WO2022163701A1 - Photosensitive resin composition and printed wiring board manufacturing method - Google Patents

Photosensitive resin composition and printed wiring board manufacturing method Download PDF

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Publication number
WO2022163701A1
WO2022163701A1 PCT/JP2022/002892 JP2022002892W WO2022163701A1 WO 2022163701 A1 WO2022163701 A1 WO 2022163701A1 JP 2022002892 W JP2022002892 W JP 2022002892W WO 2022163701 A1 WO2022163701 A1 WO 2022163701A1
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Prior art keywords
photosensitive resin
resin composition
viscosity
photosensitive
dpa
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PCT/JP2022/002892
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French (fr)
Japanese (ja)
Inventor
薫 間中
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太陽インキ製造株式会社
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Priority to JP2022578444A priority Critical patent/JP7439307B2/en
Publication of WO2022163701A1 publication Critical patent/WO2022163701A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition, and particularly to a photosensitive resin composition that is suitably used for forming a solder resist. Furthermore, the present invention also relates to a method for producing a printed wiring board using the photosensitive resin composition.
  • solder is applied to the board on which the circuit pattern is formed in order to prevent solder from adhering to unnecessary parts.
  • a solder-resist layer is formed on the area except for the connection holes.
  • the solder resist layer is currently formed by applying a photosensitive resin composition to the substrate, drying it, exposing it, and developing it to form a pattern.
  • the mainstream method is to use a so-called photosolder resist, in which a patterned resin is fully cured by heating or light irradiation.
  • a coating method such as a spray coating method or a curtain coating method has attracted attention.
  • a spray coating method, a curtain coating method, and the like are required to have a low viscosity in consideration of their characteristics.
  • an object of the present invention is to provide a photosensitive resin composition which, even when adjusted to have a low viscosity, exhibits excellent covering properties and developability for the edges of the circuit of a printed wiring board during application. be.
  • Another object of the present invention is to provide a printed wiring board capable of forming a sufficiently thick solder resist layer even on the edges of the circuit of the printed wiring board by applying the above photosensitive resin composition in a low viscosity region. is to provide a manufacturing method of
  • the present inventors have found that when applying a photosensitive resin composition containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent to a low viscosity, the photosensitive resin
  • the above problems can be solved by adjusting the viscosity and volume resistivity of the composition so as to satisfy a specific relational expression.
  • the present inventors found that the viscosity of the photosensitive resin composition and the volume resistivity value are in a linear relationship, and found that the applicability of the photosensitive resin composition in the low viscosity region and the developability of the photosensitive resin composition As a result of considering the balance, it was found that the above problem can be solved by setting the slope of the above-described straight line within a specific range.
  • the present invention is based on such findings.
  • the photosensitive resin composition according to the present invention is a photosensitive resin composition containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent, Let A (dPa s) be the viscosity of the photosensitive resin composition at 25°C, and B (M ⁇ ) be the volume resistivity of the photosensitive resin composition at 25°C.
  • the photosensitive resin composition preferably further contains a quaternary ammonium salt compound.
  • the quaternary ammonium salt compound is preferably at least one selected from tetrabutylammonium bromide and tetrapropylammonium bromide.
  • the organic solvent is selected from the group consisting of diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monoethyl ether acetate. At least one is preferred.
  • the photosensitive resin composition is preferably used for coating with a spray coater, and more preferably used for coating with an electrostatic spray.
  • the photosensitive resin composition is preferably used for solder resist formation.
  • a method for manufacturing a printed wiring board having a solder resist layer wherein the above photosensitive resin composition is applied onto a substrate with a spray coater, exposed to light and heat.
  • a method for manufacturing a printed wiring board is provided, which comprises curing with at least one of them to form a solder resist layer.
  • the present invention it is possible to provide a photosensitive resin composition that is excellent in covering the edges of the circuit of a printed wiring board, even when the composition is adjusted to have a low viscosity. Furthermore, the photosensitive resin composition of the present invention can be excellent in developability. Further, according to another aspect of the present invention, a sufficiently thick solder resist layer can be formed on the edge portion of the circuit of the printed wiring board by applying the above photosensitive resin composition in a low viscosity region. A method for manufacturing a printed wiring board can be provided.
  • the photosensitive resin composition according to the present invention contains at least a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer (reactive diluent), and an organic solvent (non-reactive diluent), and contains a quaternary ammonium salt.
  • Other ingredients such as compounds, photoinitiators, colorants, curing catalysts, inorganic fillers, and additives may also be included.
  • the viscosity of the photosensitive resin composition can be adjusted using the above organic solvent and, if necessary, an inorganic filler or the like.
  • the viscosity of the photosensitive resin composition is not particularly limited, and can be adjusted to a suitable viscosity by appropriately diluting with propylene glycol monomethyl ether.
  • the photosensitive resin composition is measured according to the JIS Z8803:2011 10 conical-flat rotary viscometer viscosity measurement method at 25° C., 5 rpm, 30 seconds, and 1°34′ ⁇ R24 as a cone rotor.
  • the viscosity measured using a cone-plate viscometer is 300 dPa ⁇ s or less at 25° C., preferably 200 dPa ⁇ s or less.
  • the photosensitive resin composition is usually adjusted to 1.3 dPa ⁇ s or more and 5.0 dPa ⁇ s or less, preferably 1.5 dPa ⁇ s or more and 4.5 dPa ⁇ s or less, when electrostatic spray coating is applied. used after adjusting to By diluting the photosensitive resin composition in the above viscosity range and using it, it is possible to form a resin layer with a sufficient thickness on the edge portion of the circuit of the printed wiring board at the time of coating in the low viscosity region. Heat resistance and plating resistance can be improved.
  • the viscosity of the photosensitive resin composition at 25 ° C. is defined as A (dPa s), and the volume resistivity of the photosensitive resin composition at 25 ° C. is defined as B (M ⁇ ).
  • a (dPa s) the volume resistivity of the photosensitive resin composition at 25 ° C.
  • B (M ⁇ ) the volume resistivity value at A 2 is B 2 (M ⁇ )
  • (A 1 ⁇ A 2 )/(B 1 ⁇ B 2 )” indicates the change in volume resistivity when the photosensitive resin composition is diluted to a suitable viscosity range for coating. .
  • a photosensitive resin composition in which the above “(A 1 ⁇ A 2 )/(B 1 ⁇ B 2 )” is less than 1.4 has a too large increase in the volume resistivity value when the viscosity increases, so the viscosity is low. It is considered that the adhesiveness of the photosensitive resin composition is deteriorated when it is adjusted to and applied.
  • a photosensitive resin composition having a value of more than 40 is considered to have poor developability because the increase in volume resistivity is too small when the viscosity increases.
  • the value of B2 is usually 0.01 to 5.0, preferably 0.03 to 2.0 , more preferably 0.05 to 1.2, still more preferably 0.07. ⁇ 1.1, and even more preferably between 0.1 and 1.0. If the value of B2 is within the above range, it can be developed and has excellent covering properties for the edge part of the circuit of the printed wiring board when applied in the low viscosity region, so that unevenness of the uneven part of the substrate can be reduced. , the underlying circuit can be prevented from being exposed.
  • the volume resistivity of the photosensitive resin composition at 25° C. is measured by the electrode (electrode area : 1 cm 2 , distance between electrodes: 1 cm) is immersed.
  • carboxyl group-containing resin conventionally known various resins having a carboxyl group in the molecule can be used. By including a carboxyl group-containing resin in the photosensitive resin composition, alkali developability can be imparted to the photosensitive resin composition.
  • a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance.
  • the ethylenically unsaturated double bonds are preferably derived from acrylic acid or methacrylic acid or derivatives thereof.
  • composition photocurable
  • a compound having a plurality of ethylenically unsaturated groups in the molecule i.e., a photosensitive
  • the composition is made photosensitive by using a photopolymerizable monomer together.
  • carboxyl group-containing resins include the following compounds (both oligomers and polymers).
  • Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylates, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols, and polyether-based Polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • a diisocyanate such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin (Reaction product with carboxylic acid compound having ethylenically unsaturated double bond such as meth)acrylic acid Partial acid anhydride modified product, carboxyl group-containing photosensitive urethane obtained by polyaddition reaction of carboxyl group-containing dialcohol compound and diol compound resin.
  • a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin (Reaction product with carboxylic acid compound having ethylenically unsaturated double bond such as meth)acrylic acid Partial acid anhydride modified product, carboxyl group-containing photosensitive urethane obtained by polyaddition reaction of carboxyl group-containing
  • one isocyanate group and one or more (meth)acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • a carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functionalities and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
  • Group-containing photosensitive resin A carboxyl obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group.
  • a bifunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is treated with a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid
  • a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • Carboxyl group-containing polyester resin to which acid anhydride is added.
  • an epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol;
  • a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
  • (11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group.
  • a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • a carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (1) to (11).
  • (meth)acrylate is a generic term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.
  • the acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g.
  • the acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g.
  • the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferable to be 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, the developability and storage stability can be improved. More preferably from 5,000 to 100,000.
  • the blending amount of the carboxyl group-containing resin is preferably 20% by mass or more and 60% by mass or less in terms of solid content in the photosensitive resin composition. By making it 20% by mass or more, the strength of the cured coating film can be improved. Further, when the content is 60% by mass or less, the viscosity becomes appropriate, and the ability to cover the edges of the circuit of the printed wiring board at the time of coating with a spray coater is improved. More preferably, it is 30% by mass or more and 50% by mass or less.
  • thermosetting resins used in the present invention include known and commonly used resins such as amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, oxetane compounds and episulfide resins.
  • Preferred thermosetting resins among these are epoxy resins.
  • epoxy resins examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type epoxy resin. Resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, and the like. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Examples of commercially available epoxy resins include jER 828, 806, 807, 834, YX8000, 8034 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059 manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • Examples include ST-3000, EPICLON 830, 840, 850 and N-695 manufactured by DIC Corporation, and RE-310S manufactured by Nippon Kayaku Co., Ltd.
  • the epoxy group equivalent weight of the epoxy resin in the photosensitive resin composition is preferably 0.3 to 3.0 per 1 carboxyl group equivalent weight of the carboxyl group-containing resin in terms of solid content.
  • amount By setting the amount to 0.3 equivalent or more, it is possible to prevent carboxyl groups from remaining in the cured film and obtain good heat resistance, alkali resistance, electrical insulation, and the like.
  • compounding amount By setting the above compounding amount to 3.0 equivalents or less, it is possible to prevent the low-molecular-weight cyclic (thio)ether group from remaining in the dried coating film, and to ensure good strength, etc. of the cured coating film. can.
  • thermosetting catalyst can be further added to the photosensitive resin composition of the present invention.
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzyl amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphos
  • commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., and U-CAT 3513N manufactured by San-Apro Co., Ltd. , trade names of dimethylamine compounds), DBU, DBN, U-CAT SA 102 (all of which are amidine compounds and salts thereof).
  • it is not limited to these, and it may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or any one that promotes the reaction between at least one of an epoxy group and an oxetanyl group and a carboxyl group.
  • a mixture of seeds or more may be used.
  • the amount of the thermosetting catalyst is calculated as a solid content of cyclic (thio) in the molecule. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the thermosetting component having an ether group.
  • the photosensitive resin composition of the present invention contains a photosensitive monomer.
  • a photosensitive monomer is a monomer having an ethylenically unsaturated double bond.
  • Examples of photosensitive monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates.
  • hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate
  • glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol
  • N,N-dimethylacrylamide N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide
  • aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate
  • hexanediol trimethylolpropane
  • Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as their ethyloxide adducts, propylene oxide adducts, or ⁇ -caprolactone adducts
  • Epoxy acrylate resin obtained by reacting acrylic acid with polyfunctional epoxy resin such as cresol novolak type epoxy resin, and half urethane of hydroxy acrylate such as pentaerythritol triacrylate and diisocyanate such as isophorone diisocyanate for the hydroxyl group of the epoxy acrylate resin.
  • polyfunctional epoxy resin such as cresol novolak type epoxy resin
  • half urethane of hydroxy acrylate such as pentaerythritol triacrylate and diisocyanate such as isophorone diisocyanate for the hydroxyl group of the epoxy acrylate resin.
  • Such an epoxy acrylate resin can improve the photocurability without deteriorating the dryness to the touch.
  • the amount of the photosensitive monomer compounded in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, in terms of solid content. Part by mass or less.
  • the amount of the photosensitive monomer compounded in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, in terms of solid content. Part by mass or less.
  • the photosensitive monomer especially when using a carboxyl group-containing non-photosensitive resin that does not have an ethylenically unsaturated double bond, it is necessary to use a photosensitive monomer in combination to make the composition photocurable. It is valid.
  • Organic solvents used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol and butyl carbitol.
  • propylene glycol monomethyl ether dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Esters such as monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, solvent naphtha, etc.
  • organic solvents esters are preferred, and diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether are more preferred, and propylene glycol monomethyl ether acetate is preferred. , dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether are more preferred.
  • These organic solvents may be used individually by 1 type, and may use 2 or more types together. The blending amount of the organic solvent can be appropriately set according to the desired viscosity of the photosensitive resin composition. It is preferable that these organic solvents are provided for industrial use, are unsealed, take out the required amount, and are used immediately.
  • Quaternary ammonium salt compound A quaternary ammonium salt compound can be further added to the photosensitive resin composition of the present invention.
  • Quaternary ammonium salt compounds include, for example, tetraalkyl (or aryl) ammonium compounds. Specific examples include tetraalkylammonium halides, tetraalkylammonium acetates, tetraalkylammonium hydrogensulfate, tetraalkylammonium hydrogensulfate, tetramethylammonium hydroxide and the like.
  • quaternary ammonium salt compounds it is preferable to use tetraalkylammonium halide from the viewpoint of improving the covering property of the edge portion of the circuit of the printed wiring board during coating with a spray coater.
  • quaternary phosphonium salt compounds and tertiary sulfonium salt compounds may also be used.
  • a quaternary ammonium salt compound can be used individually or in combination of 2 or more types.
  • tetraalkylanimonium halides include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetradecylammonium bromide, trimethylcetylammonium bromide, triethylcetylammonium bromide, and triethylmethylammonium bromide.
  • lauryltrimethylammonium bromide trioctylmethylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, phenyltrimethylammonium bromide, phenyltriethylammonium bromide, hexyltrimethylammonium bromide, octyltrimethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, dococenyloctadecyltrimethylammonium bromide, dilauryldimethylammonium bromide, distearyldimethylammonium bromide,
  • tetraalkylammonium acetate examples include tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, benzyltrimethylammonium acetate, benzyltriethylammonium acetate, and benzyltributylammonium acetate.
  • tetraalkylammonium hydrogensulfate examples include tetramethylammonium hydrogensulfate, tetraethylammonium hydrogensulfate, and tetrabutylammonium hydrogensulfate.
  • tetramethylammonium hydroxide examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, monohydroxyethyl-trimethylammonium hydroxide, and the like. ;
  • quaternary ammonium salt compounds include, in addition to the above, di-cured tallow alkyldimethylammonium acetate, benzyldimethylammonium perchlorate, and the like.
  • Particularly preferable quaternary ammonium salt compounds include tetrabutylammonium bromide and tetrapropylammonium bromide.
  • the amount of the quaternary ammonium salt compound is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 100 parts by mass of the carboxyl group-containing resin in terms of solid content in the photosensitive resin composition. is 0.5 parts by mass or more and 3 parts by mass or less. If the amount of the inorganic filler to be blended is within the above range, properties such as adhesion, mechanical strength, and coefficient of linear expansion of the cured product can be improved while adjusting the desired viscosity.
  • photopolymerization initiators can be used for photopolymerization of the above photosensitive resin composition.
  • photopolymerization initiators include oxime ester photopolymerization initiators having an oxime ester group, titanocene photopolymerization initiators, ⁇ -aminoacetophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and the like. mentioned. Of these, ⁇ -aminoacetophenone-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators are preferred.
  • a photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.
  • ⁇ -aminoacetophenone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, Examples include N,N-dimethylaminoacetophenone.
  • Commercially available products include Omnirad 369, Omnirad 379 and Omnirad 907 manufactured by IGM Resins.
  • acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2, 6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and the like.
  • Commercially available products include Omnirad 819 manufactured by IGM Resins.
  • a photoinitiation aid or a sensitizer may be used in combination with the photopolymerization initiator described above.
  • Photoinitiation aids or sensitizers include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, and the like.
  • Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are particularly preferred. Inclusion of a thioxanthone compound can improve deep-part curability.
  • thioxanthone compounds include DETX and ITX manufactured by LAMBSON. These compounds can be used as a photopolymerization initiator in some cases, but are preferably used in combination with the photopolymerization initiator. Also, the photoinitiation aids or sensitizers may be used singly or in combination of two or more.
  • photopolymerization initiators since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, the sensitivity may be lowered in some cases, and they may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the composition. It absorbs light of a specific wavelength as needed to increase the photoreactivity of the surface, change the line shape and opening of the resist to vertical, tapered, and reverse tapered shapes, and improve the accuracy of the line width and opening diameter. can be improved.
  • the photosensitive resin composition of the present invention may further contain an inorganic filler.
  • inorganic fillers include barium sulfate, barium titanate, silicon oxide powder, fine powder silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. be done.
  • the amount of the inorganic filler compounded in the photosensitive resin composition is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is 150 mass parts or less. If the amount of the inorganic filler to be blended is within the above range, properties such as adhesion, mechanical strength, and coefficient of linear expansion of the cured product can be improved while adjusting the desired viscosity.
  • a coloring agent can be further added to the photosensitive resin composition of the present invention.
  • known coloring agents such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments can be used. However, it is preferable not to contain a halogen from the viewpoint of environmental load reduction and influence on the human body.
  • red colorants examples include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone colorants.
  • -Index C.I.; issued by The Society of Dyers and Colorists) numbered ones.
  • Monoazo red coloring agents include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 and the like.
  • Disazo-based red colorants include Pigment Red 37, 38, 41 and the like.
  • Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, 208 and the like.
  • Perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 and the like.
  • Examples of diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, 272 and the like.
  • Examples of condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242.
  • Examples of anthraquinone-based red colorants include Pigment Red 168, 177, 216 and Solvent Red 149, 150, 52, 207.
  • examples of quinacridone-based red colorants include Pigment Red 122, 202, 206, 207, 209 and the like.
  • blue colorants include phthalocyanine-based and anthraquinone-based coloring agents, and pigment-based compounds classified as pigments, for example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67 and the like can be used as dyes.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • yellow colorants examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone colorants.
  • anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like.
  • isoindolinone-based yellow colorants include Pigment Yellow 110, 109, 139, 179, 185 and the like.
  • condensed azo yellow colorants examples include Pigment Yellow 93, 94, 95, 128, 155, 166, 180 and the like.
  • benzimidazolone yellow colorants examples include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like.
  • Pigment Yellow 1 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183 and the like.
  • Disazo yellow coloring agents include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. are mentioned.
  • coloring agents such as purple, orange, brown, black, and white may be added.
  • Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29 , 32, 36, 38, 42, Solvent Violet 13, 36, C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, Titanium oxide etc. are mentioned.
  • the photosensitive resin composition of the present invention may further contain components such as antifoaming agents, flame retardants, adhesion promoters, antioxidants, ultraviolet absorbers and dispersants, if necessary.
  • components such as antifoaming agents, flame retardants, adhesion promoters, antioxidants, ultraviolet absorbers and dispersants, if necessary.
  • antifoaming agents flame retardants, adhesion promoters, antioxidants, ultraviolet absorbers and dispersants
  • those known in the field of electronic materials can be used.
  • At least one of known and commonly used additives such as
  • the photosensitive resin composition according to the present invention is coated on a substrate including a circuit-formed substrate by dip coating, flow coating, roll coating, bar coating, spray coating, screen printing, curtain coating, or the like. Apply according to method.
  • application by the spray coating method can be preferably used.
  • application by an electrostatic spray coating method can be used more preferably.
  • the photosensitive resin composition according to the present invention is particularly suitable for forming cured films in printed wiring boards, and can be used for forming solder resists, interlayer insulating materials, marking inks, coverlays, and solder dams. can. Among these, it can be suitably used for forming a solder resist. Moreover, the photosensitive resin composition according to the present invention may be one-component or two-component or more.
  • the above photosensitive resin composition is applied on a substrate with a spray coater, exposed, and cured by at least one of light and heat to form a solder resist layer. to form.
  • a solder resist layer An example of the method for forming the solder resist layer will be described below.
  • the solder resist layer is adjusted to a viscosity suitable for the coating method of the photosensitive resin composition, is applied to the entire surface of the circuit-formed substrate by a spray coater, and is included in the composition at a temperature of about 60 to 100 ° C.
  • a tack-free dry coating film can be formed.
  • the film thickness after drying is preferably 30 to 50 ⁇ m.
  • a patterned photomask After that, it is selectively exposed to active energy rays through a patterned photomask by a contact method (or a non-contact method), and the unexposed areas are developed with a dilute alkaline aqueous solution (eg, 0.3 to 3% aqueous solution of sodium carbonate). Then, a resist pattern is formed. Further, for example, by heating to a temperature of about 140 to 180° C. for thermal curing, a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed. can be done.
  • Base materials used for the circuit-formed substrate include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene/PPO. ⁇ Copper-clad laminates of all grades (FR-4, etc.) using materials such as copper-clad laminates for high-frequency circuits using cyanate ester, etc., other polyimide films, PET films, glass substrates, ceramic substrates, Wafer plates and the like can be mentioned.
  • low-pressure mercury lamps low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. are suitable as irradiation light sources used for active energy ray irradiation.
  • a laser beam or the like can also be used as an active energy ray.
  • Examples of the developing method include a dipping method, a shower method, a spray method, and a brush method.
  • Examples of the developing solution include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate Dilute alkaline aqueous solutions such as ammonia and amines can be used.
  • This reaction product was cooled to 80 to 90° C., 106 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and taken out.
  • the carboxyl group-containing resin thus obtained had a solid content of 65%, a solid acid value of 100 mgKOH/g, and a weight average molecular weight Mw of about 3,500.
  • the measurement of the weight average molecular weight of the obtained resin was measured by GPC.
  • the unexposed area of the photosensitive resin composition was removed by developing with a 1% sodium carbonate aqueous solution. Thereafter, the photosensitive resin composition was thermally cured at 150° C. for 60 minutes in a hot air circulating drying oven to prepare an evaluation substrate.
  • the covering property of the circuit edge portion was evaluated according to the following criteria, and the evaluation results are shown in Tables 3 and 4. [Evaluation criteria] A: The circuit was very well covered with the resist. ⁇ : The circuit was sufficiently covered with the resist. ⁇ : A thin portion of the resist was generated on the circuit. x: An extremely thin portion of the resist was generated on the circuit.
  • solder heat resistance> A solder flow test was performed at 260° C. for 30 seconds using a rosin-based flux on the evaluation board prepared in ⁇ Covering property of the circuit edge>, and the solder heat resistance was evaluated according to the following criteria. Shown in Tables 3 and 4. It should be noted that those evaluated for developability as "x" were not evaluated, and the evaluation result was given as "-”. [Evaluation criteria] ⁇ : No peeling occurred. ⁇ : There was some peeling. x: Peeling occurred.
  • ⁇ Electroless plating resistance> The evaluation substrates prepared in ⁇ Circuit Edge Covering Properties> were evaluated for electroless plating resistance according to the following criteria, and the evaluation results are shown in Tables 3 and 4. It should be noted that those evaluated for developability as "x" were not evaluated, and the evaluation result was given as "-”. [Evaluation criteria] ⁇ : No peeling occurred. ⁇ : There was some peeling. x: Peeling occurred.

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Abstract

[Problem] To provide a photosensitive resin composition that has, even when being adjusted to have a low viscosity, excellent developing properties and ability to cover edge portions of a circuit of a printed wiring board when being applied. [Means] The photosensitive resin composition according to the present invention is characterized by containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent, and is characterized in that, when the viscosity of the photosensitive resin composition at 25°C is defined as A (dPa·s) and the volume resistivity value of the photosensitive resin composition at 25°C is defined as B (MΩ) and when the viscosity of the photosensitive resin composition is adjusted to A1=5.0 (dPa·s) and A2=1.5(dPa·s) by using propylene glycol monomethyl ether, B1 (MΩ) that represents the volume resistivity value at A1 and B2 (MΩ) that represents the volume resistivity value at A2 satisfy formula: 1.4≤(A1-A2)/(B1-B2)≤40.

Description

感光性樹脂組成物およびプリント配線板の製造方法Photosensitive resin composition and method for producing printed wiring board
　本発明は、感光性樹脂組成物に関し、特に、ソルダーレジスト形成用として好適に用いられる感光性樹脂組成物に関する。さらに、本発明は、該感光性樹脂組成物を用いたプリント配線板の製造方法にも関する。 The present invention relates to a photosensitive resin composition, and particularly to a photosensitive resin composition that is suitably used for forming a solder resist. Furthermore, the present invention also relates to a method for producing a printed wiring board using the photosensitive resin composition.
　一般に、電子機器などに用いられるプリント配線板において、プリント配線板に電子部品を実装する際には、不要な部分にはんだが付着するのを防止するために、回路パターンの形成された基板上の接続孔を除く領域にソルダーレジスト層が形成されている。 In general, when mounting electronic components on a printed wiring board used in electronic equipment, etc., solder is applied to the board on which the circuit pattern is formed in order to prevent solder from adhering to unnecessary parts. A solder-resist layer is formed on the area except for the connection holes.
　近年の電子機器の軽薄短小化によるプリント配線板の高精度、高密度化に伴い、現在、ソルダーレジスト層は、基板に感光性樹脂組成物を塗布、乾燥し、露光、現像によりパターン形成した後、パターン形成された樹脂を加熱ないし光照射によって本硬化させる、いわゆるフォトソルダーレジストによって形成されるのが主流となっている。さらに近年では生産性の観点から、スプレーコート法やカーテンコート法などの塗布方法が注目されている。スプレーコート法やカーテンコート法などは特性を考慮すると低粘度であるものが求められている。 With the increasing precision and density of printed wiring boards due to the recent miniaturization of electronic devices, the solder resist layer is currently formed by applying a photosensitive resin composition to the substrate, drying it, exposing it, and developing it to form a pattern. The mainstream method is to use a so-called photosolder resist, in which a patterned resin is fully cured by heating or light irradiation. Furthermore, in recent years, from the viewpoint of productivity, a coating method such as a spray coating method or a curtain coating method has attracted attention. A spray coating method, a curtain coating method, and the like are required to have a low viscosity in consideration of their characteristics.
　従来、基板上に有機溶剤を含む感光性樹脂組成物を塗布した場合、一見ムラが無く感光性樹脂組成物を塗布できていたとしても、塗布後や乾燥時にはじきやダレが発生して、乾燥後に均一な乾燥塗膜を形成できないという技術的課題が存在した。このような技術的課題に対して、カルボキシル基含有樹脂、熱硬化性樹脂、感光性モノマー、および有機溶剤を含む低粘度の感光性樹脂組成物において、有機溶剤として、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、およびプロピレングリコールモノメチルエーテルアセテートを用いることが提案されている（特許文献１参照。） Conventionally, when a photosensitive resin composition containing an organic solvent is applied on a substrate, even if the photosensitive resin composition can be applied without unevenness at first glance, repelling or sagging occurs after application or during drying. There was a technical problem that a uniform dry coating could not be formed afterwards. In order to solve such technical problems, in a low-viscosity photosensitive resin composition containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, The use of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate has been proposed (see Patent Document 1).
特開２０１９－１７４７８８号公報JP 2019-174788 A
　しかしながら、特許文献１で提案されている低粘度の感光性樹脂組成物を塗布した際にプリント配線板の回路のエッジ部分に十分な膜厚の樹脂層を形成することができないという技術的課題を発見した。 However, there is a technical problem that when the low-viscosity photosensitive resin composition proposed in Patent Document 1 is applied, a resin layer having a sufficient thickness cannot be formed on the edge portion of the circuit of the printed wiring board. discovered.
　したがって、本発明の目的は、低粘度に調整した場合であっても、塗布時のプリント配線板の回路のエッジ部分へのカバーリング性と現像性に優れる感光性樹脂組成物を提供することである。また、本発明の別の目的は、上記の感光性樹脂組成物を用いた低粘度領域での塗布によってプリント配線板の回路のエッジ部分にも十分な厚みのソルダーレジスト層を形成できるプリント配線板の製造方法を提供することである。 Accordingly, an object of the present invention is to provide a photosensitive resin composition which, even when adjusted to have a low viscosity, exhibits excellent covering properties and developability for the edges of the circuit of a printed wiring board during application. be. Another object of the present invention is to provide a printed wiring board capable of forming a sufficiently thick solder resist layer even on the edges of the circuit of the printed wiring board by applying the above photosensitive resin composition in a low viscosity region. is to provide a manufacturing method of
　本発明者らは、鋭意研究した結果、カルボキシル基含有樹脂、熱硬化性樹脂、感光性モノマー、および有機溶剤を含む感光性樹脂組成物を低粘度に調整して塗布する際に、感光性樹脂組成物の粘度および体積固有抵抗値を特定の関係式を満たすように調節することで、上記課題を解決できるとの知見を得た。すなわち、本発明者は感光性樹脂組成物の粘度と体積固有抵抗値が直線関係にあることを見出し、感光性樹脂組成物の低粘度領域での塗布性と感光性樹脂組成物の現像性のバランスを考慮した結果、前述の直線の傾きが特定の範囲内にあることで、上記課題を解決できるとの知見を得た。本発明はかかる知見によるものである。 As a result of intensive research, the present inventors have found that when applying a photosensitive resin composition containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent to a low viscosity, the photosensitive resin We have found that the above problems can be solved by adjusting the viscosity and volume resistivity of the composition so as to satisfy a specific relational expression. That is, the present inventors found that the viscosity of the photosensitive resin composition and the volume resistivity value are in a linear relationship, and found that the applicability of the photosensitive resin composition in the low viscosity region and the developability of the photosensitive resin composition As a result of considering the balance, it was found that the above problem can be solved by setting the slope of the above-described straight line within a specific range. The present invention is based on such findings.
　すなわち、本発明による感光性樹脂組成物は、カルボキシル基含有樹脂、熱硬化性樹脂、感光性モノマー、および有機溶剤を含む感光性樹脂組成物であって、
　前記感光性樹脂組成物の２５℃における粘度をＡ（ｄＰａ・ｓ）とし、前記感光性樹脂組成物の２５℃における体積固有抵抗値をＢ（ＭΩ）とすると、プロピレングリコールモノメチルエーテルを用いて前記感光性樹脂組成物の粘度をＡ１＝５．０（ｄＰａ・ｓ）、Ａ２＝１．５（ｄＰａ・ｓ）に調整した時、Ａ１の時の体積固有抵抗値をＢ１（ＭΩ）、Ａ２の時の体積固有抵抗値をＢ２（ＭΩ）が、
下記式：
　１．４≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦４０
を満たすことを特徴とするものである。 That is, the photosensitive resin composition according to the present invention is a photosensitive resin composition containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent,
Let A (dPa s) be the viscosity of the photosensitive resin composition at 25°C, and B (MΩ) be the volume resistivity of the photosensitive resin composition at 25°C. When the viscosity of the photosensitive resin composition is adjusted to A 1 = 5.0 (dPa s) and A 2 = 1.5 (dPa s), the volume resistivity value at A 1 is B 1 (MΩ ), the volume specific resistance value at A 2 is B 2 (MΩ),
The formula below:
1.4≦(A 1 −A 2 )/(B 1 −B 2 )≦40
It is characterized by satisfying
　本発明の態様においては、感光性樹脂組成物は、第四級アンモニウム塩化合物をさらに含むことが好ましい。 In the aspect of the present invention, the photosensitive resin composition preferably further contains a quaternary ammonium salt compound.
　本発明の態様においては、前記第四級アンモニウム塩化合物が、テトラブチルアンモニウムブロマイド、およびテトラプロピルアンモニウムブロマイドから選択される少なくとも１種であることが好ましい。 In the aspect of the present invention, the quaternary ammonium salt compound is preferably at least one selected from tetrabutylammonium bromide and tetrapropylammonium bromide.
　本発明の態様においては、前記有機溶剤が、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、およびプロピレングリコ－ルモノエチルエーテルアセテートからなる群から選択される少なくとも１種であることが好ましい。 In aspects of the present invention, the organic solvent is selected from the group consisting of diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monoethyl ether acetate. At least one is preferred.
　本発明の態様においては、感光性樹脂組成物は、スプレーコーターでの塗布に用いられることが好ましく、特に静電スプレーでの塗布に用いられることがより好ましい。 In the aspect of the present invention, the photosensitive resin composition is preferably used for coating with a spray coater, and more preferably used for coating with an electrostatic spray.
　本発明の態様においては、感光性樹脂組成物は、ソルダーレジスト形成用として用いられることが好ましい。 In the aspect of the present invention, the photosensitive resin composition is preferably used for solder resist formation.
　本発明の別の態様によれば、ソルダーレジスト層を備えるプリント配線板の製造方法であって、上記の感光性樹脂組成物を、スプレーコーターで基板上に塗布し、露光し、光および熱のいずれか少なくとも１種によって硬化させて、ソルダーレジスト層を形成することを特徴とするプリント配線板の製造方法が提供される。 According to another aspect of the present invention, there is provided a method for manufacturing a printed wiring board having a solder resist layer, wherein the above photosensitive resin composition is applied onto a substrate with a spray coater, exposed to light and heat. A method for manufacturing a printed wiring board is provided, which comprises curing with at least one of them to form a solder resist layer.
　本発明によれば、低粘度に調整した場合の塗布であってもプリント配線板の回路のエッジ部分へのカバーリング性に優れる感光性樹脂組成物を提供することができる。さらに、本発明の感光性樹脂組成物は、現像性に優れるものにすることができる。また、本発明の別の形態によれば、上記の感光性樹脂組成物を用いて、低粘度領域での塗布によってプリント配線板の回路のエッジ部分にも十分な厚みのソルダーレジスト層を形成できるプリント配線板の製造方法を提供することができる。 According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in covering the edges of the circuit of a printed wiring board, even when the composition is adjusted to have a low viscosity. Furthermore, the photosensitive resin composition of the present invention can be excellent in developability. Further, according to another aspect of the present invention, a sufficiently thick solder resist layer can be formed on the edge portion of the circuit of the printed wiring board by applying the above photosensitive resin composition in a low viscosity region. A method for manufacturing a printed wiring board can be provided.
［感光性樹脂組成物］
　本発明による感光性樹脂組成物について説明する。本発明による感光性樹脂組成物は、少なくとも、カルボキシル基含有樹脂、熱硬化性樹脂、感光性モノマー（反応性希釈剤）、および有機溶剤（非反応性希釈剤）を含み、第四級アンモニウム塩化合物、光重合開始剤、着色剤、硬化触媒、無機充填材、および添加剤等の他の成分をさらに含んでもよい。 [Photosensitive resin composition]
A photosensitive resin composition according to the present invention will be described. The photosensitive resin composition according to the present invention contains at least a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer (reactive diluent), and an organic solvent (non-reactive diluent), and contains a quaternary ammonium salt. Other ingredients such as compounds, photoinitiators, colorants, curing catalysts, inorganic fillers, and additives may also be included.
　本発明においては、上記の有機溶剤や、必要に応じて無機充填材等を用いて感光性樹脂組成物の粘度を調節することができる。感光性樹脂組成物の粘度は、特に限定されずに、適宜、プロピレングリコールモノメチルエーテルで希釈して、好適な粘度に調節することができる。通常、感光性樹脂組成物は、ＪＩＳ　Ｚ８８０３：２０１１の１０　円すい－平板形回転粘度計による粘度測定方法に準じ、２５℃、５ｒｐｍ、３０秒値とし、コーン・ロータとして１°３４′×Ｒ２４を用いたコーンプレート型粘度計（東機産業株式会社製、ＴＶＥ－３３Ｈ）を用いて測定した粘度が、２５℃で３００ｄＰａ・ｓ以下であり、好ましくは２００ｄＰａ・ｓ以下である。感光性樹脂組成物は、静電スプレー塗布の際には、通常１．３ｄＰａ・ｓ以上５．０ｄＰａ・ｓ以下に調節して用いられ、好ましくは１．５ｄＰａ・ｓ以上４．５ｄＰａ・ｓ以下に調節して用いられる。感光性樹脂組成物を上記粘度範囲に希釈して用いることで、低粘度領域での塗布時のプリント配線板の回路のエッジ部分に十分な膜厚の樹脂層を形成することができるため、はんだ耐熱性やめっき耐性を向上させることができる。 In the present invention, the viscosity of the photosensitive resin composition can be adjusted using the above organic solvent and, if necessary, an inorganic filler or the like. The viscosity of the photosensitive resin composition is not particularly limited, and can be adjusted to a suitable viscosity by appropriately diluting with propylene glycol monomethyl ether. Usually, the photosensitive resin composition is measured according to the JIS Z8803:2011 10 conical-flat rotary viscometer viscosity measurement method at 25° C., 5 rpm, 30 seconds, and 1°34′×R24 as a cone rotor. The viscosity measured using a cone-plate viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) is 300 dPa·s or less at 25° C., preferably 200 dPa·s or less. The photosensitive resin composition is usually adjusted to 1.3 dPa·s or more and 5.0 dPa·s or less, preferably 1.5 dPa·s or more and 4.5 dPa·s or less, when electrostatic spray coating is applied. used after adjusting to By diluting the photosensitive resin composition in the above viscosity range and using it, it is possible to form a resin layer with a sufficient thickness on the edge portion of the circuit of the printed wiring board at the time of coating in the low viscosity region. Heat resistance and plating resistance can be improved.
　本発明においては、感光性樹脂組成物の２５℃における粘度をＡ（ｄＰａ・ｓ）とし、感光性樹脂組成物の２５℃における体積固有抵抗値をＢ（ＭΩ）とすると、プロピレングリコールモノメチルエーテルを用いて前記感光性樹脂組成物の粘度をＡ１＝５．０（ｄＰａ・ｓ）、Ａ２＝１．５（ｄＰａ・ｓ）に調整した時、Ａ１の時の体積固有抵抗値をＢ１（ＭΩ）、Ａ２の時の体積固有抵抗値をＢ２（ＭΩ）が、
下記式：
　１．４≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦４０
を満たすものであり、好ましくは、
　２．０≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦３５
を満たすものであり、より好ましくは、
　３．０≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦３０
を満たすものであり、さらに好ましくは、
　５．０≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦２５
を満たすものであり、さらにより好ましくは、
　１０≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦２０
を満たすものである。
　本発明においては、上記式における「（Ａ１－Ａ２）／（Ｂ１－Ｂ２）」が１．４以上４０以下である感光性樹脂組成物を用いることで、現像可能で、低粘度領域での塗布時のプリント配線板の回路のエッジ部分へのカバーリング性に優れるため、基板の凹凸部のムラを低減し、下地の回路の露出を防止することができる。この理由は必ずしも明らかではないが以下のように推察される。上記「（Ａ１－Ａ２）／（Ｂ１－Ｂ２）」は、感光性樹脂組成物を塗布する際に好適な粘度範囲に希釈した場合の体積固有抵抗値の変化を示すものである。上記「（Ａ１－Ａ２）／（Ｂ１－Ｂ２）」が１．４未満となる感光性樹脂組成物は、粘度上昇時の体積固有抵抗値の上昇幅が大き過ぎるため、低粘度に調整し塗布した際の感光性樹脂組成物の付着性が悪化すると考えられる。一方、４０超となる感光性樹脂組成物は、粘度上昇時の体積固有抵抗値の上昇幅が小さ過ぎるため、感光性樹脂組成物の現像性が悪化すると考えられる。
　また、Ｂ２の値は、通常０．０１～５．０であり、好ましくは０．０３～２．０であり、より好ましくは０．０５～１．２であり、さらに好ましくは０．０７～１．１であり、さらにより好ましくは０．１～１．０である。Ｂ２の値が上記範囲内であれば、現像可能で、低粘度領域での塗布時のプリント配線板の回路のエッジ部分へのカバーリング性に優れるため、基板の凹凸部のムラを低減し、下地の回路の露出を防止することができる。　なお、本発明においては、感光性樹脂組成物の２５℃における体積固有抵抗値は、感光性組成物中に静電テスター（旭サナック株式会社製、商品名：ＥＭ－ＩＶ）の電極（電極面積：１ｃｍ２、電極間距離：１ｃｍ）を浸漬したときの体積固有抵抗値（ＭΩ）である。以下、本発明による感光性樹脂組成物を構成する各成分について説明する。 In the present invention, the viscosity of the photosensitive resin composition at 25 ° C. is defined as A (dPa s), and the volume resistivity of the photosensitive resin composition at 25 ° C. is defined as B (MΩ). When the viscosity of the photosensitive resin composition is adjusted to A 1 = 5.0 ( dPa s) and A 2 = 1.5 (dPa s) using B 1 (MΩ), the volume resistivity value at A 2 is B 2 (MΩ),
The formula below:
1.4≦(A 1 −A 2 )/(B 1 −B 2 )≦40
and preferably
2.0≦(A 1 −A 2 )/(B 1 −B 2 )≦35
and more preferably,
3.0≦(A 1 −A 2 )/(B 1 −B 2 )≦30
and more preferably,
5.0≦(A 1 −A 2 )/(B 1 −B 2 )≦25
and more preferably,
10≦(A 1 −A 2 )/(B 1 −B 2 )≦20
It satisfies
In the present invention, by using a photosensitive resin composition in which “(A 1 −A 2 )/(B 1 −B 2 )” in the above formula is 1.4 or more and 40 or less, developable, low-viscosity Since it is excellent in covering the edges of the circuit of the printed wiring board when applied in a region, it is possible to reduce the unevenness of the unevenness of the substrate and prevent the underlying circuit from being exposed. The reason for this is not necessarily clear, but is presumed as follows. The above “(A 1 −A 2 )/(B 1 −B 2 )” indicates the change in volume resistivity when the photosensitive resin composition is diluted to a suitable viscosity range for coating. . A photosensitive resin composition in which the above “(A 1 −A 2 )/(B 1 −B 2 )” is less than 1.4 has a too large increase in the volume resistivity value when the viscosity increases, so the viscosity is low. It is considered that the adhesiveness of the photosensitive resin composition is deteriorated when it is adjusted to and applied. On the other hand, a photosensitive resin composition having a value of more than 40 is considered to have poor developability because the increase in volume resistivity is too small when the viscosity increases.
Also, the value of B2 is usually 0.01 to 5.0, preferably 0.03 to 2.0 , more preferably 0.05 to 1.2, still more preferably 0.07. ~1.1, and even more preferably between 0.1 and 1.0. If the value of B2 is within the above range, it can be developed and has excellent covering properties for the edge part of the circuit of the printed wiring board when applied in the low viscosity region, so that unevenness of the uneven part of the substrate can be reduced. , the underlying circuit can be prevented from being exposed. In the present invention, the volume resistivity of the photosensitive resin composition at 25° C. is measured by the electrode (electrode area : 1 cm 2 , distance between electrodes: 1 cm) is immersed. Each component constituting the photosensitive resin composition according to the present invention will be described below.
［カルボキシル基含有樹脂］
　カルボキシル基含有樹脂としては、分子中にカルボキシル基を有している従来公知の各種樹脂を使用できる。感光性樹脂組成物が、カルボキシル基含有樹脂を含むことにより、感光性樹脂組成物に対しアルカリ現像性を付与することができる。特に、分子中にエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂が、光硬化性や耐現像性の面から好ましい。エチレン性不飽和二重結合は、アクリル酸もしくはメタクリル酸またはそれらの誘導体由来であることが好ましい。エチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のみを用いる場合、組成物を光硬化性とするためには、後述する分子中に複数のエチレン性不飽和基を有する化合物、即ち感光性モノマーを併用することによって、組成物を感光性とする。
　カルボキシル基含有樹脂の具体例としては、以下のような化合物（オリゴマーおよびポリマーのいずれでもよい）を挙げることができる。 [Carboxyl Group-Containing Resin]
As the carboxyl group-containing resin, conventionally known various resins having a carboxyl group in the molecule can be used. By including a carboxyl group-containing resin in the photosensitive resin composition, alkali developability can be imparted to the photosensitive resin composition. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. The ethylenically unsaturated double bonds are preferably derived from acrylic acid or methacrylic acid or derivatives thereof. When only a carboxyl group-containing resin having no ethylenically unsaturated double bonds is used, in order to make the composition photocurable, a compound having a plurality of ethylenically unsaturated groups in the molecule, i.e., a photosensitive The composition is made photosensitive by using a photopolymerizable monomer together.
Specific examples of carboxyl group-containing resins include the following compounds (both oligomers and polymers).
　（１）（メタ）アクリル酸等の不飽和カルボン酸と、スチレン、α－メチルスチレン、低級アルキル（メタ）アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。 (1) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene.
　（２）脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネートと、ジメチロールプロピオン酸、ジメチロールブタン酸等のカルボキシル基含有ジアルコール化合物およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールＡ系アルキレンオキサイド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。 (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols, and polyether-based Polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
　（３）ジイソシアネートと、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂等の２官能エポキシ樹脂と（メタ）アクリル酸等のエチレン性不飽和二重結合を有する者カルボン酸化合物との反応物部分酸無水物変性物、カルボキシル基含有ジアルコール化合物およびジオール化合物の重付加反応によるカルボキシル基含有感光性ウレタン樹脂。 (3) a diisocyanate, a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Reaction product with carboxylic acid compound having ethylenically unsaturated double bond such as meth)acrylic acid Partial acid anhydride modified product, carboxyl group-containing photosensitive urethane obtained by polyaddition reaction of carboxyl group-containing dialcohol compound and diol compound resin.
　（４）前記（２）または（３）の樹脂の合成中に、ヒドロキシアルキル（メタ）アクリレート等の分子内に１つの水酸基と１つ以上の（メタ）アクリロイル基を有する化合物を加え、末端（メタ）アクリル化したカルボキシル基含有感光性ウレタン樹脂。 (4) During the synthesis of the resin (2) or (3), a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added, and the terminal ( Meta) acrylated carboxyl group-containing photosensitive urethane resin.
　（５）前記（２）または（３）の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子内に１つのイソシアネート基と１つ以上の（メタ）アクリロイル基を有する化合物を加え末端（メタ）アクリル化したカルボキシル基含有感光性ウレタン樹脂。 (5) During the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth)acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin that is terminally (meth)acrylated by adding a compound having
　（６）２官能またはそれ以上の多官能（固形）エポキシ樹脂に（メタ）アクリル酸を反応させ、側鎖に存在する水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 (6) A carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functionalities and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
　（７）２官能（固形）エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に（メタ）アクリル酸を反応させ、生じた水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 (7) A carboxyl obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group. Group-containing photosensitive resin.
　（８）２官能オキセタン樹脂にアジピン酸、フタル酸、ヘキサヒドロフタル酸等のジカルボン酸を反応させ、生じた１級の水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の２塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。 (8) A bifunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is treated with a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Carboxyl group-containing polyester resin to which acid anhydride is added.
　（９）１分子中に複数のエポキシ基を有するエポキシ化合物に、ｐ－ヒドロキシフェネチルアルコール等の１分子中に少なくとも１個のアルコール性水酸基と１個のフェノール性水酸基を有する化合物と、（メタ）アクリル酸等の不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、アジピン酸等の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (9) an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol; Maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid to the alcoholic hydroxyl group of the reaction product obtained by reacting with a monocarboxylic acid containing an unsaturated group such as acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
　（１０）１分子中に複数のフェノール性水酸基を有する化合物とエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (10) A reaction obtained by reacting a reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide and reacting an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting the product with a polybasic acid anhydride.
　（１１）１分子中に複数のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネート等の環状カーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
　（１２）前記（１）～（１１）の樹脂にさらに１分子内に１つのエポキシ基と１つ以上の（メタ）アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。
　なお、本明細書において、（メタ）アクリレートとは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語で、他の類似の表現についても同様である。 (12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (1) to (11).
In this specification, (meth)acrylate is a generic term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.
　カルボキシル基含有樹脂の酸価は、４０～１５０ｍｇＫＯＨ／ｇであることが好ましい。カルボキシル基含有樹脂の酸価が４０ｍｇＫＯＨ／ｇ以上とすることにより、アルカリ現像が良好になる。また、酸価を１５０ｍｇＫＯＨ／ｇを以下とすることで、良好なレジストパターンの描画をし易くできる。より好ましくは、５０～１３０ｍｇＫＯＨ／ｇである。 The acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g. By setting the acid value of the carboxyl group-containing resin to 40 mgKOH/g or more, the alkali development becomes good. Also, by setting the acid value to 150 mgKOH/g or less, it is possible to facilitate drawing of a good resist pattern. More preferably, it is 50 to 130 mgKOH/g.
　カルボキシル基含有樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に２，０００～１５０，０００であることが好ましい。重量平均分子量が２，０００以上とすることにより、タックフリー性能や解像度を向上させることができる。また、重量平均分子量が１５０，０００以下とすることで、現像性や貯蔵安定性を向上させることができる。より好ましくは、５，０００～１００，０００である。 Although the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferable to be 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, the developability and storage stability can be improved. More preferably from 5,000 to 100,000.
　カルボキシル基含有樹脂の配合量は、感光性樹脂組成物中において、固形分換算で、２０質量％以上６０質量％以下であることが好ましい。２０質量％以上とすることにより硬化塗膜強度を向上させることができる。また６０質量％以下とすることで粘性が適当となり、スプレーコーターでの塗布時のプリント配線板の回路のエッジ部分へのカバーリング性が向上する。より好ましくは、３０質量％以上５０質量％以下である。 The blending amount of the carboxyl group-containing resin is preferably 20% by mass or more and 60% by mass or less in terms of solid content in the photosensitive resin composition. By making it 20% by mass or more, the strength of the cured coating film can be improved. Further, when the content is 60% by mass or less, the viscosity becomes appropriate, and the ability to cover the edges of the circuit of the printed wiring board at the time of coating with a spray coater is improved. More preferably, it is 30% by mass or more and 50% by mass or less.
［熱硬化性樹脂］
　本発明で用いられる熱硬化性樹脂としては、アミノ樹脂、マレイミド化合物、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、エポキシ化合物、オキセタン化合物、エピスルフィド樹脂などの公知慣用のものが挙げられる。これらの中でも好ましい熱硬化性樹脂は、エポキシ樹脂である。 [Thermosetting resin]
The thermosetting resins used in the present invention include known and commonly used resins such as amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, oxetane compounds and episulfide resins. Preferred thermosetting resins among these are epoxy resins.
　使用することができるエポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡのノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂等が挙げられる。これらエポキシ樹脂は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of epoxy resins that can be used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type epoxy resin. Resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, and the like. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.
　市販されるエポキシ樹脂としては、例えば、三菱ケミカル株式会社製のｊＥＲ　８２８、８０６、８０７、８３４、ＹＸ８０００、８０３４、日鉄ケミカル＆マテリアル株式会社製のＹＤ－１２８、ＹＤＦ－１７０、ＺＸ－１０５９、ＳＴ－３０００、ＤＩＣ株式会社製のＥＰＩＣＬＯＮ　８３０、８４０、８５０、Ｎ－６９５および日本化薬株式会社製のＲＥ－３１０Ｓ等が挙げられる。 Examples of commercially available epoxy resins include jER 828, 806, 807, 834, YX8000, 8034 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059 manufactured by Nippon Steel Chemical & Materials Co., Ltd. Examples include ST-3000, EPICLON 830, 840, 850 and N-695 manufactured by DIC Corporation, and RE-310S manufactured by Nippon Kayaku Co., Ltd.
　感光性樹脂組成物におけるエポキシ樹脂のエポキシ基の当量は、固形分換算で、カルボキシル基含有樹脂のカルボキシル基の当量１に対して、０．３～３．０であることが好ましい。０．３当量以上とすることで、硬化被膜におけるカルボキシル基の残存を防止して、良好な耐熱性や耐アルカリ性、電気絶縁性等を得ることができる。一方、上記配合量を３．０当量以下とすることで、低分子量の環状（チオ）エーテル基が乾燥塗膜に残存することを防止して、硬化被膜の強度等を良好に確保することができる。 The epoxy group equivalent weight of the epoxy resin in the photosensitive resin composition is preferably 0.3 to 3.0 per 1 carboxyl group equivalent weight of the carboxyl group-containing resin in terms of solid content. By setting the amount to 0.3 equivalent or more, it is possible to prevent carboxyl groups from remaining in the cured film and obtain good heat resistance, alkali resistance, electrical insulation, and the like. On the other hand, by setting the above compounding amount to 3.0 equivalents or less, it is possible to prevent the low-molecular-weight cyclic (thio)ether group from remaining in the dried coating film, and to ensure good strength, etc. of the cured coating film. can.
［熱硬化触媒］
　本発明の感光性樹脂組成物には、熱硬化触媒をさらに配合することができる。熱硬化触媒としては、例えば、イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、４－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール等のイミダゾール誘導体；ジシアンジアミド、ベンジルジメチルアミン、４－（ジメチルアミノ）－Ｎ，Ｎ－ジメチルベンジルアミン、４－メトキシ－Ｎ，Ｎ－ジメチルベンジルアミン、４－メチル－Ｎ，Ｎ－ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物；トリフェニルフォスフィン等のリン化合物等が挙げられる。また、市販されているものとしては、例えば四国化成工業株式会社製２ＭＺ－Ａ、２ＭＺ－ＯＫ、２ＰＨＺ、２Ｐ４ＢＨＺ、２Ｐ４ＭＨＺ（いずれもイミダゾール系化合物の商品名）、サンアプロ株式会社製のＵ－ＣＡＴ　３５１３Ｎ、ジメチルアミン系化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ－ＣＡＴ　ＳＡ　１０２（いずれもアミジン化合物およびその塩）などが挙げられる。特に、これらに限られるものではなく、エポキシ樹脂やオキセタン化合物の熱硬化触媒、もしくはエポキシ基およびオキセタニル基の少なくともいずれか１種とカルボキシル基の反応を促進するものであればよく、単独でまたは２種以上を混合して使用してもかまわない。また、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、２，４－ジアミノ－６－メタクリロイルオキシエチル－Ｓ－トリアジン、２－ビニル－２，４－ジアミノ－Ｓ－トリアジン、２－ビニル－４，６－ジアミノ－Ｓ－トリアジン・イソシアヌル酸付加物、２，４－ジアミノ－６－メタクリロイルオキシエチル－Ｓ－トリアジン・イソシアヌル酸付加物等のＳ－トリアジン誘導体を用いることもできる。 [Thermal curing catalyst]
A thermosetting catalyst can be further added to the photosensitive resin composition of the present invention. Examples of thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzyl amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., and U-CAT 3513N manufactured by San-Apro Co., Ltd. , trade names of dimethylamine compounds), DBU, DBN, U-CAT SA 102 (all of which are amidine compounds and salts thereof). In particular, it is not limited to these, and it may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or any one that promotes the reaction between at least one of an epoxy group and an oxetanyl group and a carboxyl group. A mixture of seeds or more may be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as S-triazine/isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adducts can also be used.
　熱硬化触媒の配合量は、感光性樹脂組成物中に、エポキシ樹脂等分子中に環状（チオ）エーテル基を有する熱硬化性成分を含む場合、固形分換算で、分子中に環状（チオ）エーテル基を有する熱硬化性成分１００質量部に対して、好ましくは０．１質量部以上２０質量部以下、より好ましくは０．５質量部以上１５．０質量部以下である。 When the photosensitive resin composition contains a thermosetting component having a cyclic (thio) ether group in the molecule, such as an epoxy resin, the amount of the thermosetting catalyst is calculated as a solid content of cyclic (thio) in the molecule. It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the thermosetting component having an ether group.
［感光性モノマー］
　本発明の感光性樹脂組成物は、感光性モノマーを含む。感光性モノマーは、エチレン性不飽和二重結合を有するモノマーである。感光性モノマーとしては、例えば、慣用公知のポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ウレタン（メタ）アクリレート、カーボネート（メタ）アクリレート、エポキシ（メタ）アクリレートなどが挙げられる。具体的には、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類；エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類；Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス－ヒドロキシエチルイソシアヌレートなどの多価アルコールまたはこれらのエチレオキサイド付加物、プロピレンオキサイド付加物、もしくはε－カプロラクトン付加物などの多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート、およびこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類；グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類；前記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類およびメラミンアクリレート、および前記アクリレートに対応する各メタクリレート類の少なくともいずれか１種から適宜選択して用いることができる。このような感光性モノマーは、反応性希釈剤としても用いることができる。 [Photosensitive monomer]
The photosensitive resin composition of the present invention contains a photosensitive monomer. A photosensitive monomer is a monomer having an ethylenically unsaturated double bond. Examples of photosensitive monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N,N-dimethylacrylamide , N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as their ethyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate, bisphenol A di Polyvalent acrylates such as acrylates and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyvalent acrylates; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, and polyester polyols, or urethane acrylated via diisocyanate, and the above acrylates can be appropriately selected from at least one of the methacrylates corresponding to and used. Such photosensitive monomers can also be used as reactive diluents.
　クレゾールノボラック型エポキシ樹脂などの多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレートなどのヒドロキシアクリレートとイソホロンジイソシアネートなどのジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物などを感光性モノマーとして用いてもよい。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる。 Epoxy acrylate resin obtained by reacting acrylic acid with polyfunctional epoxy resin such as cresol novolak type epoxy resin, and half urethane of hydroxy acrylate such as pentaerythritol triacrylate and diisocyanate such as isophorone diisocyanate for the hydroxyl group of the epoxy acrylate resin. You may use the epoxy urethane acrylate compound etc. which reacted the compound as a photosensitive monomer. Such an epoxy acrylate resin can improve the photocurability without deteriorating the dryness to the touch.
　感光性モノマーの配合量は、感光性樹脂組成物中に、固形分換算で、カルボキシル基含有樹脂１００質量部に対して好ましくは１質量部以上５０質量部以下、より好ましくは５質量部以上４０質量部以下である。感光性モノマーの配合量を１質量部以上とすることにより、感光性樹脂組成物の光硬化性が向上する。また、配合量を５０質量部以下とすることにより、硬化塗膜硬度を向上させることができる。 The amount of the photosensitive monomer compounded in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, in terms of solid content. Part by mass or less. By setting the blending amount of the photosensitive monomer to 1 part by mass or more, the photocurability of the photosensitive resin composition is improved. Further, by setting the blending amount to 50 parts by mass or less, the hardness of the cured coating film can be improved.
　感光性モノマーは、特にエチレン性不飽和二重結合を有さないカルボキシル基含有非感光性樹脂を使用した場合、組成物を光硬化性とするために感光性モノマーを併用する必要があるため、有効である。 The photosensitive monomer, especially when using a carboxyl group-containing non-photosensitive resin that does not have an ethylenically unsaturated double bond, it is necessary to use a photosensitive monomer in combination to make the composition photocurable. It is valid.
［有機溶剤］
　本発明で用いられる有機溶剤には、メチルエチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類；オクタン、デカン等の脂肪族炭化水素類；石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤等が挙げられる。これらの有機溶剤の中でも、エステル類が好ましく、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、およびプロピレングリコールモノメチルエーテル等がより好ましく、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、およびプロピレングリコールモノメチルエーテルがさらに好ましい。これらの有機溶剤は、１種を単独で用いてもよく、２種以上を併用してもよい。有機溶剤の配合量は、感光性樹脂組成物を目的の粘度に応じて適宜設定することができる。これらの有機溶剤は工業用に提供されたものを開封して必要量取り出してすぐに使用し、使用後は密栓をして冷暗所に保管するのが好ましい。 [Organic solvent]
Organic solvents used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol and butyl carbitol. , propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Esters such as monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, solvent naphtha, etc. and petroleum-based solvents. Among these organic solvents, esters are preferred, and diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether are more preferred, and propylene glycol monomethyl ether acetate is preferred. , dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether are more preferred. These organic solvents may be used individually by 1 type, and may use 2 or more types together. The blending amount of the organic solvent can be appropriately set according to the desired viscosity of the photosensitive resin composition. It is preferable that these organic solvents are provided for industrial use, are unsealed, take out the required amount, and are used immediately.
［第四級アンモニウム塩化合物］
　本発明の感光性樹脂組成物には、第四級アンモニウム塩化合物をさらに配合することができる。第四級アンモニウム塩化合物としては、例えば、テトラアルキル（またはアリール）アンモニウム化合物が挙げられる。具体的には、テトラアルキルアンモニウムハライド、酢酸テトラアルキルアンモニウム、硫酸水素テトラアルキルアンモニウム、硫酸水素テトラアルキルアンモニウム、テトラメチルアンモニウムハイドロオキサイド等が挙げられる。これらの中でもスプレーコーターでの塗布時のプリント配線板の回路のエッジ部分のカバーリング性の向上の観点から、テトラアルキルアンモニウムハライドを使用することが好ましい。なお、第四級アンモニウム塩化合物の他にも、第四級ホスホニウム塩化合物、第三級スルホニウム塩化合物を使用してもよい。第四級アンモニウム塩化合物は単独で又は２種以上を組み合わせて使用することができる。 [Quaternary ammonium salt compound]
A quaternary ammonium salt compound can be further added to the photosensitive resin composition of the present invention. Quaternary ammonium salt compounds include, for example, tetraalkyl (or aryl) ammonium compounds. Specific examples include tetraalkylammonium halides, tetraalkylammonium acetates, tetraalkylammonium hydrogensulfate, tetraalkylammonium hydrogensulfate, tetramethylammonium hydroxide and the like. Among these, it is preferable to use tetraalkylammonium halide from the viewpoint of improving the covering property of the edge portion of the circuit of the printed wiring board during coating with a spray coater. In addition to the quaternary ammonium salt compounds, quaternary phosphonium salt compounds and tertiary sulfonium salt compounds may also be used. A quaternary ammonium salt compound can be used individually or in combination of 2 or more types.
　上記テトラアルキルアニモニウムハライドとして具体的には、テトラメチルアンモニウムブロマイド、テトラエチルアンモニウムブロマイド、テトラプロピルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド、テトラデシルアンモニウムブロマイド、トリメチルセチルアンモニウムブロマイド、トリエチルセチルアンモニウムブロマイド、トリエチルメチルアンモニウムブロマイド、ラウリルトリメチルアンモニウムブロマイド、トリオクチルメチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムブロマイド、ベンジルトリエチルアンモニウムブロマイド、ベンジルトリブチルアンモニウムブロマイド、フェニルトリメチルアンモニウムブロマイド、フェニルトリエチルアンモニウムブロマイド、ヘキシルトリメチルアンモニウムブロマイド、オクチルトリメチルアンモニウムブロマイド、デシルトリメチルアンモニウムブロマイド、ドデシルトリメチルアンモニウムブロマイド、テトラデシルトリメチルアンモニウムブロマイド、ヘキサデシルトリメチルアンモニウムブロマイド、オクタデシルトリメチルアンモニウムブロマイド、ドコセニルオクタデシルトリメチルアンモニウムブロマイド、ジラウリルジメチルアンモニウムブロマイド、ジステアリルジメチルアンモニウムブロマイド等；
　エチルトリメチルアンモニウムアイオダイド、エチルトリ－ｎ－プロピルアンモニウムアイオダイド、フェニルトリエチルアンモニウムアイオダイド、フェニルトリメチルアンモニウムアイオダイド、テトラ－ｎ－アミルアンモニウムアイオダイド、テトラ－ｎ－ブチルアンモニウムアイオダイド、テトラエチルアンモニウムアイオダイド、テトラブチルアンモニウムアイオダイド、テトラ－ｎ－オクチルアンモニウムアイオダイド、テトラ－ｎ－プロピルアンモニウムアイオダイド、トリエチルベンジルアンモニウムアイオダイド等が挙げられる。 Specific examples of the tetraalkylanimonium halides include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetradecylammonium bromide, trimethylcetylammonium bromide, triethylcetylammonium bromide, and triethylmethylammonium bromide. , lauryltrimethylammonium bromide, trioctylmethylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, phenyltrimethylammonium bromide, phenyltriethylammonium bromide, hexyltrimethylammonium bromide, octyltrimethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, dococenyloctadecyltrimethylammonium bromide, dilauryldimethylammonium bromide, distearyldimethylammonium bromide, etc.;
ethyltrimethylammonium iodide, ethyltri-n-propylammonium iodide, phenyltriethylammonium iodide, phenyltrimethylammonium iodide, tetra-n-amylammonium iodide, tetra-n-butylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, tetra-n-octylammonium iodide, tetra-n-propylammonium iodide, triethylbenzylammonium iodide and the like.
　上記酢酸テトラアルキルアンモニウムとして具体的には、酢酸テトラメチルアンモニウム、酢酸テトラエチルアンモニウム、酢酸テトラブチルアンモニウム、酢酸ベンジルトリメチルアンモニウム、酢酸ベンジルトリエチルアンモニウム、酢酸ベンジルトリブチルアンモニウム；等が挙げられる。 Specific examples of the tetraalkylammonium acetate include tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, benzyltrimethylammonium acetate, benzyltriethylammonium acetate, and benzyltributylammonium acetate.
　上記硫酸水素テトラアルキルアンモニウムとして具体的には、硫酸水素テトラメチルアンモニウム、硫酸水素テトラエチルアンモニウム、硫酸水素テトラブチルアンモニウム等；が挙げられる。 Specific examples of the tetraalkylammonium hydrogensulfate include tetramethylammonium hydrogensulfate, tetraethylammonium hydrogensulfate, and tetrabutylammonium hydrogensulfate.
　上記テトラメチルアンモニウムハイドロオキサイドとして具体的には、テトラメチルアンモニウムハイドロオキサイド、テトラエチルアンモニウムハイドロオキサイド、テトラプロピルアンモニウムハイドロオキサイド、テトラブチルアンモニウムハイドロオキサイド、ベンジルトリメチルアンモニウムハイドロオキサイド、モノハイドロキシエチル・トリメチルアンモニウムハイドロオキサイド等；が挙げられる。 Specific examples of the tetramethylammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, monohydroxyethyl-trimethylammonium hydroxide, and the like. ;
　第四級アンモニウム塩化合物としては、上記以外にもジ硬化牛脂アルキルジメチルアンモニウムアセテート、ベンジルジメチルアンモニウムパークロレイトなどが挙げられる。 Examples of quaternary ammonium salt compounds include, in addition to the above, di-cured tallow alkyldimethylammonium acetate, benzyldimethylammonium perchlorate, and the like.
　第四級アンモニウム塩化合物としては、テトラブチルアンモニウムブロマイドおよびテトラプロピルアンモニウムブロマイド等が特に好ましいものとして挙げられる。 Particularly preferable quaternary ammonium salt compounds include tetrabutylammonium bromide and tetrapropylammonium bromide.
　第四級アンモニウム塩化合物の配合量は、感光性樹脂組成物中に、固形分換算で、カルボキシル基含有樹脂１００質量部に対して、好ましくは０．１質量部以上５質量部以下、より好ましくは０．５質量部以上３質量部以下である。無機充填材の配合量が上記範囲内であれば、所望の粘度に調節しながら、硬化物の密着性、機械的強度、線膨張係数などの特性を向上させることができる。 The amount of the quaternary ammonium salt compound is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 100 parts by mass of the carboxyl group-containing resin in terms of solid content in the photosensitive resin composition. is 0.5 parts by mass or more and 3 parts by mass or less. If the amount of the inorganic filler to be blended is within the above range, properties such as adhesion, mechanical strength, and coefficient of linear expansion of the cured product can be improved while adjusting the desired viscosity.
［光重合開始剤］
　本発明において、上記した感光性樹脂組成物を光重合させるために使用される光重合開始剤としては、公知のものを用いることができる。光重合開始剤としては、例えば、オキシムエステル基を有するオキシムエステル系光重合開始剤、チタノセン系光重合開始剤、α－アミノアセトフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤等が挙げられる。なかでも、α－アミノアセトフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤が好ましい。光重合開始剤は１種を単独で用いてもよく、２種以上を併用して用いてもよい。 [Photoinitiator]
In the present invention, known photopolymerization initiators can be used for photopolymerization of the above photosensitive resin composition. Examples of photopolymerization initiators include oxime ester photopolymerization initiators having an oxime ester group, titanocene photopolymerization initiators, α-aminoacetophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and the like. mentioned. Of these, α-aminoacetophenone-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators are preferred. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.
　α－アミノアセトフェノン系光重合開始剤としては、具体的には、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－１―プロパノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、Ｎ，Ｎ－ジメチルアミノアセトフェノンなどが挙げられる。市販品としては、ＩＧＭ　Ｒｅｓｉｎｓ社製Ｏｍｎｉｒａｄ　３６９、Ｏｍｎｉｒａｄ　３７９、Ｏｍｎｉｒａｄ　９０７などが挙げられる。 Specific examples of α-aminoacetophenone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, Examples include N,N-dimethylaminoacetophenone. Commercially available products include Omnirad 369, Omnirad 379 and Omnirad 907 manufactured by IGM Resins.
　アシルフォスフィンオキサイド系光重合開始剤としては、具体的には２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイドなどが挙げられる。市販品としては、ＩＧＭ　Ｒｅｓｉｎｓ社製Ｏｍｎｉｒａｄ　８１９などが挙げられる。 Specific examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2, 6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and the like. Commercially available products include Omnirad 819 manufactured by IGM Resins.
　上記した光重合開始剤と併用して、光開始助剤または増感剤を用いてもよい。光開始助剤または増感剤としては、ベンゾイン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、３級アミン化合物、およびキサントン化合物などを挙げることができる。特に、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン等のチオキサントン化合物を用いることが好ましい。チオキサントン化合物が含まれることにより、深部硬化性を向上させることができる。市販品としては、チオキサントン化合物としてＬＡＭＢＳＯＮ社製ＤＥＴＸ、ＩＴＸなどが挙げられる。これらの化合物は、光重合開始剤として用いることができる場合もあるが、光重合開始剤と併用して用いることが好ましい。また、光開始助剤または増感剤は１種類を単独で用いてもよく、２種以上を併用してもよい。 A photoinitiation aid or a sensitizer may be used in combination with the photopolymerization initiator described above. Photoinitiation aids or sensitizers include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, and the like. Thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone are particularly preferred. Inclusion of a thioxanthone compound can improve deep-part curability. Commercially available thioxanthone compounds include DETX and ITX manufactured by LAMBSON. These compounds can be used as a photopolymerization initiator in some cases, but are preferably used in combination with the photopolymerization initiator. Also, the photoinitiation aids or sensitizers may be used singly or in combination of two or more.
　なお、これら光重合開始剤、光開始助剤、および増感剤は、特定の波長を吸収するため、場合によっては感度が低くなり、紫外線吸収剤として機能することがある。しかしながら、これらは組成物の感度を向上させることだけの目的に用いられるものではない。必要に応じて特定の波長の光を吸収させて、表面の光反応性を高め、レジストのライン形状および開口を垂直、テーパー状、逆テーパー状に変化させるとともに、ライン幅や開口径の精度を向上させることができる。 In addition, since these photopolymerization initiators, photoinitiator aids, and sensitizers absorb specific wavelengths, the sensitivity may be lowered in some cases, and they may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the composition. It absorbs light of a specific wavelength as needed to increase the photoreactivity of the surface, change the line shape and opening of the resist to vertical, tapered, and reverse tapered shapes, and improve the accuracy of the line width and opening diameter. can be improved.
［無機充填材］
　本発明の感光性樹脂組成物には、無機充填材をさらに配合することができる。無機充填材としては、例えば、硫酸バリウム、チタン酸バリウム、酸化ケイ素粉、微粉状酸化ケイ素、無定形シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、雲母粉等が挙げられる。 [Inorganic filler]
The photosensitive resin composition of the present invention may further contain an inorganic filler. Examples of inorganic fillers include barium sulfate, barium titanate, silicon oxide powder, fine powder silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. be done.
　無機充填材の配合量は、感光性樹脂組成物中に、固形分換算で、カルボキシル基含有樹脂１００質量部に対して、好ましくは１０質量部以上２００質量部以下、より好ましくは２０質量部以上１５０質量部以下である。無機充填材の配合量が上記範囲内であれば、所望の粘度に調節しながら、硬化物の密着性、機械的強度、線膨張係数などの特性を向上させることができる。 The amount of the inorganic filler compounded in the photosensitive resin composition is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is 150 mass parts or less. If the amount of the inorganic filler to be blended is within the above range, properties such as adhesion, mechanical strength, and coefficient of linear expansion of the cured product can be improved while adjusting the desired viscosity.
［着色剤］
　本発明の感光性樹脂組成物には、着色剤をさらに配合することができる。着色剤としては、赤、青、緑、黄等の公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。但し、環境負荷低減並びに人体への影響の観点からハロゲンを含有しないことが好ましい。 [Coloring agent]
A coloring agent can be further added to the photosensitive resin composition of the present invention. As the coloring agent, known coloring agents such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments can be used. However, it is preferable not to contain a halogen from the viewpoint of environmental load reduction and influence on the human body.
　赤色着色剤としてはモノアゾ系、ジスアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系等があり、具体的には以下のようなカラ－インデックス（Ｃ．Ｉ．；ザ　ソサイエティ　オブ　ダイヤーズ　アンド　カラリスツ（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ）発行）番号が付されているものが挙げられる。 Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone colorants. -Index (C.I.; issued by The Society of Dyers and Colorists) numbered ones.
　モノアゾ系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，８，９，１２，１４，１５，１６，１７，２１，２２，２３，３１，３２，１１２，１１４，１４６，１４７，１５１，１７０，１８４，１８７，１８８，１９３，２１０，２４５，２５３，２５８，２６６，２６７，２６８，２６９等が挙げられる。また、ジスアゾ系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　３７，３８，４１等が挙げられる。また、モノアゾレーキ系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　４８：１，４８：２，４８：３，４８：４，４９：１，４９：２，５０：１，５２：１，５２：２，５３：１，５３：２，５７：１，５８：４，６３：１，６３：２，６４：１，６８等が挙げられる。また、ベンズイミダゾロン系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７１，１７５，１７６、１８５、２０８等が挙げられる。また、ぺリレン系赤色着色剤としては、Ｓｏｌｖｅｎｔ　Ｒｅｄ　１３５，１７９，Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２３，１４９，１６６，１７８，１７９，１９０，１９４，２２４等が挙げられる。また、ジケトピロロピロール系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４，２５５，２６４，２７０，２７２等が挙げられる。また、縮合アゾ系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　２２０，１４４，１６６，２１４，２２０，２２１，２４２等が挙げられる。また、アントラキノン系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１６８，１７７，２１６、Ｓｏｌｖｅｎｔ　Ｒｅｄ　１４９，１５０，５２，２０７等が挙げられる。また、キナクリドン系赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２，２０２，２０６，２０７，２０９等が挙げられる。 Monoazo red coloring agents include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 and the like. Disazo-based red colorants include Pigment Red 37, 38, 41 and the like. Further, as a monoazo lake-based red colorant, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53: 1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68 and the like. Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, 208 and the like. Perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 and the like. Examples of diketopyrrolopyrrole-based red colorants include Pigment Red 254, 255, 264, 270, 272 and the like. Examples of condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of anthraquinone-based red colorants include Pigment Red 168, 177, 216 and Solvent Red 149, 150, 52, 207. Further, examples of quinacridone-based red colorants include Pigment Red 122, 202, 206, 207, 209 and the like.
　青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント（Ｐｉｇｍｅｎｔ）に分類されている化合物が挙げられ、例えば、Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，６０、染料系としては、Ｓｏｌｖｅｎｔ　Ｂｌｕｅ　３５，６３，６８，７０，８３，８７，９４，９７，１２２，１３６，６７等を使用することができる。上記以外にも、金属置換若しくは無置換のフタロシアニン化合物も使用することができる。 Examples of blue colorants include phthalocyanine-based and anthraquinone-based coloring agents, and pigment-based compounds classified as pigments, for example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60. Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67 and the like can be used as dyes. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
　黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等が挙げられ、例えば、アントラキノン系黄色着色剤としては、Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ　１６３，Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　２４，１０８，１９３，１４７，１９９，２０２等が挙げられる。イソインドリノン系黄色着色剤としては、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１１０，１０９，１３９，１７９，１８５等が挙げられる。縮合アゾ系黄色着色剤としては、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　９３，９４，９５，１２８，１５５，１６６，１８０等が挙げられる。ベンズイミダゾロン系黄色着色剤としては、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１２０，１５１，１５４，１５６，１７５，１８１等が挙げられる。また、モノアゾ系黄色着色剤としては、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，９，１０，１２，６１，６２，６２：１，６５，７３，７４，７５，９７，１００，１０４，１０５，１１１，１１６，１６７，１６８，１６９，１８２，１８３等が挙げられる。また、ジスアゾ系黄色着色剤としては、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１２，１３，１４，１６，１７，５５，６３，８１，８３，８７，１２６，１２７，１５２，１７０，１７２，１７４，１７６，１８８，１９８等が挙げられる。 Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone colorants. For example, anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like. Examples of isoindolinone-based yellow colorants include Pigment Yellow 110, 109, 139, 179, 185 and the like. Examples of condensed azo yellow colorants include Pigment Yellow 93, 94, 95, 128, 155, 166, 180 and the like. Examples of benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like. Further, as a monoazo yellow colorant, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183 and the like. Disazo yellow coloring agents include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. are mentioned.
　その他、紫、オレンジ、茶色、黒、白等の着色剤を加えてもよい。具体的には、Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　１，６，７，８，９，１０，１１，１２，１３，１８，２０，２５，２６，２８，２９，３０，３１，３２、Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１９、２３、２９、３２、３６、３８、４２、Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ１３，３６、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１，５，１３，１４，１６，１７，２４，３４，３６，３８，４０，４３，４６，４９，５１，６１，６３，６４，７１，７３、ＰｉｇｍｅｎｔＢｒｏｗｎ　２３，２５、カーボンブラック、酸化チタン等が挙げられる。 In addition, coloring agents such as purple, orange, brown, black, and white may be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29 , 32, 36, 38, 42, Solvent Violet 13, 36, C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, carbon black, Titanium oxide etc. are mentioned.
［他の成分］
　本発明の感光性樹脂組成物には、必要に応じてさらに、消泡剤、難燃剤、密着促進剤、酸化防止剤、紫外線吸収剤、分散剤などの成分を配合することができる。これらは、電子材料の分野において公知の物を使用することができる。また、シリコーン系、フッ素系、高分子系などの消泡剤およびレベリング剤の少なくともいずれか１種、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、防錆剤、蛍光増白剤などのような公知慣用の添加剤類の少なくとも何れか一種を配合することができる。 [Other ingredients]
The photosensitive resin composition of the present invention may further contain components such as antifoaming agents, flame retardants, adhesion promoters, antioxidants, ultraviolet absorbers and dispersants, if necessary. As these, those known in the field of electronic materials can be used. In addition, at least one of silicone-based, fluorine-based, polymer-based defoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust inhibitors, fluorescent brighteners, etc. At least one of known and commonly used additives such as
　本発明による感光性樹脂組成物は回路形成された基板を含む基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スプレーコート法、スクリーン印刷法、カーテンコート法などの方法により塗布する。これらのなかでも、スプレーコート法による塗布を好適に使用することが出来る。特に、静電式のスプレーコート法による塗布をより好適に使用することが出来る。 The photosensitive resin composition according to the present invention is coated on a substrate including a circuit-formed substrate by dip coating, flow coating, roll coating, bar coating, spray coating, screen printing, curtain coating, or the like. Apply according to method. Among these, application by the spray coating method can be preferably used. In particular, application by an electrostatic spray coating method can be used more preferably.
　本発明による感光性樹脂組成物は、プリント配線板において、特に硬化膜を形成するために好適に使用され、ソルダーレジスト、層間絶縁材、マーキングインキ、カバーレイ、ソルダーダムの形成用として使用することができる。これらのなかでも、ソルダーレジスト形成用として好適に使用することができる。また、本発明による感光性樹脂組成物は、１液性でも２液性以上でもよい。 The photosensitive resin composition according to the present invention is particularly suitable for forming cured films in printed wiring boards, and can be used for forming solder resists, interlayer insulating materials, marking inks, coverlays, and solder dams. can. Among these, it can be suitably used for forming a solder resist. Moreover, the photosensitive resin composition according to the present invention may be one-component or two-component or more.
［プリント配線板の製造方法］
　本発明のプリント配線板の製造方法は、上記の感光性樹脂組成物を、スプレーコーターで基板上に塗布し、露光し、光および熱のいずれか少なくとも１種によって硬化させて、ソルダーレジスト層を形成するものである。以下、ソルダーレジスト層の形成方法について一例を説明する。 [Method for manufacturing printed wiring board]
In the method for producing a printed wiring board of the present invention, the above photosensitive resin composition is applied on a substrate with a spray coater, exposed, and cured by at least one of light and heat to form a solder resist layer. to form. An example of the method for forming the solder resist layer will be described below.
　ソルダーレジスト層は、感光性樹脂組成物を塗布方法に適した粘度に調整し、回路形成された基板上に、スプレーコーターにより全面塗布し、約６０～１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、タックフリーの乾燥塗膜を形成できる。乾燥後の膜厚は３０～５０μｍであることが好ましい。本発明の感光性樹脂組成物を用いることで、回路のエッジ部分にも十分な膜厚のソルダーレジスト層を設けることができる。その後、接触式（または非接触方式）により、パターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液（例えば０．３～３％炭酸ソーダ水溶液）により現像してレジストパターンが形成される。さらに、例えば約１４０～１８０℃の温度に加熱して熱硬化させることにより、耐熱性、耐薬品性、耐吸湿性、密着性、電気特性などの諸特性に優れた硬化塗膜を形成することができる。 The solder resist layer is adjusted to a viscosity suitable for the coating method of the photosensitive resin composition, is applied to the entire surface of the circuit-formed substrate by a spray coater, and is included in the composition at a temperature of about 60 to 100 ° C. By vaporizing and drying the organic solvent (temporary drying), a tack-free dry coating film can be formed. The film thickness after drying is preferably 30 to 50 μm. By using the photosensitive resin composition of the present invention, a solder resist layer having a sufficient thickness can be provided even on the edge portion of the circuit. After that, it is selectively exposed to active energy rays through a patterned photomask by a contact method (or a non-contact method), and the unexposed areas are developed with a dilute alkaline aqueous solution (eg, 0.3 to 3% aqueous solution of sodium carbonate). Then, a resist pattern is formed. Further, for example, by heating to a temperature of about 140 to 180° C. for thermal curing, a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed. can be done.
　上記回路形成された基板に使用される基材としては、紙フェノール、紙エポキシ、ガラス布エポキシ、ガラスポリイミド、ガラス布／不繊布エポキシ、ガラス布／紙エポキシ、合成繊維エポキシ、フッ素・ポリエチレン・ＰＰＯ・シアネートエステル等を用いた高周波回路用銅張積層版等の材質を用いたもので全てのグレード（ＦＲ－４等）の銅張積層版、その他ポリイミドフィルム、ＰＥＴフィルム、ガラス基板、セラミック基板、ウエハ板等を挙げることができる。 Base materials used for the circuit-formed substrate include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene/PPO.・Copper-clad laminates of all grades (FR-4, etc.) using materials such as copper-clad laminates for high-frequency circuits using cyanate ester, etc., other polyimide films, PET films, glass substrates, ceramic substrates, Wafer plates and the like can be mentioned.
　また、活性エネルギー線照射に用いられる照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプまたはメタルハライドランプなどが適当である。その他、レーザー光線なども活性エネルギー線として利用できる。 In addition, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. are suitable as irradiation light sources used for active energy ray irradiation. In addition, a laser beam or the like can also be used as an active energy ray.
　前記現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などの希アルカリ水溶液が使用できる。 Examples of the developing method include a dipping method, a shower method, a spray method, and a brush method. Examples of the developing solution include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate Dilute alkaline aqueous solutions such as ammonia and amines can be used.
　次に実施例を挙げて、本発明をさらに詳細に説明するが、本発明は、これら実施例に限定されるものではない。以下の調整、測定、評価はいずれも温度２５℃、相対湿度５０％の環境下で行った。 The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. All of the following adjustments, measurements, and evaluations were performed under an environment of 25° C. temperature and 50% relative humidity.
＜カルボキシル基含有樹脂の調製＞
　クレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製、ＥＰＩＣＬＯＮ　Ｎ－６９５、エポキシ当量：２２０）２２０部を撹拌機および還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート２１４部を加え、加熱溶解した。次に、重合禁止剤としてハイドロキノン０．１部と、反応触媒としてジメチルベンジルアミン２．０部を加えた。この混合物を９５～１０５℃に加熱し、アクリル酸７２部を徐々に滴下し、１６時間反応させた。この反応生成物を８０～９０℃まで冷却し、テトラヒドロフタル酸無水物１０６部を加え、８時間反応させ、冷却後、取り出した。このようにして得られたカルボキシル基含有樹脂は、固形分６５％、固形物の酸価１００ｍｇＫＯＨ／ｇ、重量平均分子量Ｍｗ約３，５００であった。 なお、得られた樹脂の重量平均分子量の測定は、ＧＰＣにより測定した。 <Preparation of carboxyl group-containing resin>
220 parts of a cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, epoxy equivalent: 220) is placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of carbitol acetate is added, and dissolved by heating. did. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. This reaction product was cooled to 80 to 90° C., 106 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and taken out. The carboxyl group-containing resin thus obtained had a solid content of 65%, a solid acid value of 100 mgKOH/g, and a weight average molecular weight Mw of about 3,500. In addition, the measurement of the weight average molecular weight of the obtained resin was measured by GPC.
＜感光性樹脂組成物の調製＞
［実施例１～６、比較例１～３］
　下記の表１および２中に示す配合に従い、フラスコ内に各成分を配合し、３０分間撹拌機で分散させ、それぞれ感光性樹脂組成物を調製した。表中の配合量は、質量部を示す。調整した感光性樹脂組成物を用いて下記のように評価を行った。 <Preparation of photosensitive resin composition>
[Examples 1 to 6, Comparative Examples 1 to 3]
In accordance with the formulations shown in Tables 1 and 2 below, each component was blended in a flask and dispersed with a stirrer for 30 minutes to prepare each photosensitive resin composition. The compounding amount in the table indicates parts by mass. The prepared photosensitive resin composition was evaluated as follows.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１および２中の各成分の詳細は、以下の通りである。
※１：上記で合成したカルボキシル基含有樹脂
※２：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル株式会社製、商品名：ｊＥＲ　８２８）
※３：トリアジン環エポキシ樹脂（日産化学工業株式会社製、商品名：ＴＥＰＩＣ－Ｓ）
※４：ジシアンジアミド（日本カーバイド工業株式会社製、商品名：ジシアンジアミド）
※５：メラミン（日化トレーディング株式会社製、商品名：メラミン）
※６：ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、商品名：ＫＡＹＡＲＡＤ　ＤＰＨＡ）
※７：２－［４－（メチルチオ）ベンゾイル］－２－（４－モルホリニル）プロパン（ＩＧＭ　Ｒｅｓｉｎｓ株式会社製、商品名：Ｏｍｎｉｒａｄ　９０７）
※８：２，４－ジエチルチオキサントン（日本化薬株式会社製、商品名：ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ）
※９：テトラブチルアンモニウムブロマイド（富士フイルム和光純薬株式会社製、商品名：テトラブチルアンモニウムブロミド）
※１０：テトラプロピルアンモニウムブロマイド（富士フイルム和光純薬株式会社製、商品名：Ｔｅｔｒａｐｒｏｐｙｌａｍｍｏｎｉｕｍ　Ｂｒｏｍｉｄｅ）
※１１：硫酸バリウム（堺化学工業株式会社製、商品名：Ｂ－１００）
※１２：フタロシアニングリーン（ＤＩＣ株式会社製、商品名：ＦＡＳＴＯＧＥＮ　ＧＲＥＥＮ　Ｓ）
※１３：消泡剤（信越化学工業株式会社製、商品名：ＫＳ－６６）
※１４：プロピレングリコールモノメチルエーテルアセテート
※１５：ジプロピレングリコールモノメチルエーテル
※１６：トルエン Details of each component in Tables 1 and 2 are as follows.
* 1: Carboxyl group-containing resin synthesized above * 2: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER 828)
*3: Triazine ring epoxy resin (manufactured by Nissan Chemical Industries, Ltd., product name: TEPIC-S)
*4: Dicyandiamide (manufactured by Nippon Carbide Industry Co., Ltd., trade name: dicyandiamide)
*5: Melamine (manufactured by Nikka Trading Co., Ltd., product name: melamine)
* 6: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)
*7: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (manufactured by IGM Resins, trade name: Omnirad 907)
* 8: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYACURE DETX-S)
*9: Tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: tetrabutylammonium bromide)
* 10: Tetrapropylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: Tetrapropylammonium Bromide)
* 11: Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., product name: B-100)
*12: Phthalocyanine green (manufactured by DIC Corporation, product name: FASTOGEN GREEN S)
*13: Antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-66)
*14: Propylene glycol monomethyl ether acetate *15: Dipropylene glycol monomethyl ether *16: Toluene
＜粘度の調整＞
　上記の実施例および比較例で調整した感光性樹脂組成物を、プロピレングリコールモノメチルエーテルを用いて希釈し、ＪＩＳ　Ｚ８８０３：２０１１の１０　円すい－平板形回転粘度計による粘度測定方法に準じ、２５℃、５ｒｐｍ、３０秒値とし、コーン・ロータとして１°３４′×Ｒ２４を用いたコーンプレート型粘度計（東機産業株式会社製、ＴＶＥ－３３Ｈ）を用いて５ｒｐｍで測定した粘度（ｄＰａ・ｓ）がＡ１＝５．０（ｄＰａ・ｓ）、Ａ２＝１．５（ｄＰａ・ｓ）の２種類の感光性樹脂組成物を調整した。粘度調整の作業は６０分以内で完了させた。希釈後の感光性樹脂組成物はポリエチレン容器にいれ、密栓した。 <Adjustment of viscosity>
The photosensitive resin compositions prepared in the above examples and comparative examples were diluted with propylene glycol monomethyl ether, and measured at 25° C., according to the viscosity measurement method using a 10 cone-plate rotary viscometer of JIS Z8803:2011. Viscosity (dPa s) measured at 5 rpm, 30 seconds, using a cone-plate viscometer (TVE-33H manufactured by Toki Sangyo Co., Ltd.) using a cone rotor of 1°34′×R24. prepared two types of photosensitive resin compositions with A 1 =5.0 (dPa·s) and A 2 =1.5 (dPa·s). The viscosity adjustment operation was completed within 60 minutes. The diluted photosensitive resin composition was placed in a polyethylene container and sealed.
＜体積固有抵抗値の測定＞
　上記で調製したＡ１＝５．０（ｄＰａ・ｓ）、Ａ２＝１．５（ｄＰａ・ｓ）に希釈後の各２種類の感光性樹脂組成物の温度を２５℃にして、該組成物中に静電テスター（旭サナック株式会社製、商品名：ＥＭ－ＩＶ）の電極（電極面積：１ｃｍ２、電極間距離：１ｃｍ）を浸漬したときの体積固有抵抗値Ｂ（ＭΩ）を測定した。なお、粘度Ａ１のときの体積固有抵抗値をＢ１（ＭΩ）、粘度Ａ２のときの体積固有抵抗値をＢ２（ＭΩ）とした。さらに、「（Ａ１－Ａ２）／（Ｂ１－Ｂ２）」の値を算出した。測定結果および算出結果を表３および４に示した。体積固有抵抗値の測定は２０分以内に完了させた。 <Measurement of volume resistivity>
The temperature of each of the two photosensitive resin compositions after dilution to A 1 = 5.0 (dPa s) and A 2 = 1.5 (dPa s) prepared above was set to 25 ° C., and the composition Measure the volume specific resistance value B (MΩ) when the electrodes (electrode area: 1 cm 2 , distance between electrodes: 1 cm) of an electrostatic tester (manufactured by Asahi Sunac Co., Ltd., trade name: EM-IV) are immersed in the object. did. The volume resistivity value at viscosity A1 was B 1 (MΩ), and the volume resistivity value at viscosity A2 was B 2 ( MΩ). Furthermore, the value of "(A 1 -A 2 )/(B 1 -B 2 )" was calculated. The measurement results and calculation results are shown in Tables 3 and 4. The volume resistivity measurements were completed within 20 minutes.
＜回路エッジ部のカバーリング性＞
　上記の実施例および比較例で調製したＡ２＝１．５（ｄＰａ・ｓ）に希釈後の感光性樹脂組成物を用いて、バフ研磨後の長さ１５ｃｍ、幅９．５ｃｍ、厚み１．６ｍｍ、回路厚３５μｍのＦＲ－４銅張積層基板に静電スプレー塗布（吐出条件；ｗｅｔ．９０ｇ／ｍ２）した。これを熱風循環式乾燥炉で８０℃３０分間の条件で乾燥させて溶剤を揮発させた後、３００ｍＪ／ｃｍ２の積算光量で露光した。次に、１％の炭酸ナトリウム水溶液で現像して未露光部の感光性樹脂組成物を除去した。その後、熱風循環式乾燥炉で１５０℃６０分間の条件で感光性樹脂組成物を熱硬化させて、評価基板を作製した。回路エッジ部のカバーリング性を以下の基準にて評価し、評価結果を表３および４に示した。
［評価基準］
　◎： 回路上がレジストで非常に良くカバーされた。
　○： 回路上がレジストで十分にカバーされた。
　△： 回路上でレジストの薄い部分が発生した。
　×： 回路上にレジストが極端に薄い部分が発生した。 <Covering property of circuit edge part>
Using the photosensitive resin composition diluted to A 2 =1.5 (dPa·s) prepared in the above Examples and Comparative Examples, a length of 15 cm, a width of 9.5 cm, and a thickness of 1.5 cm after buffing were applied. An FR-4 copper-clad laminate substrate having a thickness of 6 mm and a circuit thickness of 35 μm was electrostatically spray-coated (discharge conditions: wet.90 g/m 2 ). This was dried in a hot air circulating drying oven at 80° C. for 30 minutes to volatilize the solvent, and then exposed to an integrated light quantity of 300 mJ/cm 2 . Next, the unexposed area of the photosensitive resin composition was removed by developing with a 1% sodium carbonate aqueous solution. Thereafter, the photosensitive resin composition was thermally cured at 150° C. for 60 minutes in a hot air circulating drying oven to prepare an evaluation substrate. The covering property of the circuit edge portion was evaluated according to the following criteria, and the evaluation results are shown in Tables 3 and 4.
[Evaluation criteria]
A: The circuit was very well covered with the resist.
◯: The circuit was sufficiently covered with the resist.
Δ: A thin portion of the resist was generated on the circuit.
x: An extremely thin portion of the resist was generated on the circuit.
＜現像性＞
　＜回路エッジ部のカバーリング性＞で作製した評価基板の基板上のレジスト残渣を以下の基準にて評価し、評価結果を表３および４に示した。
　◎：現像残渣がなかった。
　〇：若干の現像残渣あったが、実用上問題無かった。
　×：現像残渣があった。 <Developability>
The resist residue on the evaluation substrate prepared in <Covering property of the circuit edge> was evaluated according to the following criteria, and the evaluation results are shown in Tables 3 and 4.
A: There was no development residue.
◯: Some development residue was found, but there was no practical problem.
x: Development residue was found.
＜はんだ耐熱性＞
　＜回路エッジ部のカバーリング性＞で作製した評価基板で、ロジン系フラックスを用いて、２６０℃で３０秒、はんだフロー試験を行い、はんだ耐熱性を以下の基準にて評価し、評価結果を表３および４に示した。なお、現像性の評価が「×」であったものは評価せずに、評価結果は「－」とした。
［評価基準］
　○：剥がれがなかった。
　△：若干の剥がれがあった。 
　×：剥がれがあった。 <Solder heat resistance>
A solder flow test was performed at 260° C. for 30 seconds using a rosin-based flux on the evaluation board prepared in <Covering property of the circuit edge>, and the solder heat resistance was evaluated according to the following criteria. Shown in Tables 3 and 4. It should be noted that those evaluated for developability as "x" were not evaluated, and the evaluation result was given as "-".
[Evaluation criteria]
◯: No peeling occurred.
Δ: There was some peeling.
x: Peeling occurred.
＜無電解めっき耐性＞
　＜回路エッジ部のカバーリング性＞で作製した評価基板で無電解めっき耐性を以下の基準にて評価し、評価結果を表３および４に示した。なお、現像性の評価が「×」であったものは評価せずに、評価結果は「－」とした。
［評価基準］
　○：剥がれがなかった。
　△：若干の剥がれがあった。
　×：剥がれがあった。 <Electroless plating resistance>
The evaluation substrates prepared in <Circuit Edge Covering Properties> were evaluated for electroless plating resistance according to the following criteria, and the evaluation results are shown in Tables 3 and 4. It should be noted that those evaluated for developability as "x" were not evaluated, and the evaluation result was given as "-".
[Evaluation criteria]
◯: No peeling occurred.
Δ: There was some peeling.
x: Peeling occurred.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３および４の評価結果からも明らかなように、感光性樹脂組成物の２５℃における粘度をＡ（ｄＰａ・ｓ）とし、前記感光性樹脂組成物の２５℃における体積固有抵抗値をＢ（ＭΩ）とすると、プロピレングリコールモノメチルエーテルを用いて前記感光性樹脂組成物の粘度をＡ１＝５．０（ｄＰａ・ｓ）、Ａ２＝１．５（ｄＰａ・ｓ）に調整した時、Ａ１の時の体積固有抵抗値をＢ１（ＭΩ）、Ａ２の時の体積固有抵抗値をＢ２（ＭΩ）が、
式：　１．４≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦４０
を満たす感光性樹脂組成物（実施例１～６）においては、カバーリング性、現像性、はんだ耐熱性、めっき耐性のそれぞれに関して優れていることがわかる。
　一方、上記式を満たさない感光性樹脂組成物（比較例１～３）ではカバーリング性、現像性、はんだ耐熱性、めっき耐性のそれぞれをバランス良く向上させることができないことがわかる。 As is clear from the evaluation results in Tables 3 and 4, the viscosity of the photosensitive resin composition at 25°C is A (dPa s), and the volume resistivity of the photosensitive resin composition at 25°C is B ( MΩ), when the viscosity of the photosensitive resin composition is adjusted to A 1 = 5.0 (dPa s) and A 2 = 1.5 (dPa s) using propylene glycol monomethyl ether, A B 1 (MΩ) is the volume resistivity value at 1 , and B 2 (MΩ) is the volume resistivity value at A 2 ,
Formula: 1.4≦(A 1 −A 2 )/(B 1 −B 2 )≦40
It can be seen that the photosensitive resin compositions (Examples 1 to 6) satisfying the above are excellent in terms of covering properties, developability, soldering heat resistance, and plating resistance.
On the other hand, it can be seen that the photosensitive resin compositions (Comparative Examples 1 to 3) that do not satisfy the above formula cannot improve covering properties, developability, soldering heat resistance, and plating resistance in a well-balanced manner.

Claims (7)

  1. 　カルボキシル基含有樹脂、熱硬化性樹脂、感光性モノマー、および有機溶剤を含む感光性樹脂組成物であって、
    　前記感光性樹脂組成物の２５℃における粘度をＡ（ｄＰａ・ｓ）とし、前記感光性樹脂組成物の２５℃における体積固有抵抗値をＢ（ＭΩ）とすると、プロピレングリコールモノメチルエーテルを用いて前記感光性樹脂組成物の粘度をＡ１＝５．０（ｄＰａ・ｓ）、Ａ２＝１．５（ｄＰａ・ｓ）に調整した時、Ａ１の時の体積固有抵抗値をＢ１（ＭΩ）、Ａ２の時の体積固有抵抗値をＢ２（ＭΩ）が、
    下記式：
    　１．４≦（Ａ１－Ａ２）／（Ｂ１－Ｂ２）≦４０
    を満たすことを特徴とする、感光性樹脂組成物。     A photosensitive resin composition containing a carboxyl group-containing resin, a thermosetting resin, a photosensitive monomer, and an organic solvent,
    Let A (dPa s) be the viscosity of the photosensitive resin composition at 25°C, and B (MΩ) be the volume resistivity of the photosensitive resin composition at 25°C. When the viscosity of the photosensitive resin composition is adjusted to A 1 = 5.0 (dPa s) and A 2 = 1.5 (dPa s), the volume resistivity value at A 1 is B 1 (MΩ ), the volume specific resistance value at A 2 is B 2 (MΩ),
    The formula below:
    1.4≦(A 1 −A 2 )/(B 1 −B 2 )≦40
    A photosensitive resin composition characterized by satisfying:
  2. 　第四級アンモニウム塩化合物をさらに含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, further comprising a quaternary ammonium salt compound.
  3. 　前記第四級アンモニウム塩化合物が、テトラブチルアンモニウムブロマイドおよびテトラプロピルアンモニウムブロマイドから選択される少なくとも１種である、請求項２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 2, wherein the quaternary ammonium salt compound is at least one selected from tetrabutylammonium bromide and tetrapropylammonium bromide.
  4. 　前記有機溶剤が、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテル、およびプロピレングリコールモノメチルエーテルからなる群から選択される少なくとも１種である、請求項１～３のいずれか一項に記載の感光性樹脂組成物。 Claims 1-, wherein the organic solvent is at least one selected from the group consisting of diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether. 4. The photosensitive resin composition according to any one of 3.
  5. 　スプレーコーターでの塗布に用いられる、請求項１～４のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, which is used for coating with a spray coater.
  6. 　ソルダーレジスト形成用として用いられる、請求項１～５のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, which is used for forming a solder resist.
  7. 　ソルダーレジスト層を備えるプリント配線板の製造方法であって、
    　請求項１～６のいずれか一項に記載の感光性樹脂組成物を、スプレーコーターで基板上に塗布し、露光し、光および熱のいずれか少なくとも１種によって硬化させて、ソルダーレジスト層を形成することを特徴とする、プリント配線板の製造方法。     A method for manufacturing a printed wiring board comprising a solder resist layer,
    The photosensitive resin composition according to any one of claims 1 to 6 is applied on a substrate with a spray coater, exposed, and cured by at least one of light and heat to form a solder resist layer. A method for manufacturing a printed wiring board, comprising:
PCT/JP2022/002892 2021-01-28 2022-01-26 Photosensitive resin composition and printed wiring board manufacturing method WO2022163701A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006131679A (en) * 2004-11-02 2006-05-25 Daicel Chem Ind Ltd Photo and/or heat curable resin composition
JP2006220861A (en) * 2005-02-09 2006-08-24 Fuji Photo Film Co Ltd Photosensitive composition, photosensitive film, permanent pattern, and forming method thereof
JP2010175608A (en) * 2009-01-27 2010-08-12 Sekisui Chem Co Ltd Photosensitive composition and solder resist composition
WO2019073926A1 (en) * 2017-10-11 2019-04-18 東レ株式会社 Photosensitive conductive paste, and film for forming conductive pattern

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006131679A (en) * 2004-11-02 2006-05-25 Daicel Chem Ind Ltd Photo and/or heat curable resin composition
JP2006220861A (en) * 2005-02-09 2006-08-24 Fuji Photo Film Co Ltd Photosensitive composition, photosensitive film, permanent pattern, and forming method thereof
JP2010175608A (en) * 2009-01-27 2010-08-12 Sekisui Chem Co Ltd Photosensitive composition and solder resist composition
WO2019073926A1 (en) * 2017-10-11 2019-04-18 東レ株式会社 Photosensitive conductive paste, and film for forming conductive pattern

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