the present invention has an epoxy resin softening point (measured according to JIS K7234) of 100 to 130 ° C. and an epoxy compound (a) having two or more glycidyl groups in the molecule, ethylenic in the molecule. An ethylenically unsaturated group-containing epoxy resin (A), which is a reaction product of a monocarboxylic acid compound (b) having an unsaturated group and a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule as an optional component; It contains a photopolymerization initiator (B) and a crosslinking agent (C).

  The epoxy compound (a) having two or more glycidyl groups in the molecule used for obtaining the ethylenically unsaturated group-containing epoxy resin (A) of the photosensitive resin composition of the present invention is an epoxy resin according to JIS K7234. In the method for measuring the softening point, there is no particular limitation as long as it is an epoxy compound having a softening point of 100 to 130 ° C., but a novolak type epoxy resin obtained from metacresol and / or paracresol is preferable.

  A novolak resin obtained from metacresol and / or paracresol has been conventionally used as a binder resin for a positive resist for semiconductor processing and is relatively easily available.

  As said novolak-type epoxy resin, the resin which introduce | transduced the epoxy group into the novolak resin obtained from the cresol mixture whose molar ratio of metacresol and paracresol is 7: 3 to 3: 7 is especially preferable. In the novolak resin, if the proportion of metacresol is high, the molecular weight of the resin becomes too large, causing gelation in the worst case. Conversely, if the proportion of paracresol is high, the molecular weight of the resin is reduced, but cyclized to calex arene. It becomes a structure and a resin insoluble in an organic solvent is formed, and in any case, epoxidation may be difficult.

  The introduction of an epoxy group into a novolak resin can be performed by a conventional method. For example, a novolak resin and epichlorohydrin are mixed with an organic solvent such as methanol, ethanol or dimethyl sulfoxide, and a base such as sodium hydroxide or potassium hydroxide. The method of making it react using is mentioned.

As the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule used for obtaining the ethylenically unsaturated group-containing epoxy resin (A) of the photosensitive resin composition of the present invention, for example, acrylic Examples thereof include acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydride, and (meth) acrylate having one hydroxyl group in one molecule. Half-esters that are equimolar reactants with derivatives, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, and the like.
The monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is particularly preferably (meth) acrylic acid, (meth) acrylic acid and ε from the viewpoint of photosensitivity when a photosensitive resin composition is used. -Reaction products with caprolactone or cinnamic acid.

  Specific examples of the monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule that may be used to obtain the ethylenically unsaturated group-containing epoxy resin (A) of the photosensitive resin composition of the present invention Examples thereof include polyhydroxycarboxylic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid. Preferable examples include dimethylolpropionic acid and dimethylolbutanoic acid.

  The ethylenically unsaturated group-containing epoxy resin (A) used in the photosensitive resin composition of the present invention includes the above-described epoxy compound (a), monocarboxylic acid compound (b), and monocarboxylic acid compound as an optional component ( It is a reaction product with c), and is obtained by mixing and reacting each component at an appropriate ratio at the reaction temperature described later. Specific examples of organic solvents that can be used include ketones such as acetone, ethyl methyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Glycol ethers such as propylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl Ether acetate, dialkyl glutarate (eg, dimethyl glutarate, etc.) Esters such as dialkyl (eg dimethyl succinate), dialkyl adipate (eg dimethyl adipate); cyclic esters such as γ-butyrolactone; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Petroleum solvents; and further, single or mixed organic solvents such as a crosslinking agent (C) described later.

  During the reaction, it is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction, and the amount used is about 0.05 to 10% by weight with respect to the epoxy compound (a). Examples of the thermal polymerization inhibitor that can be used include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-butyl-p-cresol.

  Moreover, it is preferable to use a catalyst in order to promote reaction at the time of this reaction, and the usage-amount is about 0.1 to 10 weight% with respect to an epoxy compound (a). Examples of the catalyst that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, and octanoic acid. Examples include zinc and zirconium octoate.

  The reaction temperature of the reaction is about 60 to 150 ° C., and the reaction time is preferably 3 to 60 hours.

  Specific examples of the photopolymerization initiator (B) used in the photosensitive resin composition of the present invention include, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, Acetophenones such as 2-hydroxy-1-phenyl-4-ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanone Anthraquinones such as laquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone and 2-isopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4- Benzophenones such as benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like And phosphine oxides.

  These can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester and the like. It can be used in combination with a benzoic acid derivative or the like.

  Specific examples of the crosslinking agent (C) used in the photosensitive resin composition of the present invention include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,4-butanediol mono (Meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono ( Half ester, polyethylene glycol, which is a reaction product of acid anhydrides (for example, succinic acid, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) Di (meth) acrylate, tripropylene Glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, and ε-caprolactone adduct of hydroxypivalic acid neopenglycol Di (meth) acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meth) as a reaction product of dipentaerythritol and ε-caprolactone Examples thereof include acrylate, dipentaerythritol poly (meth) acrylate, epoxy (meth) acrylate which is a reaction product of a mono- or polyglycidyl compound and (meth) acrylic acid, and the like. Examples of the mono- or polyglycidyl compound include butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin poly Examples thereof include glycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether and the like.

  The amount of the ethylenically unsaturated group-containing epoxy resin (A), photopolymerization initiator (B), and cross-linking agent (C) contained in the photosensitive resin composition of the present invention is 100% of the non-volatile components of the photosensitive resin composition. In the case of weight%, the component (A) is 10 to 80% by weight, the component (B) is 0.5 to 30% by weight, and the component (C) is about 1 to 60% by weight.

  The photosensitive resin composition of the present invention is used as a resist ink such as a solder mask for a printed wiring circuit board, and is also useful as a permanent ink for filling an insulating material between electronic components and through holes. Furthermore, it can be used as an anti-sticking agent, a paint, a coating agent, an adhesive and the like.

The manufacturing method of the hardened | cured material by irradiation of active energy rays, such as an ultraviolet-ray, to the photosensitive resin composition of this invention is also contained in this invention. Irradiation of active energy rays such as ultraviolet rays can be performed by a conventional method. For example, in the case of irradiating ultraviolet rays, an ultraviolet ray generator such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used. More specifically, the photosensitive resin composition of the present invention dissolved in a solvent similar to the organic solvent in the reaction for obtaining the ethylenically unsaturated group-containing epoxy resin (A) is applied to a printed circuit board as a screen. It is applied at a film thickness of 5 to 160 μm by a method such as a printing method, a spray method, a roll coating method, an electrostatic coating method, or a curtain coating method, and the coating film is usually at a temperature of 50 to 120 ° C., preferably 60 to 100 ° C. Dry to form a coating film without tackiness. Next, irradiation may be performed collectively through a desired mask pattern, or irradiation may be performed using a laser irradiation apparatus while scanning. Irradiation is performed at about 10 to 2,000 mJ / cm ^{2 in} the case of ultraviolet rays. Thereafter, development processing is performed with the above-described organic solvent as necessary to remove unirradiated portions. Furthermore, if necessary, a cured product satisfying various properties such as adhesion, solder heat resistance, chemical resistance, gold plating resistance, and electrical characteristics can be obtained by thermosetting at a temperature of 100 to 200 ° C.

  In the present invention, the cured layer of the photosensitive resin composition of the present invention obtained by the above production method is used for electrical / electronic parts such as printed circuit boards as an interlayer insulating material for, for example, a solder resist or a build-up method. The base material in carrying out is also included. The thickness of the cured product layer is usually about 0.5 to 160 μm, preferably about 1 to 60 μm.

  Articles that can use the substrate having the cured product layer of the present invention include, for example, automobiles, trains, airplanes and other transport products; televisions, air conditioners, refrigerators, washing machines and other household appliances; mobile phones, computers and peripheral devices Information equipment and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example. In this example, the acid value and the epoxy equivalent mean the same as those usually used.

Synthesis example 1
In a 1 L flask equipped with a stirrer and a reflux tube, 155 g of propylene glycol monomethyl ether acetate as a reaction solvent, and an epoxy compound (a) having two or more glycidyl groups in the molecule, the softening point of the epoxy resin according to JIS K7234 Monocarboxylic acid compound having a softening point of 114 ° C., an epoxy equivalent of 216 g / equivalent, a metacresol / paracresol ratio = 5/5 of an epoxy compound (216.0 g), and an ethylenically unsaturated group in the molecule (b ) 72.1 g of acrylic acid (molecular weight: 72.06), 1.3 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor and 1. 1 of triphenylphosphine as a reaction catalyst. Charge 3g and keep the acid value of the reaction solution at 2 ℃ KOH / g or less at 110 ℃. To obtain a resin solution containing 65% by weight of an ethylenically unsaturated group-containing epoxy resin. The reaction time at this time was 26 hours. This resin solution is designated as A-1.

Synthesis example 2
In a 1 L flask equipped with a stirrer and a reflux tube, 165 g of propylene glycol monomethyl ether acetate as a reaction solvent, and an epoxy compound (a) having two or more glycidyl groups in the molecule, the softening point of the epoxy resin according to JIS K7234 A monocarboxylic acid compound having a softening point of 114 ° C., an epoxy equivalent of 216 g / equivalent, an epoxy compound having a metacresol / paracresol ratio = 5/5, 216.0 g, and an ethylenically unsaturated group in the molecule ( 50.4 g of acrylic acid (molecular weight: 72.06) as b), 40.2 g of dimethylolpropionic acid (molecular weight: 134.13) as a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule 2,6-di-tert-butyl-p-creso as a thermal polymerization inhibitor 1.4 g of triphenylphosphine as a reaction catalyst and 1.4 g of triphenylphosphine as a reaction catalyst are reacted until the acid value of the reaction solution becomes 2 mgKOH / g or less at a temperature of 110 ° C., and an epoxy resin containing an ethylenically unsaturated group A resin solution containing 65 wt% was obtained. The reaction time at this time was 28 hours. This resin solution is designated as A-2.

Synthesis example 3
Softening of epoxy resin according to JIS K7234 as 157 g of propylene glycol monomethyl ether acetate as a reaction solvent and epoxy compound (a) having two or more glycidyl groups in the molecule in a 1 L flask equipped with a stirrer and a reflux tube In the point measurement method, the softening point is 92 ° C., the epoxy equivalent: 220 g / equivalent orthocresol novolac type epoxy compound 220.0 g, acrylic acid (molecular weight as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule 72.1 g), 1.3 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 1.3 g of triphenylphosphine as a reaction catalyst were charged at 110 ° C. The reaction solution is reacted at a temperature until the acid value of the reaction solution becomes 2 mgKOH / g or less. A resin solution containing 65% by weight of a tylene unsaturated group-containing epoxy resin was obtained. The reaction time at this time was 26 hours. This resin solution is used as a comparative resin.

Examples 1 and 2, Comparative Example (A-1), (A-2) or (Comparative Resin) obtained in the above synthesis example and other components were mixed at a blending ratio (% by weight) shown in Table 1, If necessary, the mixture was kneaded with a three-roll mill to obtain a photosensitive resin composition. This was applied to a copper circuit printed circuit board by a bar coating method so as to have a thickness of 15 to 25 μm, and the coating film was dried by a hot air dryer at 80 ° C. for 60 minutes. After cooling to room temperature, the tackiness test described later was performed.

Next, the mask film on which the pattern was drawn was brought into close contact, and ultraviolet rays having an ultraviolet ray amount described below were irradiated using an ultraviolet exposure device (USHIO: 500 W multilight). Next, development was performed by immersing in propylene glycol monomethyl ether acetate as a developing solvent for 30 seconds, followed by rinsing with isopropyl alcohol.
Subsequently, it was dried with a hot air dryer at 150 ° C. for 60 minutes to obtain a cured film which was thermally cured. Tests such as photosensitivity, surface gloss, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold plating resistance were conducted. The results are shown in Table 2. The test method and evaluation method are as follows.

(Tackiness) Absorbent cotton was rubbed on the dried film applied to the substrate, and the tackiness of the film was evaluated.
○ ·········· Do not stick absorbent cotton.
× ··· Absorbent cotton lint sticks to the membrane.

(Photosensitivity) The coating film is irradiated with ultraviolet rays. It was observed whether absorbent cotton adhered. The following criteria were used:
○ ··· Irradiation amount 200 mJ / cm ² or less × ··· Irradiation amount 200 mJ / cm ² or more

(Surface gloss) The coating film irradiated with ultraviolet rays of 500 mJ / cm ² is immersed in ethanol for 60 seconds, and the cured film after drying is observed. The following criteria were used:
○ ・ ・ ・ ・ No cloudiness is seen at all × ・ ・ ・ ・ Slight cloudiness is seen

(Substrate sled) The coating film is exposed to 500 mJ / cm ² of ultraviolet rays. The following criteria were used:
○ ···· No warpage on the substrate.
Δ ················································································.
× ······················ Swarf of the substrate is seen.

(Adhesion) The coating film is exposed to 500 mJ / cm ² of ultraviolet rays. In accordance with JIS K5400, 100 1-mm galleys were made on the test piece, and a peeling test was performed using cello tape (registered trademark). The peeled state of the goblet was observed and evaluated according to the following criteria.
○ ··················································

(Pencil hardness) The coating film is exposed to 500 mJ / cm ² of ultraviolet rays. Evaluation was performed according to JIS K5400.

(Solvent resistance) The coating film irradiated with ultraviolet rays of 500 mJ / cm ² is immersed in isopropyl alcohol at room temperature for 30 minutes. It was confirmed that there was no abnormality in the appearance.
○ ・ ・ ・ ・ No cloudiness is seen at all × ・ ・ ・ ・ Slight cloudiness is seen

(Acid resistance) The coating film irradiated with ultraviolet rays of 500 mJ / cm ² is immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ········

(Heat resistance) A rosin-based plax was applied to a coating film irradiated with ultraviolet rays of 500 mJ / cm ² and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as 1 cycle and repeated 3 cycles. After being allowed to cool to room temperature, a peeling test with Cellotape (registered trademark) was conducted, and the following criteria were evaluated.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ········

(Gold-resistant plating property) The coating film irradiated with 500 mJ / cm ² of ultraviolet rays was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) at 30 ° C. for 3 minutes, and then washed with water. The test substrate was immersed in a 4 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes and then washed with water. Further, the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water. Next, this substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and then 85 ° C. nickel plating solution (Meltex, Mel Plate Ni-865M). Was immersed in a 20 vol% aqueous solution, pH 4.6) for 20 minutes, nickel-plated, and then immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Next, the test substrate was immersed in a gold plating solution at 95 ° C. (Meltex, an aqueous solution of Aurolectroles UP 15 vol% and potassium gold cyanide 3 vol%, pH 6) for 10 minutes, subjected to electroless gold plating, washed with water, and further washed at 60 ° C. Was immersed in warm water for 3 minutes, washed with water and dried. Cellophane tape (registered trademark) was adhered to the obtained electroless gold plating evaluation substrate, and the state when peeled was observed.
○ ···· No abnormality at all.
× ······ Slightly peeled off.

Table 1
Note Example Comparative Example
1 2
Ethylenically unsaturated group-containing epoxy resin A-1 34.00
A-2 34.00
Comparative resin 34.00
Cross-linking agent (C)
DPHA * 1 12.00 12.00 12.00
Photopolymerization initiator (B)
Irg 907 * 2 10.00 10.00 10.00
DETX-S * 3 2.00 2.00 2.00
EPA * 4 2.00 2.00 2.00
Filler Silica 10.00 10.00 10.00
Barium sulfate 22.00 22.00 22.00
Talc 5.00 5.00 5.00

Pigment 1.00 1.00 1.00
Additive BYK-354 * 5 1.00 1.00 1.00
KS-66 * 6 1.00 1.00 1.00

* 1 Nippon Kayaku acrylate monomer dipentaerythritol hexaacrylate * 2 Irgacure 907; Ciba Specialty Chemicals photopolymerization initiator 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane * 3 Nippon Kayaku photopolymerization initiator 2,4-diethylthioxanthone * 4 Nippon Kayaku sensitizer 4-dimethylaminobenzoic acid ethyl ester * 5 Big Chemie leveling agent * 6 Shin-Etsu Chemical defoamer

Table 2
Examples Comparative examples
1 2
Evaluation item tackiness ○ ○ ×
Light sensitivity ○ ○ ×
Surface gloss ○ ○ ○
Board sled ○ ○ ○
Adhesiveness ○ ○ ○
Pencil hardness 7H 5H 7H
Solvent resistance ○ ○ ○
Acid resistance ○ ○ ○
Heat resistance ○ ○ ○
Gold plating resistance ○ ○ ○

  As is clear from the results in Table 2, the photosensitive resin composition of the present invention gives particularly excellent results in tackiness and photosensitivity. Further, the cured film is at an excellent level in solder heat resistance, chemical resistance and gold plating resistance.

The photosensitive resin composition of the present invention is excellent in photosensitivity in the formation of a coating film by exposure and curing with ultraviolet rays, and the obtained cured product has adhesion, pencil hardness, solvent resistance, acid resistance, and heat resistance. Further, it is sufficiently satisfied with the gold plating resistance and can be suitably used for a light curable paint, a light curable adhesive, and the like.

Claims (7)

An epoxy compound (a) having a softening point (measured according to JIS K7234) of 100 to 130 ° C. and having two or more glycidyl groups in the molecule, a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and As an optional component, an ethylenically unsaturated group-containing epoxy resin (A), a photopolymerization initiator (B), and a crosslinking agent (C), which are reaction products of a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule A photosensitive resin composition comprising: The photosensitive resin composition according to claim 1, wherein the epoxy compound (a) is a cresol novolac type epoxy resin. 3. The photosensitive resin composition according to claim 2, wherein the cresol novolac type epoxy resin is a novolac type epoxy resin obtained from metacresol and / or paracresol. The photosensitive resin composition according to claim 2 or 3, wherein the cresol novolac type epoxy resin is a novolak type epoxy resin obtained from a cresol mixture having a molar ratio of metacresol: paracresol of 7: 3 to 3: 7. . The manufacturing method of the hardened | cured material of this photosensitive resin composition characterized by irradiating the photosensitive resin composition of any one of Claims 1-4 with an active energy ray. The base material which has a layer of the hardened | cured material obtained by the manufacturing method of Claim 5. An article comprising the substrate according to claim 6.