JP4471149B2 - Photosensitive resin composition and method for producing cured product thereof - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention can be used for a solder mask, an electroless gold plating resist, etc. in the production of a printed (wiring circuit) board, and is developed mainly with an alkaline aqueous solution. The present invention relates to a photosensitive resin composition exhibiting characteristics such as excellent heat resistance 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.

A prepolymer having at least two ethylenically unsaturated bonds in one molecule, for example, a novolak type epoxy resin, a finely divided epoxy compound having at least two epoxy groups in one molecule and hardly soluble in a diluent A photosensitive thermosetting resin composition is described in Patent Document 1.
Uses a photocurable and thermosetting liquid resist ink composition containing an active energy ray-curable resin obtained by reacting a reaction product of a novolak-type epoxy compound with an unsaturated monocarboxylic acid and a polybasic acid anhydride. A method for forming a solder resist pattern is described in Patent Document 2.

  However, the novolak type epoxy resins conventionally used for these are based on orthocresol novolak type epoxy resins having a softening point of less than 100 ° C., and when used as a composition, tack is likely to appear, and the mask film is stuck on the substrate. There were problems such as sticking.

Japanese Patent Publication No. 7-17737 Japanese Patent Publication No. 7-67008

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 improve the communication speed. Higher performance in terms of adhesion, solder heat resistance, electroless gold plating resistance and the like has been demanded. However, currently used solder masks cannot sufficiently meet these requirements.
The object of the present invention is to have excellent photosensitivity to active energy rays capable of drawing a fine pattern required for today's printed circuit wiring boards, to form a pattern by development with an aqueous alkaline solution, and to obtain a cured film 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.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed the present invention.
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 polymer obtained by reacting a polybasic acid anhydride (d) with a reaction product with a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule as an optional component. A photosensitive resin composition containing a carboxylic acid resin (A), a photopolymerization initiator (B), a crosslinking agent (C) and a curing agent (D);

(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) The photosensitive resin composition according to any one of (1) to (4) above, wherein the unsaturated group-containing polycarboxylic acid resin (A) has a solid content acid value of 40 to 160 mgKOH / g;

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

  Epoxy compound having a softening point (measured according to JIS K7234) of 100 to 130 ° C. and having two or more glycidyl groups in the molecule, particularly a novolak type epoxy resin obtained from metacresol and / or paracresol A polybasic acid anhydride to a reaction product of a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule and, if necessary, a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule It contains an ethylenically unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting (d), a photopolymerization initiator (B), a crosslinking agent (C), and a curing agent (D). The photosensitive resin composition of the present invention has no tackiness, is excellent in photosensitivity, can be patterned by development with an aqueous alkaline solution, and has active energy rays. The cured product obtained by irradiation exhibits high performance in adhesion, pencil hardness, solvent resistance, acid resistance, solder heat resistance, electroless gold plating resistance, etc., and is also suitable for photocurable paints, photocurable adhesives, etc. It can be used and is particularly suitable as a photosensitive resin composition for printed wiring 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. A polybasic acid anhydride (d) is reacted with a reaction product of a monocarboxylic acid compound (b) having an unsaturated group and, if necessary, a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule. It contains an ethylenically unsaturated group-containing polycarboxylic acid resin (A), a photopolymerization initiator (B), a crosslinking agent (C), and a curing agent (D).

The epoxy compound (a) having two or more glycidyl groups in the molecule used for obtaining the ethylenically unsaturated group-containing polycarboxylic acid resin (A) of the photosensitive resin composition of the present invention is in accordance with JIS K7234. The method for measuring the softening point of the epoxy resin is not particularly limited 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, and in the worst case, gelation is caused. 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.

  As a specific example of the method for producing the novolak resin, for example, an acidic catalyst such as oxalic acid, acetic acid, hydrochloric acid, sulfuric acid or the like is added to metacresol and / or paracresol and a formalin aqueous solution, and the mixture is heated and subjected to a condensation reaction as necessary. Can be obtained.

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

  As the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule used for obtaining the ethylenically unsaturated group-containing polycarboxylic acid resin (A) of the photosensitive resin composition of the present invention, for example, , Acrylic acid, 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.

  Particularly preferred as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is (meth) acrylic acid, (meth) acrylic acid and ε in terms of sensitivity when a photosensitive resin composition is used. -Reaction product with caprolactone or cinnamic acid. In the present invention, (meth) acrylate means methacrylate or acrylate, and (meth) acrylic acid means methacrylic acid or acrylic 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 polycarboxylic acid resin (A) of the photosensitive resin composition of the present invention Specific examples include polyhydroxycarboxylic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid. Preferred are dimethylolpropionic acid and dimethylolbutanoic acid.

  The epoxy compound (a), the monocarboxylic acid compound (b) having an ethylenically unsaturated group, and the monocarboxylic acid having a hydroxyl group as an optional component, which are used in the photosensitive resin composition of the present invention The ethylenically unsaturated group-containing epoxy resin, which is a reaction product of the compound (c), is obtained by mixing and reacting each component in an appropriate ratio at a reaction temperature described below in a solventless or organic solvent. 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 dipropylene 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.), koha Esters such as dialkyl acids (for example, dimethyl succinate), dialkyl adipates (for example, dimethyl adipate); cyclic esters such as γ-butyrolactone; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. And other petroleum solvents. Furthermore, you may use the crosslinking agent (C) etc. which are mentioned later as a solvent. These may be used alone or in combination.

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

  Specific example of polybasic acid anhydride (d) reacted with the above-mentioned ethylenically unsaturated group-containing epoxy resin to obtain the ethylenically unsaturated group-containing polycarboxylic acid resin (A) of the photosensitive resin composition of the present invention As long as it is a compound having an acid anhydride structure in the molecule, it is not particularly limited. However, from the viewpoint that the cured product is excellent in developability in alkaline aqueous solution, heat resistance, hydrolysis resistance, etc., for example, succinic anhydride, phthalic anhydride, etc. Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

The reaction with the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the reaction solution following the reaction obtained with the above-mentioned ethylenically unsaturated group-containing epoxy resin. preferable. The addition amount of the polybasic acid anhydride (d) is preferably charged with a calculated amount such that the solid content acid value of the finally obtained ethylenically unsaturated group-containing polycarboxylic acid resin (A) is 40 to 160 mgKOH / g. . If this solid content acid value is less than 40 mgKOH / g, the developability of the aqueous alkaline resin solution of the photosensitive resin composition may be significantly reduced, and development may not be possible. If the solid content acid value exceeds 160 mgKOH / g, development may occur. Therefore, there is a possibility that patterning cannot be performed.
In addition, in this invention, a solid content acid value is the quantity (mg) of potassium hydroxide required in order to neutralize the acidity of the carboxylic acid in 1 g of resin. If the concentration of the resin in the solution is known, the solid content acid value can be calculated from the acid value of the solution. In the present invention, the acid value is the amount (mg) of potassium hydroxide required to neutralize 1 g of a solution containing an acidic substance such as a resin, and is measured by a normal neutralization titration method according to JIS K0070. The
The reaction temperature is, for example, about 60 to 150 ° C., and the reaction time is preferably about 2 to 8 hours.

  Specific examples of the photopolymerization initiator (B) contained 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, 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 Phosphine oxides and the like.

  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 It can be used in combination with a polymerization reaction accelerator such as a benzoic acid derivative.

  Specific examples of the crosslinking agent (C) contained 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 ( (Meth) acrylates) and polybasic acid anhydrides (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) ) Acrylate, tripropylene glycol Di () -caprolactone adduct of (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, hydroxypivalic acid neopenglycol (Meth) acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, Examples thereof include dipentaerythritol poly (meth) acrylate, epoxy (meth) acrylate that 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, and glycerin. Examples include polyglycidyl ether, glycerin polyethoxy glycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, and the like.

  As the curing agent (D) used in the photosensitive resin composition of the present invention, it reacts by heating with carboxyl groups and hydroxyl groups remaining in the resin coating film after curing of the photosensitive resin composition by irradiation with active energy rays, The compound is not particularly limited as long as it is a compound that gives a cured coating film having strong chemical resistance, and examples thereof include an epoxy compound and an oxazine compound.

  Specific examples of the epoxy compound as the curing agent (D) include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, Examples thereof include bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

  Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink & Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical), Epicoat 154 (made by Japan Epoxy Resin Co., Ltd.), RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

  Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR. -6650 (made by Union Carbide Co., Ltd.), ESCN-195 (made by Sumitomo Chemical Co., Ltd.), etc. are mentioned.

  As the trishydroxyphenylmethane type epoxy resin, for example, EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epicort E1032H60 (Japan Epoxy Resin Co., Ltd.).

  Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.), TACTIX-556 (manufactured by Dow Chemical Co., Ltd.), and the like.

  Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (all manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (manufactured by Union Carbide Co., Ltd.), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei ( Bisphenol-F type epoxy resin, etc.).

  Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H (both manufactured by Nippon Kayaku Co., Ltd.), and bixylenol such as YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.). Type epoxy resin, YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

  Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like.

  Examples of the naphthalene skeleton-containing epoxy resin include NC-7000, NC-7300 (all manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.), and the like.

  Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).

  Examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S (all manufactured by Nissan Chemical Industries, Ltd.).

  Specific examples of the oxazine compound as the curing agent (D) include, for example, Bm type benzoxazine, Pa type benzoxazine, and Ba type benzoxazine (all manufactured by Shikoku Kasei Kogyo Co., Ltd.). It is done.

  The photosensitive resin composition of the present invention comprises an ethylenically unsaturated group-containing polycarboxylic acid resin (A), a photopolymerization initiator (B), a crosslinking agent (C), and a curing agent (D). When the non-volatile component is 100% by weight, the component (A) is 10 to 80% by weight, the component (B) is 0.5 to 30% by weight, the component (C) is 5 to 60% by weight, and the component (D). Is obtained by mixing at a ratio of about 5 to 30% by weight, and if necessary, diluted with an organic solvent or the like used in obtaining the ethylenically unsaturated group-containing polycarboxylic acid resin (A). May be.

  Further, the photosensitive resin composition of the present invention includes various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay and other fillers, aerosil Thixotropy imparting agents such as phthalocyanine blue, phthalocyanine green, colorants such as titanium oxide, silicone, fluorine leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, etc. It can be added as needed for the purpose.

  In addition, although the above-mentioned hardening | curing agent (D) may be previously mixed with the said resin composition, it can also be mixed and used before application | coating to a printed wiring board. That is, it contains the above-mentioned component (A) and is mixed in a two-pack type of a main agent solution containing an epoxy curing accelerator and the like and a curing agent solution containing a curing agent (D). It may be used.

  The photosensitive resin composition of the present invention can also be used for a solder mask or the like as a dry film type having a structure in which the resin composition is sandwiched between a support film and a protective film.

  The photosensitive resin composition (liquid or film) of the present invention is useful as a resist material such as an insulating material between electronic components, an optical waveguide connecting optical components, a solder mask or a coverlay for a printed circuit board. In addition, it is also used for color filters, printing inks, sealants, paints, coating agents, adhesives 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. Curing can be performed by conventional methods by irradiation with energy rays such as ultraviolet rays. For example, in the case of irradiating ultraviolet rays, an ultraviolet ray generator such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used. The production method for printed circuit boards will be described in detail by way of example. Screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc., using a liquid photosensitive resin composition as a substrate. The film is applied at a film thickness of 5 to 160 μm by the above method, and the coating film is usually dried at a temperature of 50 to 110 ° C., preferably 60 to 100 ° C., to form a coating film having no tackiness. Next, the exposed portion is cured by irradiating an active energy ray such as ultraviolet rays with an intensity of usually about 10 to 2000 mJ / cm ² directly or indirectly through a photomask having an exposure pattern such as a negative film. The unexposed portion (uncured portion) is developed using an aqueous alkali solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like. Thereafter, if necessary, ultraviolet rays are further irradiated, and then heat treatment is usually performed at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C. Thus, a printed wiring circuit board having a permanent protective film excellent in gold plating properties and excellent in various properties such as heat resistance, solvent resistance, acid resistance, and adhesion can be obtained.

  Examples of the alkaline aqueous solution used for development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, and tetramethyl hydroxide. Organic alkaline aqueous solutions such as ammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.

  The cured product layer of the photosensitive resin composition of the present invention obtained by the above production method is, for example, a resist film, an interlayer insulating material for a build-up method, an optical waveguide such as a printed board, an optoelectronic board, or an optical board. Although it can be used for electronic / optical components, these base materials and components are also included in the present invention. In this case, the thickness of the cured product layer is usually about 0.5 to 160 μm, and preferably about 1 to 100 μm.

  Examples of articles that can use the substrate and parts having the cured product layer of the present invention include transportation products such as automobiles, trains, and airplanes; household appliances such as televisions, air conditioners, refrigerators, washing machines; mobile phones, computers, and the like. Examples of such peripheral equipment include information equipment.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Synthesis example 1
In a 1 L flask equipped with a stirrer and a reflux tube, 123.5 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 have a softening point according to JIS K7234. 114 ° C., epoxy equivalent: 216 g / equivalent, 216.0 g of an epoxy compound having a metacresol / paracresol ratio = 5/5, acrylic acid (molecular weight as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule 72.06), 1.2 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 1.2 g of triphenylphosphine as a reaction catalyst, The reaction was continued at temperature until the acid value of the reaction solution reached 2 mgKOH / g or less. The reaction time was 15 hours. Next, 87.8 g of propylene glycol monomethyl ether acetate and 104.3 g of tetrahydrophthalic anhydride (molecular weight: 152.15) as polybasic acid anhydride (d) were added and reacted at a temperature of 110 ° C. for 4 hours. A resin solution containing 65% by weight of the unsaturated group-containing polycarboxylic acid resin (A) was obtained. The acid value of the resin solution was 67 mgKOH / g (solid content acid value: 103 mgKOH / g). This resin solution is designated as A-1.

Synthesis example 2
In a 1 L flask equipped with a stirrer and a reflux tube, 131.4 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 have a softening point according to JIS K7234. 114 ° C., epoxy equivalent: 216 g / equivalent, 216.0 g of an epoxy compound having a metacresol / paracresol ratio = 5/5, acrylic acid (molecular weight as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule : 72.06), 50.4 g, 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 as a thermal polymerization inhibitor , 6-Di-tert-butyl-p-cresol 1.3 g 1.3 g of rephenylphosphine was charged and reacted at a temperature of 120 ° C. until the acid value of the reaction solution reached 2 mgKOH / g or less. The reaction time was 20 hours. Next, 65.8 g of propylene glycol monomethyl ether acetate and 59.6 g of tetrahydrophthalic anhydride (molecular weight: 152.15) as polybasic acid anhydride (d) were added and reacted at a temperature of 110 ° C. for 4 hours. A resin solution containing 65% by weight of the unsaturated group-containing polycarboxylic acid resin (A) was obtained. The acid value of the resin solution was 40 mgKOH / g (solid content acid value: 62 mgKOH / g). This resin solution is designated as A-2.

Synthesis example 3
In a 1 L flask equipped with a stirrer and a reflux tube, 128.8 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 have a softening point according to JIS K7234. 114 ° C., epoxy equivalent: 216 g / equivalent, 216.0 g of an epoxy compound having a metacresol / paracresol ratio = 5/5, acrylic acid (molecular weight as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule : 72.06), 57.7 g, 26.8 g of dimethylolpropionic acid (molecular weight: 134.13) as the monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule, and 2 as the thermal polymerization inhibitor. , 6-Di-tert-butyl-p-cresol 1.3 g 1.3 g of rephenylphosphine was charged and reacted at a temperature of 120 ° C. until the acid value of the reaction solution reached 2 mgKOH / g or less. The reaction time was 18 hours. Next, 52.4 g of propylene glycol monomethyl ether acetate and 36.0 g of succinic anhydride (molecular weight: 100.01) as polybasic acid anhydride (d) were added and reacted at a temperature of 110 ° C. for 4 hours. A resin solution containing 65% by weight of a saturated group-containing polycarboxylic acid resin (A) was obtained. The acid value of the resin solution was 42 mgKOH / g (solid content acid value: 65 mgKOH / g). This resin solution is designated as A-3.

Synthesis example 4
In a 1 L flask equipped with a stirrer and a reflux tube, 125.2 g of propylene glycol monomethyl ether acetate as a reaction solvent, an epoxy compound having two or more glycidyl groups in the molecule, a softening point according to JIS K7234 of 92 ° C., Epoxy equivalent: 220.0 g of 220 g / equivalent orthocresol epoxy compound, 72.1 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, thermal polymerization Introducing 1.3 g of 2,6-di-tert-butyl-p-cresol as an inhibitor and 1.3 g of triphenylphosphine as a reaction catalyst, the acid value of the reaction solution was 2 mgKOH / g at a temperature of 120 ° C. The reaction was continued until: The reaction time was 15 hours. Next, 89.0 g of propylene glycol monomethyl ether acetate and 105.7 g of tetrahydrophthalic anhydride (molecular weight: 152.15) as polybasic acid anhydride (d) were added and reacted at a temperature of 110 ° C. for 4 hours. A resin solution containing 65% by weight of an unsaturated group-containing polycarboxylic acid resin was obtained. The acid value of the resin solution was 66 mgKOH / g (solid content acid value: 102 mgKOH / g). This resin solution is used as a comparative resin.

Examples 1-3, Comparative Example 1
(A-1), (A-2), (A-3) or (Comparative Resin) obtained in the above synthesis example is mixed at a blending ratio shown in Table 1, and kneaded with a three-roll mill as necessary. The present invention or a comparative photosensitive resin composition was obtained. 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, absorbent cotton was attached to the coating film and the tackiness was observed.

  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, spray development (spray pressure: 0.2 MPa) was performed for 60 seconds using a 2% aqueous sodium carbonate solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film. Tests of photosensitivity, surface gloss, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold plating resistance were conducted, and 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.
○ ······ Absorbent cotton does not stick.
× ··· 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.
X ··· Irradiation amount 200 mJ / cm ² or more.

(Surface gloss) 200 mJ / cm ² of ultraviolet rays are irradiated, and a heat treatment is performed for 40 minutes with a dryer at 150 ° C. The obtained coating film 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.
Δ ··· Slightly cloudy.
×: Cloudy.

(Adhesiveness) Irradiation with 200 mJ / cm ² ultraviolet rays is performed, and heat treatment is performed for 40 minutes with a dryer at 150 ° C. In accordance with JIS K5400, 100 cured 1-mm bars were prepared 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.
○ ・ ・ ・ ・ No peeling.
× ···· peeled off.

(Pencil hardness) An ultraviolet ray of 200 mJ / cm ² is irradiated, and a heat treatment is performed with a dryer at 150 ° C. for 40 minutes. The obtained coating film was evaluated according to JIS K5400.

(Solvent resistance) 200mJ / cm < ² > of ultraviolet rays are irradiated, and a heat treatment is performed with a dryer at 150 [deg.] C. for 40 minutes. The obtained coating film 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 observed.

(Acid resistance) Irradiated with 200 mJ / cm ² of ultraviolet rays, and heat-treated for 40 minutes with a dryer at 150 ° C. The obtained coating film is immersed in a 10% aqueous hydrochloric acid 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) Irradiate with 200 mJ / cm ² of ultraviolet rays, and heat-treat with a dryer at 150 ° C. for 40 minutes. The obtained coating film was coated with rosin-based plax and immersed in a solder bath at 260 ° C. for 5 seconds. This was set 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 resistance) Irradiation with 200 mJ / cm ² ultraviolet rays and heat treatment for 40 minutes with a dryer at 150 ° C. The obtained coating film was immersed in an acidic degreasing solution at 30 ° C. (manufactured by Nippon McDermitt, 20 vol% aqueous solution of Metex L-5B) for 3 minutes, then washed with water, and then in a 14.4 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes After immersion, the substrate was washed with water, and 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 85 ° C. nickel plating solution (Meltex, Melplate Ni— After immersing in 865M 20vol% aqueous solution, pH 4.6) for 20 minutes and nickel plating, the substrate was immersed in 10vol% sulfuric acid aqueous solution for 1 minute at room temperature and washed with water. Next, the test substrate was immersed in a gold plating solution at 95 ° C. (Meltex, an aqueous solution of Ourolectroles UP15 vol% and potassium gold cyanide 3 vol%, pH 6) for 10 minutes, subjected to electroless gold plating, washed with water, and further washed with 60 It was immersed in warm water at 0 ° C. 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
Examples Comparative examples
1 2 3 1
Note Unsaturated group-containing polycarboxylic acid resin A-1 38.15
A-2 38.15
A-3 38.15
Comparative resin 38.15
Photopolymerization initiator (B)
Irg 907 1 3.58 3.58 3.58 3.58
DETX-S 2 0.36 0.36 0.36 0.36
Cross-linking agent (C)
DPHA 3 5.16 5.16 5.16 5.16
TMPTA 4 2.00 2.00 2.00 2.00
Curing agent (D)
YX-4000 5 3.58 3.58 3.58 3.58
TEPIC 6 7.16 7.16 7.16 7.16
Filler Melamine 1.07 1.07 1.07 1.07
Silica 7.88 7.88 7.88 7.88
Barium sulfate 17.53 17.53 17.53 17.53

Pigment 0.47 0.47 0.47 0.47
Additive BYK-354 7 0.72 0.72 0.72 0.72
KS-66 8 0.72 0.72 0.72 0.72
Concentration adjusting solvent PGMEA 9 11.62 11.62 11.62 11.62

Note 1 Photopolymerization initiator manufactured by Ciba Specialty Chemicals, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane 2 Photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd., 2,4- Diethylthioxanthone 3 Nippon Kayaku Co., Ltd. acrylate monomer, dipentaerythritol hexaacrylate 4 Nippon Kayaku Co., Ltd. acrylate monomer, trimethylolpropane triacrylate 5 JER epoxy resin, 3, 3 ', 4, 4'- Tetramethylbiphenyl-4,4′-diglycidyl ether 6 Nissan Chemical Co., Ltd. epoxy resin, triglycidyl isocyanurate 7 Big Chemie leveling agent 8 Shin-Etsu Chemical Co., Ltd. defoaming agent 9 Propylene glycol monomethyl ether acetate

Table 2
Examples Comparative examples
1 2 3 1
Evaluation item tackiness ○ ○ ○ ×
Photosensitivity ○ ○ ○ ×
Surface gloss ○ ○ ○ △
Adhesiveness ○ ○ ○ ○
Pencil hardness 8H 5H 6H 7H
Solvent resistance ○ ○ ○ ○
Acid resistance ○ ○ ○ ×
Heat resistance ○ ○ ○ ○
Gold plating resistance ○ ○ ○ ×

As is apparent from the results in Table 2, the photosensitive resin composition of the present invention has high tackiness without tackiness, and its cured film is also excellent in surface gloss, acid resistance, gold plating resistance, etc. Suitable for printed circuit boards.

Claims (6)

Cresol novolak-type epoxy resin obtained from metacresol and / or paracresol as 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 polybasic acid anhydride (d) is reacted with a monocarboxylic acid compound (b) having an ethylenically unsaturated group and a monocarboxylic acid compound (c) having at least two hydroxyl groups in the molecule as an optional component. A photosensitive resin composition containing an ethylenically unsaturated group-containing polycarboxylic acid resin (A), a photopolymerization initiator (B), a crosslinking agent (C), and a curing agent (D) obtained by reacting. 2. The photosensitive resin composition according to claim 1, 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 photosensitive resin composition according to claim 1 or 2 , wherein the ethylenically unsaturated group-containing polycarboxylic acid resin (A) has a solid acid value of 40 to 160 mgKOH / g. 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 1-3 with an active energy ray. The base material which has the layer of the hardened | cured material obtained by the manufacturing method of Claim 4 . An article comprising the substrate according to claim 5 .