WO2016129265A1 - Solder resist composition, and coated printed wiring board - Google Patents

Solder resist composition, and coated printed wiring board Download PDF

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Publication number
WO2016129265A1
WO2016129265A1 PCT/JP2016/000649 JP2016000649W WO2016129265A1 WO 2016129265 A1 WO2016129265 A1 WO 2016129265A1 JP 2016000649 W JP2016000649 W JP 2016000649W WO 2016129265 A1 WO2016129265 A1 WO 2016129265A1
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WO
WIPO (PCT)
Prior art keywords
solder resist
resist composition
colorant
compound
value
Prior art date
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PCT/JP2016/000649
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French (fr)
Japanese (ja)
Inventor
倫也 樋口
尚 丸澤
貴 荒井
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互応化学工業株式会社
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Application filed by 互応化学工業株式会社 filed Critical 互応化学工業株式会社
Priority to KR1020177000382A priority Critical patent/KR101856579B1/en
Priority to CN201680002036.0A priority patent/CN106537253A/en
Publication of WO2016129265A1 publication Critical patent/WO2016129265A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • 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 solder resist composition and a coated printed wiring board. More specifically, the present invention relates to a liquid solder resist composition that is photocurable and developable with an alkaline solution, and a coated printed wiring board including a solder resist layer formed from the solder resist composition.
  • the solder resist layer of consumer and industrial printed wiring boards is sometimes formed by a method using a liquid solder resist composition instead of a screen printing method.
  • the method using a liquid solder resist is excellent in resolution and developable, and therefore, a printed wiring board having high-density wiring can be formed.
  • a colored solder resist layer particularly a black solder resist layer
  • a black solder resist layer contains a large amount of black colorant
  • the resolution can be lowered by light absorption of the black colorant.
  • Japanese Patent Publication No. 2008-257045 discloses a black solder resist composition containing carbon black as a black colorant and phthalocyanine blue and anthraquinone red as colorants other than black.
  • this black solder resist composition contains a colorant other than black, the amount of black colorant used is reduced. As a result, the resolution of the solder resist layer formed from the solder resist composition is improved.
  • An object of the present invention is to provide a solder resist composition capable of forming a solder resist layer having required resolution and concealment, and a coated printed wiring board including a solder resist layer formed from the solder resist composition. Is to provide.
  • the solder resist composition according to one embodiment of the present invention is a photopolymerizable compound (B) containing at least one selected from the group consisting of a carboxyl group-containing resin (A), a photopolymerizable monomer, and a photopolymerizable prepolymer. ), A photopolymerization initiator (C), a thermosetting component (D), a perylene-based black colorant (E1), and a colorant other than black (E2), and the solder resist
  • the composition is photocured on a copper plate and then thermally cured, the film of the solder resist composition having any thickness within the range of 18 to 22 ⁇ m has an L * value of 40 or less and an a * value. Is in the range of 5.1 to 55, and the b * value is in the range of ⁇ 15 to 15.
  • the colorant (E2) is a red colorant.
  • the colorant (E2) is an anthraquinone red colorant.
  • thermosetting component (D) includes a compound having a cyclic ether skeleton.
  • the carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A2) having a photopolymerizable functional group.
  • a coated printed wiring board according to an aspect of the present invention includes a printed wiring board and a solder resist layer formed from the above solder resist composition and covering the printed wiring board.
  • a second resist layer covering the solder resist layer is provided.
  • the second resist layer includes a first region and a second region having a light transmittance higher than that of the first region.
  • the second solder resist layer contains a green colorant.
  • the L * value of the first region is 35 or more, the a * value is ⁇ 15 or less, the b * value is in the range of ⁇ 5 to 5, and the L * value of the second region is 32.
  • the a * value is in the range of ⁇ 10 to 10
  • the b * value is in the range of ⁇ 5 to 5.
  • solder resist layer having required resolution and concealing properties can be obtained.
  • 1A to 1C are cross-sectional views illustrating an example of a manufacturing process of a coated printed wiring board according to an embodiment.
  • 2A to 2C are cross-sectional views showing an example of a manufacturing process of a coated printed wiring board according to another embodiment.
  • (meth) acryl means at least one of “acryl” and “methacryl”.
  • (meth) acrylate means at least one of acrylate and methacrylate.
  • the solder resist composition includes a carboxyl group-containing resin (A), a photopolymerizable compound (B) containing at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer, and a photopolymerization initiator. (C), a thermosetting component (D), a perylene-based black colorant (E1), and a kind of colorant (E2) other than black.
  • the film of the solder resist composition having any thickness within the range of 18 to 22 ⁇ m has an L * value of 40 or less,
  • the a * value is in the range of 5.1 to 55, and the b * value is in the range of ⁇ 15 to 15.
  • the solder resist composition includes a perylene-based black colorant (E1) and a colorant other than black (E2), and a film formed from the solder resist composition has a specific range of L * value, a * value, and By having the b * value, when the film of the solder resist composition is exposed, the film can be sufficiently cured from the surface layer to the deep part. Thereby, the resolution and concealment property of the soldering resist layer formed from a soldering resist composition can be improved.
  • E1 perylene-based black colorant
  • E2 colorant other than black
  • solder resist composition according to one embodiment will be described in more detail.
  • the carboxyl group-containing resin (A) can impart developability with an alkaline solution, that is, alkali developability, to the film formed from the solder resist composition.
  • the carboxyl group-containing resin (A) can contain a carboxyl group-containing resin (A1) that has a carboxyl group and does not have a photopolymerizable functional group.
  • the carboxyl group-containing resin (A1) contains, for example, a polymer of an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group.
  • the ethylenically unsaturated monomer may include an ethylenically unsaturated compound having no carboxyl group.
  • the ethylenically unsaturated compound having a carboxyl group can contain an appropriate polymer and prepolymer, for example, a compound having only one ethylenically unsaturated group. More specifically, ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate.
  • the ethylenically unsaturated compound having a carboxyl group can also contain a compound having a plurality of ethylenically unsaturated groups. More specifically, ethylenically unsaturated compounds having a carboxyl group are pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentane. You may contain the compound obtained by reaction with the polyfunctional (meth) acrylate which has any hydroxyl group among methacrylate, and a dibasic acid anhydride. These compounds may be used alone or in combination.
  • the ethylenically unsaturated compound having no carboxyl group may be a compound copolymerizable with the ethylenically unsaturated compound having a carboxyl group.
  • the ethylenically unsaturated compound having no carboxyl group may contain both a compound having an aromatic ring and a compound having no aromatic ring.
  • the compound having no aromatic ring is, for example, a linear or branched aliphatic or alicyclic (but may have an unsaturated bond in the ring) (meth) acrylic acid ester, hydroxyalkyl (meth) It may contain at least one compound selected from the group consisting of acrylates, alkoxyalkyl (meth) acrylates, etc .; and N-substituted maleimides such as N-cyclohexylmaleimide.
  • Compounds that do not have an aromatic ring include ethylene glycol in one molecule such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.
  • the type, ratio, and the like of the compound used to obtain the carboxyl group-containing resin (A1) are appropriately selected.
  • the acid value of the carboxyl group-containing resin (A1) is preferably in the range of 20 to 180 mgKOH / g, more preferably in the range of 35 to 165 mgKOH / g.
  • the carboxyl group-containing resin (A) can contain a carboxyl group-containing resin (A2) having a photopolymerizable functional group.
  • the photopolymerizable functional group is, for example, an ethylenically unsaturated group.
  • the carboxyl group-containing resin (A2) includes, for example, at least one of the epoxy groups in the epoxy compound (a1) having two or more epoxy groups in one molecule, an ethylenically unsaturated compound (a2) having a carboxyl group, and And a resin having a structure to which at least one compound (a3) selected from the group consisting of polyvalent carboxylic acids and anhydrides is added (hereinafter referred to as first resin (a)) can be contained. .
  • the epoxy compound (a1) includes, for example, a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A-novolak type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, It can contain at least one compound selected from the group consisting of polymers of ethylenically unsaturated compounds including biphenyl aralkyl type epoxy resins, triglycidyl isocyanurates, alicyclic epoxy resins, and compounds having epoxy groups.
  • the epoxy compound (a1) may contain a polymer of an ethylenically unsaturated compound (p) including a compound (p1) having an epoxy group.
  • the ethylenically unsaturated compound (p) may contain only the compound (p1) having an epoxy group, or may contain the compound (p1) having an epoxy group and the compound (p2) not having an epoxy group. Good.
  • the compound (p1) having an epoxy group can contain at least one selected from the group consisting of an appropriate polymer and a prepolymer.
  • the compound (p1) having an epoxy group includes epoxy cyclohexyl derivatives of acrylic acid, epoxy cyclohexyl derivatives of methacrylic acid, alicyclic epoxy derivatives of acrylate, alicyclic epoxy derivatives of methacrylate, ⁇ -methylglycidyl acrylate And at least one component selected from the group consisting of ⁇ -methylglycidyl methacrylate.
  • the compound (p1) having an epoxy group contains glycidyl (meth) acrylate which is widely used and easily available.
  • the compound (p2) having no epoxy group may be a compound copolymerizable with the compound (p1) having an epoxy group, for example.
  • the compound having no epoxy group (p2) may further contain a compound having two or more ethylenically unsaturated groups in one molecule.
  • a compound having two or more ethylenically unsaturated groups in one molecule include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth). It can contain at least one compound selected from the group consisting of acrylates.
  • a polymer is obtained by polymerizing the ethylenically unsaturated compound (p) by a known polymerization method such as a solution polymerization method or an emulsion polymerization method.
  • the solution polymerization method is a method in which an ethylenically unsaturated compound (p), a suitable organic solvent, and a polymerization initiator are heated and stirred in a nitrogen atmosphere, or an azeotropic polymerization method.
  • Examples of the organic solvent used for the polymerization of the ethylenically unsaturated compound (p) include ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, and cellosolve acetate. And at least one compound selected from the group consisting of acetate esters such as butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and dialkyl glycol ethers.
  • Examples of the polymerization initiator used for the polymerization of the ethylenically unsaturated compound (p) include hydroperoxides such as diisopropylbenzene hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di Dialkyl peroxides such as-(t-butylperoxy) -hexane, diacyl peroxides such as isobutyryl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, alkyl peresters such as t-butyl peroxybivalate , Peroxydicarbonates such as diisopropyl peroxydicarbonate, azo compounds such as azobisisobutyronitrile, and at least one compound selected from the group consisting of redox initiators.
  • hydroperoxides such as diisopropylbenzene hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2
  • the ethylenically unsaturated compound (a2) having a carboxyl group can contain at least one component selected from the group consisting of an appropriate polymer and a prepolymer.
  • the ethylenically unsaturated compound (a2) can contain a compound having only one ethylenically unsaturated group.
  • Compounds having only one ethylenically unsaturated group include, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2 -Methacryloyloxyethylphthalic acid, ⁇ -carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2-acryloyl Consists of oxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxy
  • the ethylenically unsaturated compound (a2) can contain a compound having a plurality of ethylenically unsaturated groups.
  • the compound having a plurality of ethylenically unsaturated groups is, for example, hydroxyl such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. It can contain at least one compound selected from the group consisting of a compound obtained by reacting a difunctional acid anhydride with a polyfunctional acrylate having a group and a polyfunctional methacrylate.
  • the ethylenically unsaturated compound (a2) having a carboxyl group preferably contains at least one component selected from the group consisting of acrylic acid and methacrylic acid. Since the ethylenically unsaturated group derived from acrylic acid and methacrylic acid is particularly excellent in photoreactivity, the photoreactivity of the first resin (a) can be improved.
  • the amount of the carboxyl group of the ethylenically unsaturated compound (a2) having a carboxyl group with respect to 1 mol of the epoxy group of the epoxy compound (a1) is preferably within the range of 0.4 to 1.2 mol, more preferably 0. The amount is within the range of 5 to 1.1 mol.
  • Compound (a3) (hereinafter also referred to as compound (a3)) comprising a polyvalent carboxylic acid or its anhydride is, for example, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylnadic acid, hexahydrophthalic acid, methylhexa Dicarboxylic acids such as hydrophthalic acid, succinic acid, methyl succinic acid, maleic acid, citraconic acid, glutaric acid, itaconic acid; cyclohexane-1,2,4-tricarboxylic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, It can contain at least one compound selected from the group consisting of tribasic or higher polycarboxylic acids such as methylcyclohexene tetracarboxylic acid; and anhydrides of these polycarboxylic acids.
  • the main purpose of use of the compound (a3) is to impart redispersion and resolubility with a dilute alkaline aqueous solution to the solder resist composition by giving an acid value to the first resin (a).
  • the amount of the compound (a3) used is preferably adjusted so that the acid value of the first resin (a) is 30 mgKOH / g or more, more preferably the acid value of the first resin (a) is 60 mgKOH / g.
  • the amount of the compound (a3) used is preferably adjusted so that the acid value of the first resin (a) is 160 mgKOH / g or less, more preferably 130 mgKOH / g or less. Adjusted to be.
  • an addition reaction between the epoxy compound (a1) and the ethylenically unsaturated compound (a2) having a carboxyl group, and a product (addition reaction product) and a compound ( The addition reaction with a3) is carried out by a known method.
  • the ethylenically unsaturated compound (a2) is added to the solvent solution containing the epoxy compound (a1), and thermal polymerization is performed as necessary.
  • a reactive solution is obtained by adding an inhibitor and a catalyst and mixing with stirring.
  • An addition reaction product is obtained by reacting this reactive solution by a conventional method, preferably at 60 to 150 ° C., more preferably at 80 to 120 ° C.
  • the thermal polymerization inhibitor is, for example, hydroquinone or hydroquinone monomethyl ether.
  • the catalyst include tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine.
  • the compound (a3) is added to the solvent solution containing the addition reaction product, and a thermal polymerization inhibitor and a catalyst are further added and mixed as necessary.
  • a reactive solution is obtained.
  • the first resin (a) is obtained by reacting this reactive solution by a conventional method.
  • the reaction conditions may be the same as the reaction conditions for the addition reaction between the epoxy compound (a1) and the ethylenically unsaturated compound (a2) having a carboxyl group.
  • the thermal polymerization inhibitor and the catalyst the same thermal polymerization inhibitor and catalyst used in the addition reaction of the epoxy compound (a1) and the ethylenically unsaturated compound (a2) having a carboxyl group can be used.
  • Carboxyl group-containing resin (A2) is a part of a carboxyl group in a polymer of ethylenically unsaturated monomers including an ethylenically unsaturated compound having a carboxyl group, and an ethylenically unsaturated compound having an epoxy group. You may contain resin obtained by making it react (it is called 2nd resin (b)).
  • the ethylenically unsaturated monomer may include an ethylenically unsaturated compound having no carboxyl group, if necessary.
  • the ethylenically unsaturated compound having a carboxyl group for obtaining the second resin (b) can contain an appropriate polymer and prepolymer.
  • an ethylenically unsaturated compound having a carboxyl group can contain a compound having only one ethylenically unsaturated group.
  • ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone (n ⁇ 2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate.
  • the ethylenically unsaturated compound having a carboxyl group can contain a compound having a plurality of ethylenically unsaturated groups. More specifically, for example, ethylenically unsaturated compounds having a carboxyl group are pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol.
  • a compound obtained by the reaction of a polyfunctional (meth) acrylate having a hydroxyl group selected from the group consisting of pentamethacrylate and a dibasic acid anhydride can be contained. These compounds may be used alone or in combination.
  • the ethylenically unsaturated compound having no carboxyl group for obtaining the second resin (b) can be, for example, a compound copolymerizable with an ethylenically unsaturated compound having a carboxyl group.
  • the ethylenically unsaturated compound having no carboxyl group can contain a compound having an aromatic ring and a compound having no aromatic ring.
  • the compound having no aromatic ring is, for example, a linear or branched aliphatic or alicyclic (however, the ring may partially have an unsaturated bond) (meth) acrylic acid ester, hydroxyalkyl It can contain at least one compound selected from the group consisting of (meth) acrylates, alkoxyalkyl (meth) acrylates and the like; and N-substituted maleimides such as N-cyclohexylmaleimide.
  • Compounds that do not have an aromatic ring include ethylene glycol in one molecule such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate.
  • the ethylenically unsaturated compound having an epoxy group for obtaining the second resin (b) is an appropriate polymer or prepolymer.
  • the ethylenically unsaturated compound having an epoxy group is selected from the group consisting of, for example, epoxycyclohexyl derivatives of acrylic acid or methacrylic acid; alicyclic epoxy derivatives of acrylate or methacrylate; ⁇ -methylglycidyl acrylate, ⁇ -methylglycidyl methacrylate. At least one compound. These compounds may be used alone or in combination. Preferably, glycidyl (meth) acrylate which is widely used and easily available is used.
  • Carboxyl group-containing resin (A2) is a part or all of hydroxyl groups in a polymer of an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group. And a resin obtained by adding a compound having an ethylenically unsaturated group and an isocyanate group (hereinafter referred to as a third resin (c)).
  • the ethylenically unsaturated monomer may contain an ethylenically unsaturated compound having no carboxyl group and no hydroxyl group, if necessary.
  • Examples of the ethylenically unsaturated compound having a carboxyl group for obtaining the third resin (c) were the same as the ethylenically unsaturated compound having a carboxyl group for obtaining the second resin (b). May be.
  • Examples of the ethylenically unsaturated compound having a hydroxyl group for obtaining the third resin (c) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
  • the compound having an ethylenically unsaturated group and an isocyanate group for obtaining the third resin (c) is, for example, 2-acryloyloxyethyl isocyanate (as a specific example, Showa Denko KK; product number “Karenz AOI”), 2- Methacryloyloxyethyl isocyanate (as a specific example, Showa Denko KK; product number “Karenz MOI”), methacryloyloxyethoxyethyl isocyanate (as a specific example, Showa Denko KK; product number “Karenz MOI-EG”), Karenz MOI isocyanate block ( Specific examples are Showa Denko KK; product number “Karenz MOI-BM”), Karenz MOI isocyanate block (specific examples Showa Denko KK; product number “Karenz MOI-BP”), and 1,1- (bisacryloyloxy) Methyl) ethyl Isocyanate) (
  • the weight average molecular weight of the entire carboxyl group-containing resin (A2) is preferably in the range of 800 to 100,000. In this case, particularly excellent photosensitivity and resolution are imparted to the solder resist composition.
  • the acid value of the entire carboxyl group-containing resin (A2) is preferably 30 mgKOH / g or more. In this case, good developability is imparted to the solder resist composition.
  • the acid value of the entire carboxyl group-containing resin (A2) is more preferably 60 mgKOH / g or more.
  • the acid value of the entire carboxyl group-containing resin (A2) is preferably 160 mgKOH / g or less. In this case, the amount of carboxyl groups remaining in the film formed with the solder resist composition is reduced. For this reason, it is possible to maintain good electrical characteristics, corrosion resistance, water resistance, and the like of the coating film.
  • the acid value of the entire carboxyl group-containing resin (A2) is more preferably 130 mgKOH / g or less.
  • the photopolymerizable compound (B) imparts photocurability to the solder resist composition.
  • the photopolymerizable compound (B) contains at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer.
  • the photopolymerizable monomer has, for example, an ethylenically unsaturated group.
  • Photopolymerizable monomers include, for example, monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Multifunctional (meth) such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ⁇ -caprolactone modified pentaerythritol hexaacrylate It can contain at least one compound selected from the group consisting of acrylates.
  • the photopolymerizable monomer preferably contains a phosphorus-containing compound (phosphorus-containing photopolymerizable compound).
  • Phosphorus-containing photopolymerizable compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples: product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate ( As specific examples, product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd., diphenyl-2-methacryloyloxyethyl phosphate (specific example, product number MR-260 manufactured by Daihachi Kogyo Co., Ltd.) and Showa Polymer Co., Ltd.
  • HFA series (specifically, product number HFA-6003, which is an addition reaction product of dipentaerystol hexaacrylate and HCA, and product number HFA, which is an addition reaction product of caprolactone-modified dipentaerystol hexaacrylate and HCA) -30 3, and it is selected from the group consisting of HFA-6127, etc.) containing at least one compound.
  • the photopolymerizable prepolymer is, for example, a prepolymer obtained by polymerizing a photopolymerizable monomer with an ethylenically unsaturated group added, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate. And at least one compound selected from the group consisting of oligo (meth) acrylate prepolymers such as alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate.
  • oligo (meth) acrylate prepolymers such as alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate.
  • the photopolymerization initiator (C) includes, for example, benzoin and alkyl ethers thereof; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone Thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; Compounds containing nitrogen atoms such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone;
  • the photopolymerization initiator (C) is more preferably at least two components selected from the group consisting of ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, thioxanthones, and acylphosphine oxide photopolymerization initiators. including.
  • thermosetting component (D) can impart thermosetting properties to the solder resist composition.
  • the thermosetting component (D) preferably contains a compound having a cyclic ether skeleton.
  • the compound having a cyclic ether skeleton preferably contains, for example, an epoxy compound.
  • the epoxy compound preferably has at least two epoxy groups in one molecule.
  • the epoxy compound may be a poorly solvent-soluble epoxy compound or a general-purpose solvent-soluble epoxy compound.
  • the kind of epoxy compound is not particularly limited.
  • the epoxy compound includes a phenol novolac type epoxy resin (specifically, product number EPICLON N-775 manufactured by DIC Corporation), a cresol novolac type epoxy resin (specific example, product number EPICLON N-695 manufactured by DIC Corporation), and a bisphenol A type epoxy.
  • the epoxy compound preferably contains triglycidyl isocyanurate.
  • the triglycidyl isocyanurate is preferably a ⁇ -form having a structure in which three epoxy groups are bonded in the same direction with respect to the S-triazine ring skeleton plane, or the ⁇ -form and the S-triazine ring skeleton plane. On the other hand, it is a mixture of an ⁇ -form having a structure in which one epoxy group is bonded to the other two epoxy groups in different directions.
  • the solder resist composition contains a colorant (E).
  • the colorant (E) includes a perylene black colorant (E1) and a kind of colorant (E2) other than black.
  • the solder resist composition contains a perylene-based black colorant (E1) and a colorant (E2)
  • the film formed from the solder resist composition is exposed, the film is sufficiently cured from the surface layer to the deep part. Can do. Furthermore, the concealability of the conductor wiring by the film formed from the solder resist composition can be sufficiently ensured.
  • the colorant (E) contains only a perylene-based black colorant (E1) and one kind of colorant (E2) other than black.
  • the perylene-based black colorant (E1) can contain, for example, at least one compound selected from the group consisting of a color index (CI) pigment black 31 and a color index (CI) pigment black 32. .
  • the perylene-based black colorant (E1) has no color index number, but is known as a perylene-based near-infrared transmitting black colorant, BASF's Lumogen Black FK 4280. And at least one component selected from the group consisting of Lumogen Black FK 4281.
  • a kind of colorant (E2) other than black is a kind of colorant other than black.
  • the colorant (E2) is, for example, a non-black colorant among known colorants having a color index (CI; issued by The Society of Dyer's and Colorists) number It can be.
  • the colorant (E2) is selected from the group consisting of, for example, a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, a brown colorant, and other colorants. Can be at least one colorant.
  • the one type of colorant (E2) other than black is a red colorant.
  • the solder resist composition contains a perylene-based black colorant (E1) and a red colorant
  • the film formed from the solder resist composition is exposed, the film is sufficiently cured from the surface layer to the deep part. Can do.
  • the concealability of the conductor wiring by the film formed from the solder resist composition can be more sufficiently ensured.
  • the red colorant can contain, for example, at least one pigment selected from the group consisting of an anthraquinone red pigment, an azo red pigment, a lake red pigment, a quinacridone red pigment, and a diketopyrrole red pigment.
  • the red colorant is an anthraquinone red pigment.
  • Anthraquinone red pigments include, for example, Color Index (CI) Pigment Red 83, Color Index (CI) Pigment Red 168, Color Index (CI) Pigment Red 177, and Color Index (C.I.). I.) It may be at least one pigment selected from the group consisting of Pigment Red 216.
  • the red colorant is an anthraquinone red colorant, the concealability of the conductor wiring by the film formed from the solder resist composition can be more sufficiently ensured.
  • An anthraquinone red colorant has excellent dispersibility and weather resistance.
  • the colorant (E) may further contain a colorant (E3) other than the colorant (E1) and one kind of colorant (E2) other than black. That is, the solder resist composition may contain a colorant (E3).
  • the colorant (E3) is, for example, from the group consisting of a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, a brown colorant, and a colorant of a color other than those described above. At least one colorant selected. Preferably, the colorant (E3) is at least one colorant selected from the group consisting of a red colorant, a purple colorant, an orange colorant, and a brown colorant.
  • the solder resist composition may contain an organic solvent.
  • the organic solvent is used for liquefying or varnishing the solder resist composition, adjusting the viscosity, adjusting the coating property, adjusting the film forming property, and the like.
  • Organic solvents include, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co.); cellosolves such as cellosolve and butylcellosolve; Tolls; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, cal Acetic acid esters such as tall acetate; as well as containing at least
  • the proportion of the organic solvent contained in the solder resist composition is such that when the coating film formed from the solder resist composition is dried, the organic solvent is volatilized quickly, that is, the organic solvent does not remain in the dry coating film. It is preferable to be adjusted.
  • the ratio of the organic solvent to the entire solder resist composition is preferably in the range of 5 to 99.5% by mass, more preferably in the range of 15 to 80% by mass.
  • the preferable ratio of an organic solvent changes with coating methods. For this reason, it is preferable that the ratio of the organic solvent is appropriately adjusted according to the coating method.
  • solder resist composition may further contain components other than the above components.
  • the solder resist composition includes tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanates blocked with caprolactam, oxime, malonic acid ester, etc .; melamine resin, n-butylated melamine Resins, isobutylated melamine resins, butylated urea resins, butylated melamine urea cocondensation resins, benzoguanamine-based cocondensation resins, and other amino resins; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylates; bisphenol A Resin obtained by adding (meth) acrylic acid to epoxy resin such as epoxy, phenol novolac, cresol novolac, alicyclic, etc .; and diallyl phthalate resin, phenoxy resin, urethane resin It may contain at least one resin selected from the group consisting of a polymer compound such as
  • the solder resist composition may contain a curing agent for curing the epoxy compound.
  • the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenyl
  • Examples of these commercially available compounds include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U- CAT3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).
  • the solder resist composition may contain an additive that imparts adhesion.
  • the additive include guanamine, acetoguanamine, benzoguanamine, melamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- At least one selected from the group consisting of S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct These compounds can be contained.
  • Solder resist composition includes curing accelerator; copolymer such as silicone and acrylate; leveling agent; adhesion imparting agent such as silane coupling agent; thixotropic agent; polymerization inhibitor; antihalation agent; flame retardant; An antioxidant; a surfactant; a polymer dispersant; and an inorganic filler such as barium sulfate, crystalline silica, nanosilica, carbon nanotube, talc, bentonite, aluminum hydroxide, magnesium hydroxide, magnesium oxide, and calcium carbonate. You may contain the 1 or more types of component selected from a group.
  • the solder resist composition may further contain a known photopolymerization accelerator, sensitizer and the like.
  • the solder resist composition may contain p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate and the like.
  • solder resist composition [About the compounding quantity and preparation method of each component contained in a soldering resist composition] The amount of each component in the solder resist composition is appropriately adjusted so that the solder resist composition has photocurability and can be developed with an alkaline solution.
  • the ratio is preferably in the range of 40 to 80% by mass, more preferably in the range of 45 to 75% by mass, and particularly preferably in the range of 50 to 70% by mass.
  • the ratio of the photopolymerizable compound (B) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass. Particularly preferably, it is in the range of 15 to 40% by mass.
  • the ratio of the photopolymerization initiator (C) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass. And particularly preferably in the range of 5 to 25% by mass.
  • the ratio of the thermosetting component (D) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 60% by mass. Particularly preferably, it is in the range of 15 to 45% by mass.
  • the ratio of the colorant (E) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.2 to 15% by mass, more preferably 0.5 to 10% by mass. It is within the range, and particularly preferably within the range of 1 to 8% by mass.
  • a soldering resist composition contains the coloring agent (E) of these ratios, it is easy to ensure the resolution of the soldering resist layer formed with a soldering resist composition.
  • the resolution of the soldering resist layer formed from a soldering resist composition may fall.
  • the ratio of the perylene-based black colorant (E1) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.1 to 14% by mass, more preferably 0.5 to 7 It is in the range of mass%.
  • the ratio of one kind of colorant (E2) other than black to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.1 to 12% by mass, more preferably 0.5. It is in the range of ⁇ 7% by mass.
  • the ratio of the colorant (E2) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.5 to 7% by mass. Is within.
  • the ratio of the perylene-based black colorant (E1) and the colorant (E2) contained in the solder resist composition is within the above range, when the film of the solder resist composition is cured, the depth from the surface layer of the film In particular, the concealability of the conductor wiring of the solder resist layer formed from the solder resist composition can be particularly improved.
  • the ratio of the colorant (E3) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably 0.1 to 7 mass. %.
  • the solder resist composition can be obtained, for example, by kneading the components of the solder resist composition with a three roll, ball mill, sand mill or the like.
  • this solder resist composition When this solder resist composition is photocured on a copper plate and then thermally cured to form a film, and the thickness of this film is in the range of 18 to 22 ⁇ m, the L * value of this film Is 40 or less, the a * value is in the range of 5.1 to 55, and the b * value is in the range of ⁇ 15 to 15. If the L * value, a * value, and b * value of the coating having a thickness in the range of 18 to 22 ⁇ m satisfy the above conditions, the coating having other thicknesses is It is not necessary to satisfy the conditions. For example, if the film having a thickness of 20 ⁇ m satisfies the above conditions, the film having a thickness of 18 ⁇ m may not have the above conditions.
  • the L * value, a * value, and b * value of the coating can be measured by, for example, a spectrocolorimeter.
  • This spectrocolorimeter is, for example, model number CM-600d manufactured by Konica Minolta Sensing Co., Ltd.
  • the first agent may be prepared by mixing a part of the raw material of the solder resist composition
  • the second agent may be prepared by mixing the rest of the raw material.
  • the solder resist composition may include a first agent and a second agent.
  • the first agent is prepared by previously mixing and dispersing the photopolymerizable compound (B), a part of the organic solvent, and the thermosetting component (D) among the raw materials, and the remaining part of the raw materials is mixed.
  • the second agent may be prepared by dispersing it. In this case, the required amount of the first agent and the second agent can be mixed to prepare a mixed solution, and the solder resist layer can be formed from this mixed solution.
  • solder resist composition of one embodiment is applied, for example, to form a solder resist layer on a printed wiring board. Thereby, a covering printed wiring board is manufactured.
  • a solder resist layer is formed from a solder resist composition having both photocuring properties and thermosetting properties.
  • a printed wiring board 100 is prepared, and a coating film 1 is formed on the printed wiring board using a solder resist composition.
  • a solder resist composition is applied on the surface of the printed wiring board 100 to form a wet paint film (wet paint film).
  • the method for applying the solder resist composition is selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing.
  • the wet coating film is dried at a temperature in the range of 60 to 120 ° C., for example, as shown in FIG. 1A.
  • the coating film 1 (dry coating film) is obtained.
  • the coating film 1 is formed by applying a solder resist composition on an appropriate support in advance and then drying, and printing the coating film 1
  • the coating film 1 may be provided on the printed wiring board 100 by applying pressure to the coating film 1 and the printed wiring board 100 in a state of being overlaid on the wiring board 100 (dry film method).
  • the mask 3 is applied directly or indirectly to the coating film 1, and then the active energy ray is irradiated toward the mask 3, whereby the coating film 1 is passed through the mask 3. To expose.
  • the active energy ray is selected according to the composition of the solder resist composition.
  • the active energy ray is ultraviolet light.
  • the ultraviolet light source is, for example, a light source selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, and metal halide lamps.
  • the mask 3 includes an exposure part 31 through which active energy rays are transmitted and a non-exposure part 32 through which active energy rays are shielded.
  • the shape of the exposed portion 31 matches the pattern shape of the solder resist layer.
  • This mask is, for example, a photo tool such as a mask film or a dry plate.
  • a method other than the method using a mask may be adopted as the exposure method.
  • a direct drawing method such as laser exposure may be employed.
  • the photocuring reaction proceeds efficiently from the surface layer to the deep part of the coating film 1 as described above.
  • the mask 3 is removed from the printed wiring board 100, and the coating film 1 is developed to remove the unexposed portion of the coating film 1.
  • the solder resist layer 10 that is the exposed portion of the coating film 1 remains on the surface of the printed wiring board 100.
  • an appropriate developer according to the composition of the solder resist composition can be used.
  • the developer include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous ammonium carbonate solution, an aqueous sodium hydrogen carbonate solution, an aqueous potassium hydrogen carbonate solution, an aqueous ammonium hydrogen carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, water
  • An alkaline solution such as an aqueous tetramethylammonium oxide solution or an aqueous lithium hydroxide solution may be included.
  • the developer may include organic amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine. Of these developing solutions, only one type may be used, or a plurality of types may be used in combination.
  • the solvent of the developer may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols.
  • the solder resist layer can be cured by subjecting the solder resist layer to a heat treatment.
  • the heating temperature is in the range of 120 to 180 ° C.
  • the heating time is in the range of 30 to 90 minutes.
  • the solder resist layer may be further irradiated with active energy rays.
  • the photocuring reaction of the solder resist layer can be further advanced.
  • the migration tolerance of a soldering resist layer can further be improved.
  • a coated printed wiring board including a printed wiring board and a solder resist layer that partially covers the printed wiring board is obtained.
  • the solder resist layer is sufficiently cured from the surface layer to the deep part.
  • the film thickness of the solder resist layer is, for example, preferably in the range of 5 to 60 ⁇ m, more preferably in the range of 10 to 40 ⁇ m. In this case, the concealability of the conductor wiring by the solder resist layer can be improved.
  • this solder resist layer is covered with another solder resist layer (second resist layer).
  • This second resist layer can protect the solder resist layer on the printed wiring board.
  • the coated printed wiring board according to another embodiment preferably includes a second resist layer that covers the solder resist layer.
  • the second resist layer includes a first region and a second region having a light transmittance higher than that of the first region.
  • the second resist layer includes a plurality of regions having different light transmittances, regions having different colors can be formed.
  • the marking of the first region is formed when the shape of the first region is an appropriate figure, character, or the like.
  • region may be formed because the shape of a 2nd area
  • solder resist composition (hereinafter referred to as a second resist composition) for forming the second resist layer will be described.
  • the second resist composition has a carboxyl group-containing resin (F), a photopolymerizable compound (G), a photopolymerization initiator (H), a colorant (I), a clear melting point, and has photopolymerizability.
  • the organic compound (J) which does not carry out is also hereafter called a specific organic compound (J)).
  • a second resist composition is applied onto a dried coating film (hereinafter referred to as a first coating film) of the solder resist composition. After the second coating film is formed by drying, the second coating film is exposed. Then, after developing the 1st coating film and 2nd coating film after exposure with an alkaline solution, a 1st coating film and a 2nd coating film are heated. Thereby, the covering printed wiring board provided with the soldering resist layer and the 2nd resist layer is manufactured.
  • the first part of the second coating film is irradiated with active energy rays, and the second part different from the first part of the second coating film is exposed to the first part.
  • An active energy ray having an exposure amount lower than that of the portion is irradiated, and the first region and the third region different from the second portion in the second coating film are not irradiated with the active energy ray.
  • the exposure amount of the first portion may be uniform, or the first portion may include a plurality of portions having different exposure amounts.
  • the exposure amount of the second part may be uniform, or the second part may include a plurality of parts having different exposure amounts. .
  • the heating temperature of the second coating T h ⁇ T m -30 (where, T h (° C.) is the heating temperature of the second coating film, T m, the specific The relationship of the melting point of the organic compound (J) is satisfied. That is, the heating temperature when the second coating film is heated is equal to or higher than the temperature 30 ° C. lower than the melting point of the specific organic compound (J). In other words, the melting point of the specific organic compound (J) is not more than 30 ° C. higher than the heating temperature when heating the second coating film.
  • the color of the appearance of the first region is the color of the colorant (I) contained in the second resist composition.
  • the color of the appearance of the second region is a mixed color of the color of the colorant (I) contained in the second resist composition and the color of the surface of the solder resist layer. This effect is presumed to occur for the following reason.
  • the first part Since the first part is irradiated with active energy rays when the second coating film is exposed, the first part contains a polymer produced by the photopolymerization reaction of the photopolymerizable compound (G).
  • the specific organic compound (J) in the second coating film melts and the second coating film tends to be deformed.
  • the first portion contains a polymer, it hardly deforms following the melting of the specific organic compound (J). For this reason, bubbles may be generated in the first portion.
  • the second part does not contain the polymer of the photopolymerizable compound (G), or the ratio of this polymer is lower than that of the first part.
  • the second coating film when the second coating film is heated, the second part is more likely to deform following the melting of the specific organic compound (J) than the first part. For this reason, bubbles may not be generated in the second portion, or the ratio of bubbles in the second portion may be lower than that of the first portion.
  • the heating temperature at the time of heating the second coating film is lower than the melting point of the specific organic compound (J) and not less than 30 ° C. lower than the melting point of the specific organic compound (J).
  • Bubbles are generated in the first part.
  • One of the reasons may be a melting point drop (freezing point depression) of the specific organic compound (J) due to the mixing of another compound with the specific organic compound (J) in the second coating film.
  • the heating temperature of the second coating film after exposure and development preferably satisfies the relationship of T m + 100 ⁇ T h ⁇ T m ⁇ 30. In this case, deterioration of the components in the second resist composition due to heat is suppressed.
  • the temperature of the second coating film is lower than the melting point of the specific organic compound (J) from the time when the second coating film is formed on the first coating film to the time when the exposure of the second coating film is completed. It is more preferable to maintain it. In this case, the ratio of bubbles in the first region becomes higher, and the difference between the appearance color of the first region and the appearance color of the second region becomes more remarkable. This is because the specific organic compound (J) melts in the first portion before the photopolymerizable compound (G) in the first portion is polymerized, and the specific organic compound (J) in the first portion. Therefore, even if the first part is heated after the exposure of the second coating film, it is assumed that the first part is not easily deformed.
  • the temperature of the second coating film is determined from the melting point of the specific organic compound (J) between the time when the second resist composition is placed on the wiring board and the time when the exposure of the second coating film is completed. Is maintained at a temperature lower than the temperature 30 ° C. lower.
  • This second resist composition will be described in more detail.
  • the carboxyl group-containing resin (F) can impart developability with an alkaline solution to a coating film formed from the second resist composition.
  • the carboxyl group-containing resin (F) can be, for example, the same as the carboxyl group-containing resin (A) contained in the solder resist composition.
  • the photopolymerizable compound (G) can impart photocurability to the second resist composition.
  • the photopolymerizable compound (G) can be, for example, the same as the photopolymerizable compound (B) contained in the solder resist composition.
  • the photopolymerization initiator (H) can be, for example, the same as the photopolymerization disclosure agent (C) contained in the solder resist composition.
  • the photopolymerization initiator (H) contained in the second resist composition is preferably selected from the group consisting of ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, thioxanthones, and acylphosphine oxide photopolymerization initiators. Containing at least two components.
  • the colorant (I) includes, for example, at least one material selected from the group consisting of pigments, dyes, and pigments.
  • a coloring agent is a substance which colors the film formed from the composition for film formation.
  • the colorant can include both pigments and dyes.
  • the colorant (I) is not a substance that is colored but becomes colorless when heated in the process of forming a film from the film-forming composition because it does not color the film.
  • the colorant (I) is selected from the group consisting of, for example, a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, a brown colorant, and a colorant having a color other than those described above. At least one kind of material.
  • the colorant (I) preferably contains a green colorant or a mixture of a blue colorant and a yellow colorant.
  • the color of the appearance of the first region of the second resist layer is mainly green
  • the color of the appearance of the second region of the second resist layer is the color of the green colorant and the surface of the solder resist layer. It becomes a mixed color with the color. Since the first region and the second region have distinctly different appearance colors, the marking formed by the first region and the second region can be easily distinguished.
  • the colorant (E2) contained in the solder resist composition is a red pigment and the surface color of the solder resist layer is reddish black
  • the color of the appearance of the second region is deep black.
  • the color of the appearance of the first region of the second resist layer and the color of the appearance of the second region are particularly distinct. For this reason, the marking formed by the first region and the second region is particularly easily distinguished.
  • the green colorant can contain, for example, at least one colorant selected from the group consisting of phthalocyanine green colorants, anthraquinone green colorants, perylene green colorants, and metal-substituted or unsubstituted phthalocyanine compounds.
  • Specific examples of the green colorant include colorants represented by Pigment Green 7 and Pigment Green 36.
  • the specific organic compound (J) has a clear melting point, and is preferably a low-viscosity liquid at a temperature equal to or higher than this melting point.
  • the melting point of the specific organic compound (J) is preferably in the range of 100 to 230 ° C.
  • the specific organic compound (J) can contain, for example, at least one component selected from the group consisting of a crystalline epoxy compound and a dicarboxylic acid.
  • the crystalline epoxy compound can contain at least one component selected from the group consisting of a monomer, a prepolymer and a polymer having an epoxy group and crystallinity. Such components are commercially available and are readily available.
  • the crystalline epoxy compound is 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (high melting type)
  • Product name YDC-1312 hydroquinone type crystalline epoxy resin
  • Product name YSLV-120TE thioether type crystalline epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Product name GTR manufactured by Nippon Kayaku Co., Ltd. -1800 tetrakisphenolethane type crystalline epoxy resin
  • bisphenolfluorene type crystalline epoxy resin product name YX-4000 (biphenyl type crystalline epoxy resin) manufactured by Mitsubishi Chemical Corporation
  • 1,3,5-tris (2 , 3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (low It can contain at least one component selected from the group consisting of a point type).
  • the dicarboxylic acid is, for example, at least one selected from the group consisting of malonic acid, succinic acid, adipic acid, oxalic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, and 4-cyclohexene-1,2-dicarboxylic acid. It can contain ingredients.
  • the specific organic compound (J) may be a compound contained in the photopolymerization initiator (H).
  • Such compounds include, for example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and ethanone, It may contain at least one component selected from the group consisting of 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime).
  • the second resist composition may contain an epoxy compound.
  • the epoxy compound can contain, for example, at least one component selected from the group consisting of a crystalline epoxy compound contained in the specific organic compound (J) and an amorphous epoxy compound.
  • Non-crystalline epoxy compounds include, for example, non-crystalline cresol novolac type epoxy resin (specifically, product name EPICLON N-695 manufactured by DIC Corporation), non-crystalline phenol novolac type epoxy resin (specific example is DIC Corporation).
  • Product name EPICLON N-775 amorphous bisphenol A novolak type epoxy resin (specifically, product name EPICLON N-865 manufactured by DIC Corporation), amorphous bisphenol A type epoxy resin (specifically Mitsubishi Chemical) Product name jER1001), non-crystalline bisphenol F type epoxy resin (specifically, product name jER4004P manufactured by Mitsubishi Chemical Corporation), non-crystalline bisphenol S type epoxy resin (specifically, product name manufactured by DIC Corporation) EPICLON EXA- 514), non-crystalline bisphenol AD type epoxy resin, non-crystalline hydrogenated bisphenol A type epoxy resin, non-crystalline biphenyl novolac type epoxy resin, and non-crystalline special bifunctional type epoxy resin (as specific examples) Product numbers YL7175-500 and YL7175-1000
  • the second resist composition preferably contains a curing agent for curing the epoxy compound.
  • the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylpho
  • Examples of commercially available products of these compounds are 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).
  • Curing agents include guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S, which also function as an adhesion-imparting agent.
  • S-triazine derivatives such as triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct May be.
  • the second resist composition is a known photopolymerization accelerator such as benzoic acid or tertiary amines such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester and 2-dimethylaminoethylbenzoate.
  • An agent, a sensitizer and the like may be contained.
  • the second resist composition is a sensitizer for laser exposure methods, such as coumarin derivatives such as 7-diethylamino-4-methylcoumarin and 4,6-diethyl-7-ethylaminocoumarin, other carbocyanine dyes, xanthene. It may contain a pigment system or the like.
  • the second resist composition may contain a filler.
  • the filler can contain, for example, at least one component selected from the group consisting of silica, barium sulfate, carbon nanotubes, aluminum hydroxide, and magnesium hydroxide.
  • the second resist composition may further contain appropriate additives as necessary.
  • the second resist composition includes a copolymer such as silicone and acrylate; a leveling agent; an adhesion-imparting agent such as a silane coupling agent; a thixotropic agent; a polymerization inhibitor; an antihalation agent; a flame retardant; It may contain at least one component selected from the group consisting of an inhibitor; a surfactant; and a polymer dispersant.
  • the second resist composition may contain an organic solvent.
  • the organic solvent is used for the purpose of liquefaction or varnishing of the second resist composition, viscosity adjustment, coating property adjustment, film forming property adjustment, and the like. This organic solvent may be the same as the organic solvent contained in the solder resist composition, for example.
  • the ratio of the organic solvent in the second resist composition is such that the organic solvent is volatilized quickly during the preliminary drying of the second coating film, that is, the ratio of the organic solvent in the second resist composition is after the organic solvent is dried. It is preferable to adjust so that it may not remain in the second coating film.
  • the proportion of the organic solvent in the second resist composition is preferably in the range of 5 to 99.5% by mass. In this case, good applicability of the second resist composition can be obtained.
  • the suitable ratio of an organic solvent changes with application methods etc., it is preferable that a ratio is suitably adjusted according to the application method.
  • the amount of each component contained in the second resist composition is appropriately adjusted so that the second resist composition has photocurability and can be developed with an alkaline solution.
  • the ratio of the carboxyl group-containing resin (F) to the solid content of the second resist composition is preferably in the range of 15 to 55% by mass, more preferably in the range of 20 to 50% by mass, and still more preferably. It is in the range of 25 to 45% by mass.
  • the ratio of the photopolymerizable compound (G) to the carboxyl group-containing resin (F) contained in the second resist composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass. More preferably, it is in the range of 15 to 40% by mass.
  • the ratio of the photopolymerization initiator (H) to the carboxyl group-containing resin (F) contained in the second resist composition is in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass. More preferably, it is in the range of 5 to 25% by mass.
  • the ratio of the colorant (I) to the carboxyl group-containing resin (F) contained in the second resist composition is preferably in the range of 0.2 to 15% by mass, more preferably 0.5 to 10% by mass. Is within the range.
  • the ratio of the green colorant to the solid content of the second resist composition is preferably in the range of 0.2 to 15% by mass, and more preferably in the range of 0.5 to 10% by mass.
  • the ratio of the specific organic compound (J) to the carboxyl group-containing resin (F) contained in the second resist composition is preferably in the range of 15 to 200% by mass, more preferably in the range of 20 to 100% by mass. More preferably, it is in the range of 25 to 80% by mass, and particularly preferably in the range of 30 to 60% by mass.
  • the solid content here is the total amount of all components excluding components such as a solvent that volatilizes in the process of forming the second resist layer from the second resist composition.
  • the second resist composition can be obtained, for example, by kneading the above-mentioned second resist composition raw materials with a three-roll, ball mill, sand mill or the like.
  • the first agent is prepared by mixing a part of the raw material of the second resist composition
  • the second agent is prepared by mixing the remainder of the raw material of the second resist composition.
  • the first agent is prepared by previously mixing and dispersing the photopolymerizable compound (G), a part of the organic solvent, and the specific organic compound (J).
  • the second agent may be prepared by mixing and dispersing the remainder of the raw material of the second resist composition.
  • the second resist composition can be prepared by mixing the necessary amount of the first agent and the second agent in a timely manner.
  • the printed wiring board 100 is prepared, and the first coating film 1 is formed on the printed wiring board 100 from the solder resist composition by the method described above. Further, the wet coating film is dried to volatilize the organic solvent in the solder resist composition as necessary. Thereby, the dried 1st coating film 1 (dry coating film) is obtained.
  • the second coating film 2 is formed by applying a second resist composition onto the first coating film 1.
  • the coating method of the second resist composition is a method selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing.
  • the second coating film 2 is heated (preliminary drying) in order to volatilize the organic solvent in the second resist composition as necessary.
  • the heating temperature is preferably lower than the melting point of the specific organic compound (J) in the second resist composition, more preferably from the melting point of the specific organic compound (J) in the second resist composition.
  • the temperature is lower than the temperature 30 ° C. lower. This heating temperature is in the range of 60 to 100 ° C., for example.
  • the 2nd coating composition 2 (dry film) is formed by apply
  • the dry film may be transferred onto the first coating film 1 by applying pressure to the dry film and the first coating film 1 while the dry film is stacked on the first coating film 1 (dry Film method). In this case, preliminary drying may be omitted.
  • the coating film which consists of two layers of the 2nd coating film 2 and the 1st coating film 1 by apply
  • the mask 4 is directly or indirectly applied to the second coating film 2, and then the active energy rays are applied to the mask 4, thereby allowing the second coating film 2 to pass through the mask 4. And the 1st coating film 1 is exposed.
  • the active energy ray is selected according to the composition of the solder resist composition and the second resist composition, and is, for example, ultraviolet rays.
  • the ultraviolet light source is selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps, for example.
  • the mask 4 includes three types of portions each having different light transmittance.
  • the mask 4 includes a light transmissive portion (hereinafter referred to as a transmissive portion 41), a light transmissive portion lower than the transmissive portion 41 (hereinafter referred to as a low transmissive portion 42), and a light transmissive property.
  • a portion hereinafter referred to as a non-permeable portion 43).
  • the portion corresponding to the transmissive part 41 (first portion 21) in the second coating film 2 is irradiated with light, and the second coating film 2 is exposed.
  • the portion corresponding to the low-permeability portion 42 (second portion 22) is irradiated with light having an exposure amount lower than that of the first portion 21, and corresponds to the non-permeable portion 43 of the second coating film 2.
  • the portion (third portion 23) is not irradiated with light.
  • the first portion 21 is a portion irradiated with light at the time of exposure
  • the second portion 22 is a portion irradiated with light at an exposure amount lower than that of the first portion 21 at the time of exposure.
  • the portion 23 may be a portion that is not irradiated with light during exposure.
  • the first portion 21, the second portion 22, and the third portion 23 of the mask 4 are respectively located at predetermined locations on the second coating film 2.
  • the photopolymerization reaction of the photopolymerizable compound (G) proceeds in the first portion 21 of the second coating film 2, and even in the second portion 22, although the degree is lower than that of the portion 21, the photopolymerization reaction of the photopolymerizable compound (G) proceeds. On the other hand, in the third portion 23, the photopolymerization reaction of the photopolymerizable compound (G) does not proceed.
  • the second coating 2 is irradiated with light through a mask (first mask) that shields the third portion 23 and does not shield the first portion 21 and the second portion 22, and subsequently A mask (second mask) that shields the second portion 22 and does not shield the first portion 21 is superimposed on the first mask, and further light is transmitted through the first mask and the second mask. It may be irradiated. Even in this case, the first portion 21 is irradiated with light, the second portion 22 is irradiated with light at a lower exposure amount than the first portion 21, and the third portion 23 is irradiated with light. Not irradiated.
  • the ratio of the exposure amount of the second portion 22 to the exposure amount of the first portion 21 is preferably in the range of 1 to 75%, more preferably in the range of 1.2 to 60%.
  • the exposure amount of the first portion 21 is preferably in the range of 100 to 5000 mJ / cm 2 .
  • the exposure amount of the second portion 22 is preferably in the range of 20 to 500 mJ / cm 2 .
  • the first coating film 1 is exposed simultaneously with the second coating film 2 being exposed.
  • the portions corresponding to the transmissive portion 41 and the low permeable portion 42 in the first coating film 1 are cured when irradiated with light.
  • the portion corresponding to the non-permeable portion 43 in the first coating film 1 is not irradiated with light.
  • the second coating film 2 and the first coating film 1 are developed with an alkaline developer.
  • the third portion 23 of the second coating film 2 is removed from the printed wiring board 100, and the portion corresponding to the non-permeable portion 43 in the first coating film 1 is also removed from the printed wiring board 100. Is done.
  • the first portion 21 and the second portion 22 of the second coating film 2 remain on the printed wiring board 100.
  • the second coating film 2 (first portion 21 and second portion 22) is heated.
  • the heating temperature T h of the second coating film 2 satisfies the relation of T h ⁇ T m -30, preferably satisfies the relation T m + 100 ⁇ T h ⁇ T m -30.
  • T h (° C.) is the heating temperature of the second coating film 2
  • T m (° C.) is the melting point of the specific organic compound (J).
  • the heating temperature of the second coating film 2 is, for example, in the range of 100 to 200 ° C.
  • the heating time of the second coating film 2 is, for example, in the range of 20 minutes to 5 hours.
  • the second coating film 2 after heating the second coating film 2 at a heating temperature T h, further in the range of 150 °C ⁇ 300 °C, it may be heated second coating 2 at conditions within the range of 1 to 10 minutes. Further, after heating the second coating film 2 at a heating temperature T h, it may be irradiated with ultraviolet light under conditions in the range of 100 ⁇ 5000mJ / cm 2.
  • the entire first portion 21 and the second portion 22 may be irradiated with light.
  • the photopolymerization reaction of the photopolymerizable compound (G) remaining unreacted in the first portion 21 and the second portion 22 proceeds.
  • a solder resist layer 10 made of a cured product of the first coating film 1 is formed on the printed wiring board 100, and the second coating film 2 is formed on the solder resist layer 10.
  • a second resist layer 20 made of the cured product is formed. Thereby, a covering printed wiring board is obtained.
  • the second resist layer 20 of the coated printed wiring board includes a first region 24 that is a cured product of the first portion 21 and a second region 25 that is a cured product of the second portion 22.
  • the first region 24 contains bubbles.
  • the second region 25 does not contain bubbles, or the second region 25 contains bubbles at a lower density than the first region 24. For this reason, there is a difference between the light transmittance of the first region 24 and the light transmittance of the second region 25, and the light transmittance of the second region 25 is the light transmittance of the first region 24. Higher than.
  • the ratio of bubbles contained in the first region 24 is preferably in the range of 3 to 70%, more preferably in the range of 5 to 60%. Further, the ratio of the bubbles contained in the second area 25 to the ratio of the bubbles contained in the first area 24 is preferably in the range of 0 to 5%.
  • the ratio of these bubbles is a major axis of 0.5 ⁇ m on the surface appearing by polishing the surface of the second resist layer 20 (that is, the cross section of the second resist layer 20 along the surface of the second resist layer 20).
  • This area ratio is derived based on the area of bubbles having a major axis of 0.5 ⁇ m or more on the surface of the second resist layer 20 having a surface area of 20 ⁇ m 2 , for example.
  • the ratio of these bubbles can be controlled by appropriately adjusting the exposure amount for the first portion 21 and the exposure amount for the second portion 22.
  • the thickness of the second resist layer 20 is preferably in the range of 10 to 40 ⁇ m, for example. In this case, the marking formed by the first region 24 and the second region 25 can be easily determined.
  • the ratio of bubbles in the first region 24 is preferably within a range of 5 to 70%, and the ratio of the ratio of bubbles in the second region 25 is It is preferably in the range of 0 to 5%.
  • the L * value of the first region 24 is 35 or more, the a * value is -15 or less, and the b * value is within the range of -5 to 5.
  • the second region 25 has an L * value of 32 or less, an a * value in the range of ⁇ 10 to 10, and a b * value in the range of ⁇ 5 to 5. In this case, the marking formed by the first region 24 and the second region 25 can be distinguished particularly easily.
  • the L * value of the first region 24 of the second resist layer 20 on the solder resist layer 10 is 35 or more, the a * value is ⁇ 15 or less, the b * value is in the range of ⁇ 5 to 5, and In order that the L * value of the second region 25 is 32 or less, the a * value is in the range of ⁇ 10 to 10 and the b * value is in the range of ⁇ 5 to 5, the colorant (in the solder resist composition) It is preferable that E2) is a red colorant and the colorant (I) in the second resist composition is a green colorant. In this case, since the color of the colorant (E2) and the colorant (I) have a complementary relationship, it is easy to make the color of the second region 25 deep black.
  • the L * value of the solder resist layer 10 is 40 or less, the a * value is in the range of 5.1 to 55, and the b * value is in the range of ⁇ 15 to 15. It is preferable to be within.
  • the L * value of the second region 25 in the second resist layer 20 is 35 or more, the a * value is in the range of ⁇ 100 to ⁇ 15, b * The value is preferably in the range of ⁇ 20 to 20.
  • a cresol novolac type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YDCN-700-5, epoxy equivalent 203 is placed in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer.
  • a mixture was prepared by adding 203 parts by mass, 160.1 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72.7 parts by mass of acrylic acid, and 0.6 parts by mass of dimethylbenzylamine. This mixture was heated in a flask under the conditions of a heating temperature of 110 ° C. and a heating time of 10 hours, thereby causing the addition reaction to proceed.
  • Epoxy resin 1,3,5-triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, TEPIC-HP).
  • Epoxy resin solution A solution obtained by dissolving cresol novolac type epoxy resin (manufactured by DIC Corporation, product name EPICLON N-695) in diethylene glycol monoethyl ether acetate at a solid content of 70%.
  • Photopolymerization initiator A 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, product name Irgacure 907).
  • Photopolymerization initiator B 2,4-diethylthioxanthen-9-one (DETX).
  • Photopolymerization initiator C 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, product name Irgacure TPO manufactured by BASF.
  • Photopolymerization initiator D 1-hydroxy-cyclohexyl-phenyl-ketone, product name Irgacure 184 manufactured by BASF.
  • Photopolymerizable monomer dipentaerythritol hexaacrylate (DPHA).
  • Melamine Fine melamine manufactured by Nissan Chemical Industries, Ltd.
  • Barium sulfate Product name Variace B30 manufactured by Sakai Chemical Industry Co., Ltd.
  • Fine silica Product name Leoroseal MT-10 manufactured by Tokuyama Corporation.
  • Antifoaming agent Product name KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Perylene Black A Product name Palogen Black S 0084 manufactured by BASF.
  • Perylene Black B Product name Lumogen Black FK 4280 manufactured by BASF.
  • Carbon black Product name MA7 manufactured by Mitsubishi Chemical Corporation.
  • Anthraquinone red pigment A product name HOSTAPERSM SCARLET GO manufactured by Clariant Japan Ltd. (color index is Pigment Red 168).
  • Anthraquinone red pigment B Product name Palogen Red L 4045 (Color Index Pigment Red 177) manufactured by BASF Corporation.
  • -Azo-based red pigment Product name Seika First Red 1531B manufactured by Dainichi Seika Co., Ltd.
  • Solvent diethylene glycol monoethyl ether acetate.
  • a wiring board provided with copper conductor wiring having a line width / line spacing of 0.2 mm / 0.3 mm and a thickness of 35 ⁇ m was prepared.
  • a wet coating film was formed on the surface of the wiring board by applying the solder resist composition by screen printing. This wet coating film was pre-dried by heating at 80 ° C. for 20 minutes to form a dry coating film having a thickness of 20 ⁇ m.
  • the dried coating film is applied with a mask on which solder dams having a width of 25 ⁇ m, 50 ⁇ m, 75 ⁇ m, and 100 ⁇ m are formed and irradiated with ultraviolet rays under a condition of an irradiation energy density of 400 mJ / cm 2 to dry the wiring substrate.
  • the coating was selectively exposed.
  • the exposed dried coating film was developed with an aqueous sodium carbonate solution to leave a portion cured by exposure in the dried coating film on the wiring board, and an uncured portion was removed.
  • solder resist layer including a solder dam having a thickness of 40 ⁇ m was formed on the wiring board.
  • Comparative Example 1 does not contain a pigment other than black
  • Comparative Example 2 does not contain a black pigment such as perylene black
  • the solder resist layers of Comparative Examples 1 and 2 have the required L * value, a * value, and b * is considered that the value could not be satisfied.
  • a cresol novolac type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YDCN-700-5, epoxy equivalent 203 is placed in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer.
  • a mixture was prepared by adding 203 parts by mass, 103 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 1.5 parts by mass of triphenylphosphine. This mixture was heated under the conditions of a heating temperature of 110 ° C.
  • Photopolymerizable monomer dipentaerythritol hexaacrylate (DPHA).
  • Crystalline epoxy compound 1,3,5-triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, TEPIC-HP).
  • Photopolymerization initiator A 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, product name Irgacure TPO manufactured by BASF.
  • Photopolymerization initiator B 1-hydroxy-cyclohexyl-phenyl-ketone, product name Irgacure 184 manufactured by BASF.
  • Barium sulfate Product name Variace B30 manufactured by Sakai Chemical Industry Co., Ltd. ⁇ Fine silica: Product name Leoroseal MT-10 manufactured by Tokuyama Corporation. Melamine: Fine melamine manufactured by Nissan Chemical Industries, Ltd. Green colorant: phthalocyanine green. Antifoaming agent: Product name KS-66 manufactured by Shin-Etsu Chemical Co., Ltd. Solvent: diethylene glycol monoethyl ether acetate.
  • a wiring board provided with copper conductor wiring having a line width / line spacing of 0.2 mm / 0.3 mm and a thickness of 35 ⁇ m was prepared.
  • the first coating film was formed by applying the solder resist composition used in Examples 1 to 5 and Comparative Examples 1 to 3 by screen printing. This first coating film was pre-dried by heating at 80 ° C. for 20 minutes, and the thickness was 20 ⁇ m.
  • the second coating film was formed on the first coating film by applying the second resist composition on the first coating film by a screen printing method. This second coating film was pre-dried by heating at 80 ° C. for 20 minutes. The thickness of the second coating film after drying was 40 ⁇ m.
  • the second coating film is applied with a mask on which solder dams having a width of 25 ⁇ m, 50 ⁇ m, 75 ⁇ m, and 100 ⁇ m are formed, and the first coating film and the second coating film are irradiated with ultraviolet rays through the mask. Selective exposure.
  • a first portion and a second portion were set, and two types of ultraviolet rays having different irradiation energy densities were irradiated.
  • the irradiation energy density of the ultraviolet rays irradiated to the first portion is 600 mJ / cm 2
  • the irradiation energy density of the ultraviolet rays irradiated to the second portion is 70 mJ / cm 2 .
  • the first coating film and the second coating film remaining on the wiring board were cured by heating at 150 ° C. for 60 minutes. Thereby, a solder resist layer and a second resist layer were formed.
  • the total thickness of the solder resist layer and the second resist layer was 60 ⁇ m.
  • a region corresponding to the second portion where the irradiation energy density of the irradiated ultraviolet light is small is a low exposure region, and a region corresponding to the first portion where the irradiation energy density of the irradiated ultraviolet light is large. It was a high exposure area.
  • the appearance color of the second resist layer is green in the high-exposure area, and mixed color of green and the surface color of the solder resist layer in the low-exposure area.
  • the solder resist composition is other than black.
  • Comparative Example 5 since the solder resist composition does not contain a black colorant, the first region having the required L * value, a * value, and b * value This is probably because the second resist layer including the second region could not be formed.
  • the solder resist composition according to the first aspect is at least selected from the group consisting of a carboxyl group-containing resin (A), a photopolymerizable monomer, and a photopolymerizable prepolymer.
  • a film of the solder resist composition having a thickness within the range of 18 to 22 ⁇ m when the solder resist composition is photocured on a copper plate and then thermally cured .
  • the properties are such that the value is 40 or less, the a * value is in the range of 5.1 to 55, and the b * value is in the range of ⁇ 15 to 15.
  • the colorant (E2) is a red colorant.
  • the colorant (E2) is an anthraquinone red colorant in the first or second aspect.
  • thermosetting component (D) includes a compound having a cyclic ether skeleton.
  • the carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A2) having a photopolymerizable functional group.
  • a coated printed wiring board according to a sixth aspect includes a printed wiring board and a solder resist layer formed from the solder resist composition according to any one of the first to fifth aspects, and covering the printed wiring board. Including.
  • the coated printed wiring board according to the seventh aspect includes a second resist layer covering the solder resist layer in the sixth aspect.
  • the second resist layer includes a first region and a second region having a higher light transmittance than the first region.
  • the coated printed wiring board according to the ninth aspect is the eighth aspect, wherein the L * value of the first region is 35 or more, the a * value is ⁇ 15 or less, and the b * value is within the range of ⁇ 5 to 5.
  • the second region has an L * value of 32 or less, an a * value in the range of ⁇ 10 to 10, and a b * value in the range of ⁇ 5 to 5.
  • the second resist layer contains a green colorant.

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Abstract

This solder resist composition contains a carboxyl group-containing resin (A), a photopolymerizable compound (B) containing at least one kind selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer, a photopolymerization initiator (C), a thermosetting component (D), a perylene-based black colorant (E1), and one kind of colorant (E2) other than black, the solder resist composition having such properties that the coating of the solder resist composition photocured on a copper plate and then thermoset to have any thickness within the range of 18-22 μｍ has a L ＊ value of 40 or less, an ａ＊ value in the range of 5.1-55, and a ｂ＊ value in the range of -15-15.

Description

ソルダーレジスト組成物、及び被覆プリント配線板Solder resist composition and coated printed wiring board
　本発明は、ソルダーレジスト組成物及び被覆プリント配線板に関する。本発明は、詳細には、光硬化性を有しアルカリ性溶液で現像可能な液状のソルダーレジスト組成物、及びこのソルダーレジスト組成物から形成されたソルダーレジスト層を備える被覆プリント配線板に関する。 The present invention relates to a solder resist composition and a coated printed wiring board. More specifically, the present invention relates to a liquid solder resist composition that is photocurable and developable with an alkaline solution, and a coated printed wiring board including a solder resist layer formed from the solder resist composition.
　近年、民生用及び産業用のプリント配線板のソルダーレジスト層を、スクリーン印刷法ではなく、液状ソルダーレジスト組成物を用いる方法で形成されることがある。液状ソルダーレジストを用いる方法は、解像性に優れ、現像可能であり、それゆえ、高密度配線のプリント配線板を形成することができる。 In recent years, the solder resist layer of consumer and industrial printed wiring boards is sometimes formed by a method using a liquid solder resist composition instead of a screen printing method. The method using a liquid solder resist is excellent in resolution and developable, and therefore, a printed wiring board having high-density wiring can be formed.
　有色のソルダーレジスト層、特に黒色のソルダーレジスト層でプリント配線板を覆うことにより、プリント配線板の導体配線を見えにくくなり得る。黒色のソルダーレジスト層は、黒色着色剤を多量に含むため、黒色着色剤の光吸収によって、解像性が低下し得る。例えば日本国特許公開番号第２００８－２５７０４５号には、黒色着色剤としてカーボンブラックが含まれ、黒色以外の着色剤としてフタロシアニンブルー及びアントラキノン系レッドが含まれる黒色ソルダーレジスト組成物が開示されている。この黒色ソルダーレジスト組成物が黒色以外の着色剤を含むことによって、黒色着色剤の使用量を低減される。その結果、ソルダーレジスト組成物から形成されるソルダーレジスト層の解像性を向上させている。 覆 う Covering the printed wiring board with a colored solder resist layer, particularly a black solder resist layer, may make it difficult to see the conductor wiring of the printed wiring board. Since the black solder resist layer contains a large amount of black colorant, the resolution can be lowered by light absorption of the black colorant. For example, Japanese Patent Publication No. 2008-257045 discloses a black solder resist composition containing carbon black as a black colorant and phthalocyanine blue and anthraquinone red as colorants other than black. When this black solder resist composition contains a colorant other than black, the amount of black colorant used is reduced. As a result, the resolution of the solder resist layer formed from the solder resist composition is improved.
　しかし、更なる高密度配線のプリント配線板を形成するために、解像性とソルダーレジスト層による導体配線の隠蔽性とを更に向上させることが求められている。 However, in order to form a printed wiring board with higher density wiring, it is required to further improve the resolution and the concealability of the conductor wiring by the solder resist layer.
　本発明の目的は、所要の解像性及び隠蔽性を備えるソルダーレジスト層を形成することができるソルダーレジスト組成物、及びこのソルダーレジスト組成物から形成されるソルダーレジスト層を備える被覆プリント配線板を提供することである。 An object of the present invention is to provide a solder resist composition capable of forming a solder resist layer having required resolution and concealment, and a coated printed wiring board including a solder resist layer formed from the solder resist composition. Is to provide.
　本発明の一態様に係るソルダーレジスト組成物は、カルボキシル基含有樹脂（Ａ）と、　光重合性モノマー及び光重合性プレポリマーからなる群から選択される少なくとも一種を含有する光重合性化合物（Ｂ）と、光重合開始剤（Ｃ）と、熱硬化性成分（Ｄ）と、ペリレン系黒色着色剤（Ｅ１）と、黒色以外の一種の着色剤（Ｅ２）と、を含有し、前記ソルダーレジスト組成物を銅板上で光硬化させてから熱硬化させて、１８～２２μｍの範囲内のいずれかの厚みになる前記ソルダーレジスト組成物の皮膜が、Ｌ＊値が４０以下であり、ａ＊値が５．１～５５の範囲内であり、ｂ＊値が－１５～１５の範囲内であるような性質を有する。 The solder resist composition according to one embodiment of the present invention is a photopolymerizable compound (B) containing at least one selected from the group consisting of a carboxyl group-containing resin (A), a photopolymerizable monomer, and a photopolymerizable prepolymer. ), A photopolymerization initiator (C), a thermosetting component (D), a perylene-based black colorant (E1), and a colorant other than black (E2), and the solder resist When the composition is photocured on a copper plate and then thermally cured, the film of the solder resist composition having any thickness within the range of 18 to 22 μm has an L * value of 40 or less and an a * value. Is in the range of 5.1 to 55, and the b * value is in the range of −15 to 15.
　好ましくは、前記着色剤（Ｅ２）は赤色着色剤である。 Preferably, the colorant (E2) is a red colorant.
　好ましくは、前記着色剤（Ｅ２）はアントラキノン系赤色着色剤である。 Preferably, the colorant (E2) is an anthraquinone red colorant.
　好ましくは、前記熱硬化性成分（Ｄ）は環状エーテル骨格を有する化合物を含む。 Preferably, the thermosetting component (D) includes a compound having a cyclic ether skeleton.
　好ましくは、前記カルボキシル基含有樹脂（Ａ）は光重合性官能基を備えるカルボキシル基含有樹脂（Ａ２）を含む。 Preferably, the carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A2) having a photopolymerizable functional group.
　本発明の一態様に係る被覆プリント配線板は、プリント配線板と、上記のソルダーレジスト組成物から形成され、前記プリント配線板を覆うソルダーレジスト層と、を備える。 A coated printed wiring board according to an aspect of the present invention includes a printed wiring board and a solder resist layer formed from the above solder resist composition and covering the printed wiring board.
　好ましくは、前記ソルダーレジスト層を覆う第二レジスト層を備える。 Preferably, a second resist layer covering the solder resist layer is provided.
　好ましくは、前記第二レジスト層は、第一の領域と、前記第一の領域よりも高い光透過率を有する第二の領域を含む。 Preferably, the second resist layer includes a first region and a second region having a light transmittance higher than that of the first region.
　好ましくは、前記第二ソルダーレジスト層は緑色着色剤を含有する。 Preferably, the second solder resist layer contains a green colorant.
　好ましくは、前記第一の領域のＬ＊値が３５以上、ａ＊値が－１５以下、且つｂ＊値が－５～５の範囲内であり、前記第二の領域のＬ＊値が３２以下、ａ＊値が－１０～１０の範囲内、ｂ＊値が－５～５の範囲内である。 Preferably, the L * value of the first region is 35 or more, the a * value is −15 or less, the b * value is in the range of −5 to 5, and the L * value of the second region is 32. Hereinafter, the a * value is in the range of −10 to 10, and the b * value is in the range of −5 to 5.
　本発明の一態様によれば、所要の解像性及び隠蔽性を備えるソルダーレジスト層が得られる。 According to one aspect of the present invention, a solder resist layer having required resolution and concealing properties can be obtained.
図１Ａ～図１Ｃは、一実施形態に係る被覆プリント配線板の製造工程の一例を示す断面図である。1A to 1C are cross-sectional views illustrating an example of a manufacturing process of a coated printed wiring board according to an embodiment. 図２Ａ～図２Ｃは、他の実施形態に係る被覆プリント配線板の製造工程の一例を示す断面図である。2A to 2C are cross-sectional views showing an example of a manufacturing process of a coated printed wiring board according to another embodiment.
　以下、本発明の実施形態について説明する。なお、以下の説明において、「（メタ）アクリル」とは、「アクリル」と「メタクリル」のうち少なくとも一方を意味する。例えば、（メタ）アクリレートは、アクリレートとメタクリレートとのうち少なくとも一方を意味する。 Hereinafter, embodiments of the present invention will be described. In the following description, “(meth) acryl” means at least one of “acryl” and “methacryl”. For example, (meth) acrylate means at least one of acrylate and methacrylate.
　ソルダーレジスト組成物は、カルボキシル基含有樹脂（Ａ）と、光重合性モノマー及び光重合性プレポリマーからなる群から選択される少なくとも一種を含有する光重合性化合物（Ｂ）と、光重合開始剤（Ｃ）と、熱硬化性成分（Ｄ）と、ペリレン系黒色着色剤（Ｅ１）と、黒色以外の一種の着色剤（Ｅ２）と、を含有する。このソルダーレジスト組成物を銅板上で光硬化させてから熱硬化させて、１８～２２μｍの範囲内のいずれかの厚みになる前記ソルダーレジスト組成物の皮膜は、Ｌ＊値が４０以下であり、ａ＊値が５．１～５５の範囲内であり、ｂ＊値が－１５～１５の範囲内であるような性質を有する。 The solder resist composition includes a carboxyl group-containing resin (A), a photopolymerizable compound (B) containing at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer, and a photopolymerization initiator. (C), a thermosetting component (D), a perylene-based black colorant (E1), and a kind of colorant (E2) other than black. When the solder resist composition is photocured on a copper plate and then thermally cured, the film of the solder resist composition having any thickness within the range of 18 to 22 μm has an L * value of 40 or less, The a * value is in the range of 5.1 to 55, and the b * value is in the range of −15 to 15.
　ソルダーレジスト組成物が、ペリレン系黒色着色剤（Ｅ１）及び黒色以外の着色剤（Ｅ２）を含むと共に、ソルダーレジスト組成物から形成された被膜が、特定範囲のＬ＊値、ａ＊値、及びｂ＊値を有することにより、ソルダーレジスト組成物の被膜が露光される場合際に、この被膜を表層から深部まで十分に硬化させることができる。これにより、ソルダーレジスト組成物から形成されるソルダーレジスト層の解像性及び隠蔽性を向上させることができる。 The solder resist composition includes a perylene-based black colorant (E1) and a colorant other than black (E2), and a film formed from the solder resist composition has a specific range of L * value, a * value, and By having the b * value, when the film of the solder resist composition is exposed, the film can be sufficiently cured from the surface layer to the deep part. Thereby, the resolution and concealment property of the soldering resist layer formed from a soldering resist composition can be improved.
　一実施形態に係るソルダーレジスト組成物について、更に詳しく説明する。 The solder resist composition according to one embodiment will be described in more detail.
　［カルボキシル基含有樹脂（Ａ）］
　カルボキシル基含有樹脂（Ａ）は、ソルダーレジスト組成物から形成される被膜に、アルカリ性溶液による現像性、すなわちアルカリ現像性を付与することができる。 [Carboxyl group-containing resin (A)]
The carboxyl group-containing resin (A) can impart developability with an alkaline solution, that is, alkali developability, to the film formed from the solder resist composition.
　［カルボキシル基を有し、光重合性官能基を有さないカルボキシル基含有樹脂（Ａ１）について］
　カルボキシル基含有樹脂（Ａ）は、カルボキシル基を有し、光重合官能基を有さないカルボキシル基含有樹脂（Ａ１）を含有することができる。 [Carboxyl group-containing resin (A1) having a carboxyl group and no photopolymerizable functional group]
The carboxyl group-containing resin (A) can contain a carboxyl group-containing resin (A1) that has a carboxyl group and does not have a photopolymerizable functional group.
　カルボキシル基含有樹脂（Ａ１）は、例えば、カルボキシル基を有するエチレン性不飽和化合物を含むエチレン性不飽和単量体の重合体を含有する。エチレン性不飽和単量体はカルボキシル基を有さないエチレン性不飽和化合物を含んでもよい。 The carboxyl group-containing resin (A1) contains, for example, a polymer of an ethylenically unsaturated monomer including an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may include an ethylenically unsaturated compound having no carboxyl group.
　カルボキシル基を有するエチレン性不飽和化合物は、適宜のポリマー及びプレポリマーを含有することができ、例えば、エチレン性不飽和基を１個のみ有する化合物を含有することができる。より具体的には、カルボキシル基を有するエチレン性不飽和化合物は、例えばアクリル酸、メタクリル酸、ω－カルボキシ－ポリカプロラクトン（ｎ≒２）モノアクリレート、クロトン酸、桂皮酸、２－アクリロイルオキシエチルコハク酸、２－メタクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－メタクリロイルオキシエチルフタル酸、β－カルボキシエチルアクリレート、アクリロイルオキシエチルサクシネート、メタクリロイルオキシエチルサクシネート、２－プロペノイックアシッド，３－（２－カルボキシエトキシ）－３－オキシプロピルエステル、２－アクリロイルオキシエチルテトラヒドロフタル酸、２－メタクリロイルオキシエチルテトラヒドロフタル酸、２－アクリロイルオキシエチルヘキサヒドロフタル酸、及び２－メタクリロイルオキシエチルヘキサヒドロフタル酸からなる群から選択される少なくとも一種の化合物を含有できる。カルボキシル基を有するエチレン性不飽和化合物は、エチレン性不飽和基を複数有する化合物を含有することもできる。より具体的には、カルボキシル基を有するエチレン性不飽和化合物は、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパンジメタクリレート、ジペンタエリスリトールペンタアクリレート、及びジペンタエリスリトールペンタメタクリレートのうちいずかのヒドロキシル基を有する多官能の（メタ）アクリレートと、二塩基酸無水物とを反応によって得られる化合物を含有してもよい。これらの化合物は、単独で使用されてもよく、複数併用されてもよい。 The ethylenically unsaturated compound having a carboxyl group can contain an appropriate polymer and prepolymer, for example, a compound having only one ethylenically unsaturated group. More specifically, ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate. Acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid , 3- (2-Carboxyethoxy) -3-oxypropyl ester, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethylhexyl It may contain at least one compound selected from the group consisting of sahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid. The ethylenically unsaturated compound having a carboxyl group can also contain a compound having a plurality of ethylenically unsaturated groups. More specifically, ethylenically unsaturated compounds having a carboxyl group are pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentane. You may contain the compound obtained by reaction with the polyfunctional (meth) acrylate which has any hydroxyl group among methacrylate, and a dibasic acid anhydride. These compounds may be used alone or in combination.
　カルボキシル基を有さないエチレン性不飽和化合物は、カルボキシル基を有するエチレン性不飽和化合物と共重合可能な化合物であってもよい。カルボキシル基を有さないエチレン性不飽和化合物は、芳香環を有する化合物及び芳香環を有さない化合物の両方を含有してもよい。 The ethylenically unsaturated compound having no carboxyl group may be a compound copolymerizable with the ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having no carboxyl group may contain both a compound having an aromatic ring and a compound having no aromatic ring.
　芳香環を有する化合物は、例えば、２－（メタ）アクリロイロキシエチルフタレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチルフタレート、２－（メタ）アクリロイロキシプロピルフタレート、ベンジル（メタ）アクリレート、ネオペンチルグリコールベンゾエート（メタ）アクリレート、パラクミルフェノキシエチレングリコール（メタ）アクリレート、ＥＯ変性クレゾール（メタ）アクリレート、エトキシ化フェニル（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート（ｎ＝２～１７）、ＥＣＨ変性フェノキシ（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシヘキサエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、トリブロモフェニル（メタ）アクリレート、ＥＯ変性トリブロモフェニル（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、ＰＯ変性ビスフェノールＡジ（メタ）アクリレート、変性ビスフェノールＡジ（メタ）アクリレート、ＥＯ変性ビスフェノールＦジ（メタ）アクリレート、ＥＣＨ変性フタル酸ジ（メタ）アクリレート、トリメチロールプロパンベンゾエート（メタ）アクリレート、ＥＯ変性フタル酸（メタ）アクリレート、ＥＯ、ＰＯ変性フタル酸（メタ）アクリレート、ビニルカルバゾール、スチレン、ビニルナフタレン、及びビニルビフェニルからなる群から選択される少なくとも一種の化合物を含有できる。 Examples of the compound having an aromatic ring include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, benzyl (meta ) Acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (n = 2) 17), ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol ( ) Acrylate, phenoxytetraethylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate , Modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, EO modified phthalic acid (meth) acrylate, EO, It may contain at least one compound selected from the group consisting of PO-modified phthalic acid (meth) acrylate, vinyl carbazole, styrene, vinyl naphthalene, and vinyl biphenyl.
　芳香環を有さない化合物は、例えば直鎖又は分岐の脂肪族、脂環族（但し、環中に不飽和結合を有してもよい）の（メタ）アクリル酸エステル、ヒドロキシアルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレート等；及びＮ－シクロヘキシルマレイミド等のＮ－置換マレイミド類からなる群から選択される少なくとも一種の化合物を含有できる。芳香環を有さない化合物は、更にポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の、１分子中にエチレン性不飽和基を２個以上有する化合物を含有してもよい。これらの化合物は単独で使用されてもよく、複数併用されてもよい。これらの化合物を使用することにより、ソルダーレジスト層の硬度及び油性を容易に調節することができる。 The compound having no aromatic ring is, for example, a linear or branched aliphatic or alicyclic (but may have an unsaturated bond in the ring) (meth) acrylic acid ester, hydroxyalkyl (meth) It may contain at least one compound selected from the group consisting of acrylates, alkoxyalkyl (meth) acrylates, etc .; and N-substituted maleimides such as N-cyclohexylmaleimide. Compounds that do not have an aromatic ring include ethylene glycol in one molecule such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. You may contain the compound which has 2 or more of unsaturated unsaturated groups. These compounds may be used alone or in combination. By using these compounds, the hardness and oiliness of the solder resist layer can be easily adjusted.
　カルボキシル基含有樹脂（Ａ１）の酸価を適当にするため、カルボキシル基含有樹脂（Ａ１）を得るために用いられる化合物の種類、比率等は適宜選択される。カルボキシル基含有樹脂（Ａ１）の酸価は、好ましくは２０～１８０ｍｇＫＯＨ／ｇの範囲内であり、より好ましくは３５～１６５ｍｇＫＯＨ／ｇの範囲内である。 In order to make the acid value of the carboxyl group-containing resin (A1) appropriate, the type, ratio, and the like of the compound used to obtain the carboxyl group-containing resin (A1) are appropriately selected. The acid value of the carboxyl group-containing resin (A1) is preferably in the range of 20 to 180 mgKOH / g, more preferably in the range of 35 to 165 mgKOH / g.
　［光重合性官能基を有するカルボキシル基含有樹脂（Ａ２）について］
　カルボキシル基含有樹脂（Ａ）は、光重合性官能基を有するカルボキシル基含有樹脂（Ａ２）を含有できる。光重合性官能基は、例えばエチレン性不飽和基である。 [About carboxyl group-containing resin (A2) having a photopolymerizable functional group]
The carboxyl group-containing resin (A) can contain a carboxyl group-containing resin (A2) having a photopolymerizable functional group. The photopolymerizable functional group is, for example, an ethylenically unsaturated group.
　カルボキシル基含有樹脂（Ａ２）は、例えば一分子中に二個以上のエポキシ基を有するエポキシ化合物（ａ１）における前記エポキシ基のうち少なくとも一つと、カルボキシル基を有するエチレン性不飽和化合物（ａ２）とが反応し、更に多価カルボン酸及びその無水物からなる群から選択される少なくとも一種である化合物（ａ３）が付加した構造を有する樹脂（以下、第一の樹脂（ａ）という）を含有できる。 The carboxyl group-containing resin (A2) includes, for example, at least one of the epoxy groups in the epoxy compound (a1) having two or more epoxy groups in one molecule, an ethylenically unsaturated compound (a2) having a carboxyl group, and And a resin having a structure to which at least one compound (a3) selected from the group consisting of polyvalent carboxylic acids and anhydrides is added (hereinafter referred to as first resin (a)) can be contained. .
　エポキシ化合物（ａ１）は、例えばクレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、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Ａ－ノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、トリグリシジルイソシアヌレート、脂環式エポキシ樹脂、及びエポキシ基を有する化合物を含むエチレン性不飽和化合物の重合体からなる群から選択される少なくとも一種の化合物を含有できる。 The epoxy compound (a1) includes, for example, a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A-novolak type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, It can contain at least one compound selected from the group consisting of polymers of ethylenically unsaturated compounds including biphenyl aralkyl type epoxy resins, triglycidyl isocyanurates, alicyclic epoxy resins, and compounds having epoxy groups.
　エポキシ化合物（ａ１）は、エポキシ基を備える化合物（ｐ１）を含むエチレン性不飽和化合物（ｐ）の重合体を含有してもよい。エチレン性不飽和化合物（ｐ）は、エポキシ基を備える化合物（ｐ１）のみを含有してもよく、エポキシ基を備える化合物（ｐ１）とエポキシ基を備えない化合物（ｐ２）とを含有してもよい。 The epoxy compound (a1) may contain a polymer of an ethylenically unsaturated compound (p) including a compound (p1) having an epoxy group. The ethylenically unsaturated compound (p) may contain only the compound (p1) having an epoxy group, or may contain the compound (p1) having an epoxy group and the compound (p2) not having an epoxy group. Good.
　エポキシ基を備える化合物（ｐ１）は、適宜のポリマー及びプレポリマーからなる群から選択される少なくとも一種を含有できる。具体的には、エポキシ基を備える化合物（ｐ１）は、アクリル酸のエポキシシクロヘキシル誘導体類、メタクリル酸のエポキシシクロヘキシル誘導体類、アクリレートの脂環エポキシ誘導体、メタクリレートの脂環エポキシ誘導体、β－メチルグリシジルアクリレート、及びβ－メチルグリシジルメタクリレートからなる群から選択される少なくとも一種の成分を含有できる。特に、エポキシ基を備える化合物（ｐ１）が、汎用されて入手が容易なグリシジル（メタ）アクリレートを含有することが好ましい。 The compound (p1) having an epoxy group can contain at least one selected from the group consisting of an appropriate polymer and a prepolymer. Specifically, the compound (p1) having an epoxy group includes epoxy cyclohexyl derivatives of acrylic acid, epoxy cyclohexyl derivatives of methacrylic acid, alicyclic epoxy derivatives of acrylate, alicyclic epoxy derivatives of methacrylate, β-methylglycidyl acrylate And at least one component selected from the group consisting of β-methylglycidyl methacrylate. In particular, it is preferable that the compound (p1) having an epoxy group contains glycidyl (meth) acrylate which is widely used and easily available.
　エポキシ基を備えない化合物（ｐ２）は、例えば、エポキシ基を備える化合物（ｐ１）と共重合可能な化合物であり得る。エポキシ基を備えない化合物（ｐ２）は、例えば、２－（メタ）アクリロイロキシエチルフタレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチルフタレート、２－（メタ）アクリロイロキシプロピルフタレート、ベンジル（メタ）アクリレート、ネオペンチルグリコールベンゾエート（メタ）アクリレート、パラクミルフェノキシエチレングリコール（メタ）アクリレート、ＥＯ変性クレゾール（メタ）アクリレート、エトキシ化フェニル（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート（重合度ｎ＝２～１７）、ＥＣＨ変性フェノキシ（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシヘキサエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、トリブロモフェニル（メタ）アクリレート、ＥＯ変性トリブロモフェニル（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、ＰＯ変性ビスフェノールＡジ（メタ）アクリレート、変性ビスフェノールＡジ（メタ）アクリレート、ＥＯ変性ビスフェノールＦジ（メタ）アクリレート、ＥＣＨ変性フタル酸ジ（メタ）アクリレート、トリメチロールプロパンベンゾエート（メタ）アクリレート、ＥＯ変性フタル酸（メタ）アクリレート、ＥＯ，ＰＯ変性フタル酸（メタ）アクリレート、ビニルカルバゾール、スチレン、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミド、３－マレイミド安息香酸Ｎ－スクシンイミジル、直鎖状或いは分岐を有する脂肪族又は脂環族（但し、環中に一部不飽和結合を有してもよい）の（メタ）アクリル酸エステル、ヒドロキシアルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレート、及びＮ－置換マレイミド類（例えばＮ－シクロヘキシルマレイミド）からなる群から選択される少なくとも一種の化合物を含有できる。 The compound (p2) having no epoxy group may be a compound copolymerizable with the compound (p1) having an epoxy group, for example. The compound (p2) having no epoxy group is, for example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate , Benzyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (Degree of polymerization n = 2 to 17), ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexae Ren glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di ( (Meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, EO modified phthalic acid (meth) acrylate , EO, PO modified phthalic acid (meth) acrylate, vinyl carbazole, styrene, N-phenylmaleimide, N-benzylmaleimide, 3-maleimidobenzoic acid N-succinimi , Linear or branched aliphatic or alicyclic (but may have some unsaturated bonds in the ring), (meth) acrylic acid ester, hydroxyalkyl (meth) acrylate, alkoxyalkyl It can contain at least one compound selected from the group consisting of (meth) acrylates and N-substituted maleimides (eg, N-cyclohexylmaleimide).
　エポキシ基を備えない化合物（ｐ２）は、更に、一分子中にエチレン性不飽和基を二個以上備える化合物を含有してもよい。この化合物が使用され、その配合量が調整されることで、ソルダーレジスト層の硬度及び油性を容易に調整できる。一分子中にエチレン性不飽和基を二個以上備える化合物は、例えばポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、及びペンタエリスリトールトリ（メタ）アクリレートからなる群から選択される少なくとも一種の化合物を含有できる。 The compound having no epoxy group (p2) may further contain a compound having two or more ethylenically unsaturated groups in one molecule. By using this compound and adjusting the blending amount thereof, the hardness and oiliness of the solder resist layer can be easily adjusted. Examples of the compound having two or more ethylenically unsaturated groups in one molecule include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth). It can contain at least one compound selected from the group consisting of acrylates.
　例えば、エチレン性不飽和化合物（ｐ）を、溶液重合法、エマルション重合法等の公知の重合法で重合することにより、重合体が得られる。例えば溶液重合法は、エチレン性不飽和化合物（ｐ）と適当な有機溶剤と重合開始剤とを窒素雰囲気下で加熱攪拌する方法、又は共沸重合法である。 For example, a polymer is obtained by polymerizing the ethylenically unsaturated compound (p) by a known polymerization method such as a solution polymerization method or an emulsion polymerization method. For example, the solution polymerization method is a method in which an ethylenically unsaturated compound (p), a suitable organic solvent, and a polymerization initiator are heated and stirred in a nitrogen atmosphere, or an azeotropic polymerization method.
　エチレン性不飽和化合物（ｐ）の重合のために使用される有機溶剤は、例えばメチルエチルケトン、シクロヘキサノン等のケトン類、及びトルエン、キシレン等の芳香族炭化水素類、及び酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、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等の酢酸エステル類、及びジアルキルグリコールエーテル類からなる群から選択される少なくとも一種の化合物を含有できる。 Examples of the organic solvent used for the polymerization of the ethylenically unsaturated compound (p) include ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, and cellosolve acetate. And at least one compound selected from the group consisting of acetate esters such as butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and dialkyl glycol ethers.
　エチレン性不飽和化合物（ｐ）の重合のために使用される重合開始剤は、例えばジイソプロピルベンゼンハイドロパーオキサイド等のハイドロパーオキサイド類、ジクミルパーオキサイド、２，５－ジメチル－２，５－ジ－（ｔ－ブチルパーオキシ）－ヘキサン等のジアルキルパーオキサイド類、イソブチリルパーオキサイド等のジアシルパーオキサイド類、メチルエチルケトンパーオキサイド等のケトンパーオキサイド類、ｔ－ブチルパーオキシビバレート等のアルキルパーエステル類、ジイソプロピルパーオキシジカーボネート等のパーオキシジカーボネート類、アゾビスイソブチロニトリル等のアゾ化合物、並びにレドックス系の開始剤からなる群から選択される少なくとも一種の化合物を含有できる。 Examples of the polymerization initiator used for the polymerization of the ethylenically unsaturated compound (p) include hydroperoxides such as diisopropylbenzene hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di Dialkyl peroxides such as-(t-butylperoxy) -hexane, diacyl peroxides such as isobutyryl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, alkyl peresters such as t-butyl peroxybivalate , Peroxydicarbonates such as diisopropyl peroxydicarbonate, azo compounds such as azobisisobutyronitrile, and at least one compound selected from the group consisting of redox initiators.
　カルボキシル基を有するエチレン性不飽和化合物（ａ２）は、適宜のポリマー及びプレポリマーからなる群から選択される少なくとも一種の成分を含有できる。エチレン性不飽和化合物（ａ２）は、エチレン性不飽和基を一個のみ有する化合物を含有できる。エチレン性不飽和基を一個のみ有する化合物は、例えばアクリル酸、メタクリル酸、クロトン酸、桂皮酸、２－アクリロイルオキシエチルコハク酸、２－メタクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－メタクリロイルオキシエチルフタル酸、β－カルボキシエチルアクリレート、アクリロイルオキシエチルサクシネート、メタクリロイルオキシエチルサクシネート、２－プロペノイックアシッド，３－（２－カルボキシエトキシ）－３－オキシプロピルエステル、２－アクリロイルオキシエチルテトラヒドロフタル酸、２－メタクリロイルオキシエチルテトラヒドロフタル酸、２－アクリロイルオキシエチルヘキサヒドロフタル酸、及び２－メタクリロイルオキシエチルヘキサヒドロフタル酸からなる群から選択される少なくとも一種の化合物を含有できる。更にエチレン性不飽和化合物（ａ２）は、複数のエチレン性不飽和基を備える化合物を含有できる。複数のエチレン性不飽和基を備える化合物は、例えば、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパンジメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート等のヒドロキシル基を備える多官能アクリレート、並びに多官能メタクリレートに二塩基酸無水物を反応させて得られる化合物からなる群から選択される少なくとも一種の化合物を含有できる。 The ethylenically unsaturated compound (a2) having a carboxyl group can contain at least one component selected from the group consisting of an appropriate polymer and a prepolymer. The ethylenically unsaturated compound (a2) can contain a compound having only one ethylenically unsaturated group. Compounds having only one ethylenically unsaturated group include, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2 -Methacryloyloxyethylphthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2-acryloyl Consists of oxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid It can contain at least one compound selected from the. Furthermore, the ethylenically unsaturated compound (a2) can contain a compound having a plurality of ethylenically unsaturated groups. The compound having a plurality of ethylenically unsaturated groups is, for example, hydroxyl such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. It can contain at least one compound selected from the group consisting of a compound obtained by reacting a difunctional acid anhydride with a polyfunctional acrylate having a group and a polyfunctional methacrylate.
　特にカルボキシル基を有するエチレン性不飽和化合物（ａ２）が、アクリル酸及びメタクリル酸からなる群から選択される少なくとも一種の成分を含有することが好ましい。アクリル酸及びメタクリル酸に由来するエチレン性不飽和基は特に光反応性に優れるため、第一の樹脂（ａ）の光反応性を向上させることができる。 In particular, the ethylenically unsaturated compound (a2) having a carboxyl group preferably contains at least one component selected from the group consisting of acrylic acid and methacrylic acid. Since the ethylenically unsaturated group derived from acrylic acid and methacrylic acid is particularly excellent in photoreactivity, the photoreactivity of the first resin (a) can be improved.
　エポキシ化合物（ａ１）のエポキシ基１モルに対するカルボキシル基を有するエチレン性不飽和化合物（ａ２）のカルボキシル基の量は、好ましくは０．４～１．２モルの範囲内であり、より好ましくは０．５～１．１モルの範囲内となる量である。 The amount of the carboxyl group of the ethylenically unsaturated compound (a2) having a carboxyl group with respect to 1 mol of the epoxy group of the epoxy compound (a1) is preferably within the range of 0.4 to 1.2 mol, more preferably 0. The amount is within the range of 5 to 1.1 mol.
　多価カルボン酸またはその無水物からなる化合物（ａ３）（以下、化合物（ａ３）ともいう）は、例えばフタル酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、メチルナジック酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸、コハク酸、メチルコハク酸、マレイン酸、シトラコン酸、グルタル酸、イタコン酸等のジカルボン酸；シクロヘキサン－１，２，４－トリカルボン酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、メチルシクロヘキセンテトラカルボン酸等の三塩基酸以上の多価カルボン酸；並びにこれらの多価カルボン酸の無水物からなる群から選択される少なくとも一種の化合物を含有できる。 Compound (a3) (hereinafter also referred to as compound (a3)) comprising a polyvalent carboxylic acid or its anhydride is, for example, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylnadic acid, hexahydrophthalic acid, methylhexa Dicarboxylic acids such as hydrophthalic acid, succinic acid, methyl succinic acid, maleic acid, citraconic acid, glutaric acid, itaconic acid; cyclohexane-1,2,4-tricarboxylic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, It can contain at least one compound selected from the group consisting of tribasic or higher polycarboxylic acids such as methylcyclohexene tetracarboxylic acid; and anhydrides of these polycarboxylic acids.
　化合物（ａ３）の主たる使用目的は、第一の樹脂（ａ）に酸価を与えることにより、ソルダーレジスト組成物に希アルカリ水溶液による再分散、再溶解性を付与することである。化合物（ａ３）の使用量は、好ましくは第一の樹脂（ａ）の酸価が３０ｍｇＫＯＨ／ｇ以上であるように調整され、より好ましくは第一の樹脂（ａ）の酸価が６０ｍｇＫＯＨ／ｇ以上であるように調整され、また、化合物（ａ３）の使用量は、好ましくは第一の樹脂（ａ）の酸価が１６０ｍｇＫＯＨ／ｇ以下であるように調整され、より好ましくは１３０ｍｇＫＯＨ／ｇ以下であるように調整される。 The main purpose of use of the compound (a3) is to impart redispersion and resolubility with a dilute alkaline aqueous solution to the solder resist composition by giving an acid value to the first resin (a). The amount of the compound (a3) used is preferably adjusted so that the acid value of the first resin (a) is 30 mgKOH / g or more, more preferably the acid value of the first resin (a) is 60 mgKOH / g. The amount of the compound (a3) used is preferably adjusted so that the acid value of the first resin (a) is 160 mgKOH / g or less, more preferably 130 mgKOH / g or less. Adjusted to be.
　第一の樹脂（ａ）の合成において、エポキシ化合物（ａ１）とカルボキシル基を有するエチレン性不飽和化合物（ａ２）との付加反応、並びにこの付加反応の生成物（付加反応生成物）と化合物（ａ３）との付加反応は、公知の方法により行われる。例えばエポキシ化合物（ａ１）とエチレン性不飽和化合物（ａ２）との付加反応においては、エポキシ化合物（ａ１）を含む溶剤溶液にエチレン性不飽和化合物（ａ２）を加え、更に必要に応じて熱重合禁止剤及び触媒を加えて攪拌混合することで、反応性溶液が得られる。この反応性溶液を、常法により、好ましくは６０～１５０℃で、より好ましくは８０～１２０℃で反応させることにより、付加反応生成物が得られる。熱重合禁止剤は、例えばハイドロキノン、またはハイドロキノンモノメチルエーテルである。触媒は、例えば、ベンジルジメチルアミン、トリエチルアミン等の第３級アミン類、トリメチルベンジルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド等の第４級アンモニウム塩類、トリフェニルホスフィン、トリフェニルスチビンである。 In the synthesis of the first resin (a), an addition reaction between the epoxy compound (a1) and the ethylenically unsaturated compound (a2) having a carboxyl group, and a product (addition reaction product) and a compound ( The addition reaction with a3) is carried out by a known method. For example, in the addition reaction between the epoxy compound (a1) and the ethylenically unsaturated compound (a2), the ethylenically unsaturated compound (a2) is added to the solvent solution containing the epoxy compound (a1), and thermal polymerization is performed as necessary. A reactive solution is obtained by adding an inhibitor and a catalyst and mixing with stirring. An addition reaction product is obtained by reacting this reactive solution by a conventional method, preferably at 60 to 150 ° C., more preferably at 80 to 120 ° C. The thermal polymerization inhibitor is, for example, hydroquinone or hydroquinone monomethyl ether. Examples of the catalyst include tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, triphenylphosphine, and triphenylstibine.
　付加反応生成物と化合物（ａ３）との付加反応においては、付加反応生成物を含む溶剤溶液に化合物（ａ３）を加え、更に必要に応じて熱重合禁止剤及び触媒を加えて撹拌混合することで、反応性溶液が得られる。この反応性溶液を、常法により、反応させることで、第一の樹脂（ａ）が得られる。反応条件は、エポキシ化合物（ａ１）とカルボキシル基を有するエチレン性不飽和化合物（ａ２）との付加反応の反応条件と同じ条件でよい。熱重合禁止剤及び触媒は、エポキシ化合物（ａ１）とカルボキシル基を有するエチレン性不飽和化合物（ａ２）との付加反応において使用された熱重合禁止剤及び触媒と同じものを使用することができる。 In the addition reaction between the addition reaction product and the compound (a3), the compound (a3) is added to the solvent solution containing the addition reaction product, and a thermal polymerization inhibitor and a catalyst are further added and mixed as necessary. A reactive solution is obtained. The first resin (a) is obtained by reacting this reactive solution by a conventional method. The reaction conditions may be the same as the reaction conditions for the addition reaction between the epoxy compound (a1) and the ethylenically unsaturated compound (a2) having a carboxyl group. As the thermal polymerization inhibitor and the catalyst, the same thermal polymerization inhibitor and catalyst used in the addition reaction of the epoxy compound (a1) and the ethylenically unsaturated compound (a2) having a carboxyl group can be used.
　カルボキシル基含有樹脂（Ａ２）は、カルボキシル基を有するエチレン性不飽和化合物を含むエチレン性不飽和単量体の重合体におけるカルボキシル基の一部と、エポキシ基を有するエチレン性不飽和化合物と、を反応させることで得られる樹脂（第二の樹脂（ｂ）という）を含有してもよい。エチレン性不飽和単量体は、必要に応じてカルボキシル基を有さないエチレン性不飽和化合物を含んでもよい。 Carboxyl group-containing resin (A2) is a part of a carboxyl group in a polymer of ethylenically unsaturated monomers including an ethylenically unsaturated compound having a carboxyl group, and an ethylenically unsaturated compound having an epoxy group. You may contain resin obtained by making it react (it is called 2nd resin (b)). The ethylenically unsaturated monomer may include an ethylenically unsaturated compound having no carboxyl group, if necessary.
　第二の樹脂（ｂ）を得るためのカルボキシル基を有するエチレン性不飽和化合物は、適宜のポリマー及びプレポリマーを含有できる。例えばカルボキシル基を有するエチレン性不飽和化合物は、エチレン性不飽和基を１個のみ有する化合物を含有できる。より具体的には、カルボキシル基を有するエチレン性不飽和化合物は、例えばアクリル酸、メタクリル酸、ω－カルボキシ－ポリカプロラクトン（ｎ≒２）モノアクリレート、クロトン酸、桂皮酸、２－アクリロイルオキシエチルコハク酸、２－メタクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－メタクリロイルオキシエチルフタル酸、β－カルボキシエチルアクリレート、アクリロイルオキシエチルサクシネート、メタクリロイルオキシエチルサクシネート、２－プロペノイックアシッド，３－（２－カルボキシエトキシ）－３－オキシプロピルエステル、２－アクリロイルオキシエチルテトラヒドロフタル酸、２－メタクリロイルオキシエチルテトラヒドロフタル酸、２－アクリロイルオキシエチルヘキサヒドロフタル酸、及び２－メタクリロイルオキシエチルヘキサヒドロフタル酸からなる群から選択される少なくとも一種の化合物を含有できる。カルボキシル基を有するエチレン性不飽和化合物は、エチレン性不飽和基を複数有する化合物を含有できる。より具体的には、例えばカルボキシル基を有するエチレン性不飽和化合物は、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパンジメタクリレート、ジペンタエリスリトールペンタアクリレート、及びジペンタエリスリトールペンタメタクリレートからなる群から選択されるヒドロキシル基を有する多官能の（メタ）アクリレートと、二塩基酸無水物と、の反応で得られる化合物を含有できる。これらの化合物は、単独で使用されてもよく、複数で併用されてもよい。 The ethylenically unsaturated compound having a carboxyl group for obtaining the second resin (b) can contain an appropriate polymer and prepolymer. For example, an ethylenically unsaturated compound having a carboxyl group can contain a compound having only one ethylenically unsaturated group. More specifically, ethylenically unsaturated compounds having a carboxyl group include, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≈2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloyloxyethyl succinate. Acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, β-carboxyethyl acrylate, acryloyloxyethyl succinate, methacryloyloxyethyl succinate, 2-propenoic acid , 3- (2-Carboxyethoxy) -3-oxypropyl ester, 2-acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethylhexyl It may contain at least one compound selected from the group consisting of sahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid. The ethylenically unsaturated compound having a carboxyl group can contain a compound having a plurality of ethylenically unsaturated groups. More specifically, for example, ethylenically unsaturated compounds having a carboxyl group are pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol. A compound obtained by the reaction of a polyfunctional (meth) acrylate having a hydroxyl group selected from the group consisting of pentamethacrylate and a dibasic acid anhydride can be contained. These compounds may be used alone or in combination.
　第二の樹脂（ｂ）を得るためのカルボキシル基を有さないエチレン性不飽和化合物は、例えば、カルボキシル基を有するエチレン性不飽和化合物と共重合可能な化合物であり得る。カルボキシル基を有さないエチレン性不飽和化合物は、芳香環を有する化合物と、芳香環を有さない化合物と、を含有できる。 The ethylenically unsaturated compound having no carboxyl group for obtaining the second resin (b) can be, for example, a compound copolymerizable with an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having no carboxyl group can contain a compound having an aromatic ring and a compound having no aromatic ring.
　芳香環を有する化合物は、例えば２－（メタ）アクリロイロキシエチルフタレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチルフタレート、２－（メタ）アクリロイロキシプロピルフタレート、ベンジル（メタ）アクリレート、ネオペンチルグリコールベンゾエート（メタ）アクリレート、パラクミルフェノキシエチレングリコール（メタ）アクリレート、ＥＯ変性クレゾール（メタ）アクリレート、エトキシ化フェニル（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート（ｎ＝２～１７）、ＥＣＨ変性フェノキシ（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシヘキサエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、トリブロモフェニル（メタ）アクリレート、ＥＯ変性トリブロモフェニル（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、ＰＯ変性ビスフェノールＡジ（メタ）アクリレート、変性ビスフェノールＡジ（メタ）アクリレート、ＥＯ変性ビスフェノールＦジ（メタ）アクリレート、ＥＣＨ変性フタル酸ジ（メタ）アクリレート、トリメチロールプロパンベンゾエート（メタ）アクリレート、ＥＯ変性フタル酸（メタ）アクリレート、ＥＯ，ＰＯ変性フタル酸（メタ）アクリレート、ビニルカルバゾール、スチレン、ビニルナフタレン、及びビニルビフェニルからなる群から選択される少なくとも一種の化合物を含有できる。 Examples of the compound having an aromatic ring include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, benzyl (meth) Acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (n = 2 to 17), ECH-modified phenoxy (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyhexaethylene glycol (meth) ) Acrylate, phenoxytetraethylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, Modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, EO modified phthalic acid (meth) acrylate, EO, PO It can contain at least one compound selected from the group consisting of modified phthalic acid (meth) acrylate, vinyl carbazole, styrene, vinyl naphthalene, and vinyl biphenyl.
　芳香環を有さない化合物は、例えば直鎖又は分岐の脂肪族、或いは脂環族（但し、環中に一部不飽和結合を有してもよい）の（メタ）アクリル酸エステル、ヒドロキシアルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレート等；及びＮ－シクロヘキシルマレイミド等のＮ－置換マレイミド類からなる群から選択される少なくとも一種の化合物を含有できる。芳香環を有さない化合物は、更にポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の、１分子中にエチレン性不飽和基を２個以上有する化合物を含有してもよい。これらの化合物は、単独で使用されてもよく、複数で併用されてもよい。これらの化合物を使用することにより、ソルダーレジスト層の硬度及び油性を容易に調整することができる。 The compound having no aromatic ring is, for example, a linear or branched aliphatic or alicyclic (however, the ring may partially have an unsaturated bond) (meth) acrylic acid ester, hydroxyalkyl It can contain at least one compound selected from the group consisting of (meth) acrylates, alkoxyalkyl (meth) acrylates and the like; and N-substituted maleimides such as N-cyclohexylmaleimide. Compounds that do not have an aromatic ring include ethylene glycol in one molecule such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. You may contain the compound which has 2 or more of unsaturated unsaturated groups. These compounds may be used alone or in combination. By using these compounds, the hardness and oiliness of the solder resist layer can be easily adjusted.
　第二の樹脂（ｂ）を得るためのエポキシ基を有するエチレン性不飽和化合物は、適宜のポリマー又はプレポリマーである。このエポキシ基を有するエチレン性不飽和化合物は、例えばアクリル酸又はメタクリル酸のエポキシシクロヘキシル誘導体類；アクリレート又はメタクリレートの脂環エポキシ誘導体；β－メチルグリシジルアクリレート、β－メチルグリシジルメタクリレートからなる群から選択される少なくとも一種の化合物である。これらの化合物は、単独で使用されてもよく、複数で併用されてもよい。好ましくは、汎用され、容易に入手できるグリシジル（メタ）アクリレートが用いられる。 The ethylenically unsaturated compound having an epoxy group for obtaining the second resin (b) is an appropriate polymer or prepolymer. The ethylenically unsaturated compound having an epoxy group is selected from the group consisting of, for example, epoxycyclohexyl derivatives of acrylic acid or methacrylic acid; alicyclic epoxy derivatives of acrylate or methacrylate; β-methylglycidyl acrylate, β-methylglycidyl methacrylate. At least one compound. These compounds may be used alone or in combination. Preferably, glycidyl (meth) acrylate which is widely used and easily available is used.
　カルボキシル基含有樹脂（Ａ２）は、カルボキシル基を有するエチレン性不飽和化合物、及びヒドロキシル基を有するエチレン性不飽和化合物を含むエチレン性不飽和単量体の重合体におけるヒドロキシル基の一部又は全部に、エチレン性不飽和基及びイソシアネート基を有する化合物を付加することで得られる樹脂（以下、第三の樹脂（ｃ）という）を含有してもよい。エチレン性不飽和単量体は、必要に応じて、カルボキシル基及びヒドロキシル基を有さないエチレン性不飽和化合物を含んでもよい。 Carboxyl group-containing resin (A2) is a part or all of hydroxyl groups in a polymer of an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group. And a resin obtained by adding a compound having an ethylenically unsaturated group and an isocyanate group (hereinafter referred to as a third resin (c)). The ethylenically unsaturated monomer may contain an ethylenically unsaturated compound having no carboxyl group and no hydroxyl group, if necessary.
　第三の樹脂（ｃ）を得るためのカルボキシル基を有するエチレン性不飽和化合物の例は、上述の第二の樹脂（ｂ）を得るためのカルボキシル基を有するエチレン性不飽和化合物と同じであってもよい。 Examples of the ethylenically unsaturated compound having a carboxyl group for obtaining the third resin (c) were the same as the ethylenically unsaturated compound having a carboxyl group for obtaining the second resin (b). May be.
　第三の樹脂（ｃ）を得るためのヒドロキシル基を有するエチレン性不飽和化合物は、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル(メタ)アクリレート、４－ヒドロキシブチル（メタ）アクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチルフタレート、カプロラクトン（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート、ヒドロキシブチルビニルエーテル、ヒドロキシエチルビニルエーテル、及びＮ－ヒドロキシエチル（メタ）アクリルアミドであり得る。 Examples of the ethylenically unsaturated compound having a hydroxyl group for obtaining the third resin (c) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , Cyclohexanedimethanol mono (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, caprolactone (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, trimethylolpropane di Hydroxyalkyl (meth) acrylates such as (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and hydroxybutyl vinyl ester Ether, hydroxyethyl vinyl ether, and N- hydroxyethyl (meth) may be acrylamide.
　第三の樹脂（ｃ）を得るためのエチレン性不飽和基及びイソシアネート基を有する化合物は、例えば、２－アクリロイルオキシエチルイソシアネート（具体例として昭和電工株式会社；品番「カレンズＡＯＩ」）、２－メタクリロイルオキシエチルイソシアネート（具体例として昭和電工株式会社；品番「カレンズＭＯＩ」）、メタクリロイルオキシエトキシエチルイソシアネート（具体例として昭和電工株式会社；品番「カレンズＭＯＩ－ＥＧ」）、カレンズＭＯＩのイソシアネートブロック体（具体例として昭和電工株式会社；品番「カレンズＭＯＩ一ＢＭ」）、カレンズＭＯＩのイソシアネートブロック体（具体例として昭和電工株式会社；品番「カレンズＭＯＩ－ＢＰ」）、及び１，１－（ビスアクリロイルオキシメチル）エチルイソシアネート）（具体例として昭和電工株式会社；品番「カレンズＢＥＩ」）であり得る。 The compound having an ethylenically unsaturated group and an isocyanate group for obtaining the third resin (c) is, for example, 2-acryloyloxyethyl isocyanate (as a specific example, Showa Denko KK; product number “Karenz AOI”), 2- Methacryloyloxyethyl isocyanate (as a specific example, Showa Denko KK; product number “Karenz MOI”), methacryloyloxyethoxyethyl isocyanate (as a specific example, Showa Denko KK; product number “Karenz MOI-EG”), Karenz MOI isocyanate block ( Specific examples are Showa Denko KK; product number “Karenz MOI-BM”), Karenz MOI isocyanate block (specific examples Showa Denko KK; product number “Karenz MOI-BP”), and 1,1- (bisacryloyloxy) Methyl) ethyl Isocyanate) (as a specific example Showa Denko KK; may be a part number "Karenz BEI").
　カルボキシル基含有樹脂（Ａ２）全体の重量平均分子量は、好ましくは、８００～１０００００の範囲内である。この場合、ソルダーレジスト組成物に特に優れた感光性と解像性とが付与される。 The weight average molecular weight of the entire carboxyl group-containing resin (A2) is preferably in the range of 800 to 100,000. In this case, particularly excellent photosensitivity and resolution are imparted to the solder resist composition.
　カルボキシル基含有樹脂（Ａ２）全体の酸価は、好ましくは３０ｍｇＫＯＨ／ｇ以上である。この場合、ソルダーレジスト組成物に良好な現像性が付与される。カルボキシル基含有樹脂（Ａ２）全体の酸価は、より好ましくは６０ｍｇＫＯＨ／ｇ以上である。カルボキシル基含有樹脂（Ａ２）全体の酸価は、好ましくは１６０ｍｇＫＯＨ／ｇ以下である。この場合、ソルダーレジスト組成物で形成される被膜に残留するカルボキシル基の量が低減される。このため、被膜の良好な電気特性、耐電蝕性、及び耐水性等が維持され得る。カルボキシル基含有樹脂（Ａ２）全体の酸価は、より好ましくは１３０ｍｇＫＯＨ／ｇ以下である。 The acid value of the entire carboxyl group-containing resin (A2) is preferably 30 mgKOH / g or more. In this case, good developability is imparted to the solder resist composition. The acid value of the entire carboxyl group-containing resin (A2) is more preferably 60 mgKOH / g or more. The acid value of the entire carboxyl group-containing resin (A2) is preferably 160 mgKOH / g or less. In this case, the amount of carboxyl groups remaining in the film formed with the solder resist composition is reduced. For this reason, it is possible to maintain good electrical characteristics, corrosion resistance, water resistance, and the like of the coating film. The acid value of the entire carboxyl group-containing resin (A2) is more preferably 130 mgKOH / g or less.
　［光重合性化合物（Ｂ）について］
　光重合性化合物（Ｂ）は、ソルダーレジスト組成物に光硬化性を付与する。光重合性化合物（Ｂ）は、光重合性モノマー及び光重合性プレポリマーからなる群から選択される少なくとも一種を含有する。 [About Photopolymerizable Compound (B)]
The photopolymerizable compound (B) imparts photocurability to the solder resist composition. The photopolymerizable compound (B) contains at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer.
　光重合性モノマーは、例えばエチレン性不飽和基を有する。光重合性モノマーは、例えば２－ヒドロキシエチル（メタ）アクリレート等の単官能（メタ）アクリレート；並びにジエチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ε―カプロラクトン変性ペンタエリストールヘキサアクリレート等の多官能（メタ）アクリレートからなる群から選択される少なくとも一種の化合物を含有できる。 The photopolymerizable monomer has, for example, an ethylenically unsaturated group. Photopolymerizable monomers include, for example, monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; and diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Multifunctional (meth) such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate It can contain at least one compound selected from the group consisting of acrylates.
　光重合性モノマーは、好ましくはリン含有化合物（リン含有光重合性化合物）を含有する。この場合、ソルダーレジスト組成物の硬化物の難燃性が向上する。リン含有光重合性化合物は、例えば２－メタクリロイロキシエチルアシッドホスフェート（具体例として共栄社化学株式会社製の品番ライトエステルＰ－１Ｍ、及びライトエステルＰ－２Ｍ）、２－アクリロイルオキシエチルアシッドホスフェート（具体例として共栄社化学株式会社製の品番ライトアクリレートＰ－１Ａ）、ジフェニル－２－メタクリロイルオキシエチルホスフェート（具体例として大八工業株式会社製の品番ＭＲ－２６０）、並びに昭和高分子株式会社製のＨＦＡシリーズ（具体例としてジペンタエリストールヘキサアクリレートとＨＣＡとの付加反応物である品番ＨＦＡー６００３、及びＨＦＡ－６００７、カプロラクトン変性ジペンタエリストールヘキサアクリレートとＨＣＡとの付加反応物である品番ＨＦＡー３００３、及びＨＦＡ－６１２７等）からなる群から選択される少なくとも一種の化合物を含有できる。 The photopolymerizable monomer preferably contains a phosphorus-containing compound (phosphorus-containing photopolymerizable compound). In this case, the flame retardancy of the cured product of the solder resist composition is improved. Phosphorus-containing photopolymerizable compounds include, for example, 2-methacryloyloxyethyl acid phosphate (specific examples: product number light ester P-1M and light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate ( As specific examples, product number light acrylate P-1A manufactured by Kyoeisha Chemical Co., Ltd., diphenyl-2-methacryloyloxyethyl phosphate (specific example, product number MR-260 manufactured by Daihachi Kogyo Co., Ltd.) and Showa Polymer Co., Ltd. HFA series (specifically, product number HFA-6003, which is an addition reaction product of dipentaerystol hexaacrylate and HCA, and product number HFA, which is an addition reaction product of caprolactone-modified dipentaerystol hexaacrylate and HCA) -30 3, and it is selected from the group consisting of HFA-6127, etc.) containing at least one compound.
　光重合性プレポリマーは、例えば、光重合性モノマーを重合させて得られるプレポリマーにエチレン性不飽和基を付加したプレポリマー、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート、アルキド樹脂（メタ）アクリレート、シリコーン樹脂（メタ）アクリレート、スピラン樹脂（メタ）アクリレート等のオリゴ（メタ）アクリレートプレポリマー類からなる群から選択される少なくとも一種の化合物を含有できる。 The photopolymerizable prepolymer is, for example, a prepolymer obtained by polymerizing a photopolymerizable monomer with an ethylenically unsaturated group added, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate. And at least one compound selected from the group consisting of oligo (meth) acrylate prepolymers such as alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate.
　［光重合開始剤（Ｃ）について］
　光重合開始剤（Ｃ）は、例えば、ベンゾインとそのアルキルエーテル類；アセトフェノン、ベンジルジメチルケタール等のアセトフェノン類；２－メチルアントラキノン等のアントラキノン類；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－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、２，４－ジイソプロピルチオキサントン等のチオキサントン類；ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルスルフィド等のベンゾフェノン類；２，４－ジイソプロピルキサントン等のキサントン類；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン等の窒素原子を含む化合物；１－ヒドロキシ－シクロヘキシル－フェニル-ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－2－メチル－1－プロパン－1－オン、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、フェニルグリオキシリックアシッドメチルエステル等のα-ヒドロキシアルキルフェノン類；２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、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－ブタノン等のα-アミノアルキルフェノン類；２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド、２，４，６－トリメチルベンゾイル－エチル－フェニル－ホスフィネート等のモノアシルホスフィンオキサイド系光重合開始剤；並びに、ビス－（２,４,６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）フェニルホスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－２，５－ジメチルフェニルホスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－４－プロピルフェニルホスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－１－ナフチルホスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）フェニルホ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ホスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，５－ジメチルフェニルホスフィンオキサイド、（２，５，６－トリメチルベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキサイド等のアシルホスフィン系光重合開始剤からなる群から選択される少なくとも一種の化合物を含有できる。光重合開始剤（Ｃ）は、より好ましくはα-ヒドロキシアルキルフェノン類、α-アミノアルキルフェノン類、チオキサントン類、及びアシルホスフィンオキサイド系光重合開始剤からなる群から選択される少なくとも２種の成分を含む。 [Photopolymerization initiator (C)]
The photopolymerization initiator (C) includes, for example, benzoin and alkyl ethers thereof; acetophenones such as acetophenone and benzyldimethyl ketal; anthraquinones such as 2-methylanthraquinone; 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone Thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; xanthones such as 2,4-diisopropylxanthone; Compounds containing nitrogen atoms such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone; 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy- -Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- Α-hydroxyalkylphenones such as {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester; 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino Α-aminoalkylphenones such as 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; , 6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-ethyl-phenyl-phosphinate and other monoacylphosphine oxide photoinitiators; and bis- (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl It can contain at least one compound selected from the group consisting of acylphosphine photopolymerization initiators such as phosphine oxide. The photopolymerization initiator (C) is more preferably at least two components selected from the group consisting of α-hydroxyalkylphenones, α-aminoalkylphenones, thioxanthones, and acylphosphine oxide photopolymerization initiators. including.
　［熱硬化性成分（Ｄ）について］
　熱硬化性成分（Ｄ）は、ソルダーレジスト組成物に熱硬化性を付与できる。熱硬化性成分（Ｄ）は、好ましくは環状エーテル骨格を有する化合物を含む。環状エーテル骨格を有する化合物は、例えば、好ましくはエポキシ化合物を含有する。 [About thermosetting component (D)]
The thermosetting component (D) can impart thermosetting properties to the solder resist composition. The thermosetting component (D) preferably contains a compound having a cyclic ether skeleton. The compound having a cyclic ether skeleton preferably contains, for example, an epoxy compound.
　エポキシ化合物は、好ましくは１分子中に少なくとも２個のエポキシ基を有する。エポキシ化合物は、溶剤難溶性エポキシ化合物であってもよく、汎用の溶剤可溶性エポキシ化合物であってもよい。エポキシ化合物の種類は特に限定されない。エポキシ化合物は、フェノールノボラック型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　Ｎ－７７５）、クレゾールノボラック型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　Ｎ－６９５）、ビスフェノールＡ型エポキシ樹脂（具体例として三菱化学株式会社製の品番ｊＥＲ１００１）、ビスフェノールＡ－ノボラック型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　Ｎ－８６５）、ビスフェノールＦ型エポキシ樹脂（具体例として三菱化学株式会社製の品番ｊＥＲ４００４Ｐ）、ビスフェノールＳ型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　ＥＸＡ－１５１４）、ビスフェノールＡＤ型エポキシ樹脂、ビフェニル型エポキシ樹脂（具体例として三菱化学株式会社製の品番ＹＸ４０００）、ビフェニルノボラック型エポキシ樹脂（具体例として日本化薬株式会社製の品番ＮＣ－３０００）、水添ビスフェノールＡ型エポキシ樹脂（具体例として新日鉄住金化学株式会社製の品番ＳＴ－４０００Ｄ）、ナフタレン型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　ＨＰ－４０３２、ＥＰＩＣＬＯＮ　ＨＰ－４７００、ＥＰＩＣＬＯＮ　ＨＰ－４７７０）、ハイドロキノン型エポキシ樹脂（具体例として新日鉄住金化学社製の品番ＹＤＣ－１３１２）、ターシャリーブチルカテコール型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　ＨＰ－８２０）、ジシクロペンタジエン型エポキシ樹脂（具体例としてＤＩＣ製の品番ＥＰＩＣＬＯＮ　ＨＰ－７２００）、アダマンタン型エポキシ樹脂（具体例として出光興産株式会社製の品番ＡＤＡＭＡＮＴＡＴＥ　Ｘ－Ｅ－２０１）、ビフェニルエーテル型エポキシ樹脂（具体例として新日鉄住金化学株式会社製の品番ＹＳＬＶ－８０ＤＥ、特殊二官能型エポキシ樹脂（具体例として、三菱化学株式会社製の品番ＹＬ７１７５－５００、及びＹＬ７１７５－１０００；ＤＩＣ株式会社製の品番ＥＰＩＣＬＯＮ　ＴＳＲ－９６０、ＥＰＩＣＬＯＮ　ＴＥＲ－６０１、ＥＰＩＣＬＯＮ　ＴＳＲ－２５０－８０ＢＸ、ＥＰＩＣＬＯＮ　１６５０－７５ＭＰＸ、ＥＰＩＣＬＯＮ　ＥＸＡ－４８５０、ＥＰＩＣＬＯＮ　ＥＸＡ－４８１６、ＥＰＩＣＬＯＮ　ＥＸＡ－４８２２、及びＥＰＩＣＬＯＮ　ＥＸＡ－９７２６；新日鉄住金化学株式会社製の品番ＹＳＬＶ－１２０ＴＥ）、及び前記以外のビスフェノール系エポキシ樹脂からなる群から選択される少なくとも一種の化合物を含有できる。 The epoxy compound preferably has at least two epoxy groups in one molecule. The epoxy compound may be a poorly solvent-soluble epoxy compound or a general-purpose solvent-soluble epoxy compound. The kind of epoxy compound is not particularly limited. The epoxy compound includes a phenol novolac type epoxy resin (specifically, product number EPICLON N-775 manufactured by DIC Corporation), a cresol novolac type epoxy resin (specific example, product number EPICLON N-695 manufactured by DIC Corporation), and a bisphenol A type epoxy. Resin (part number jER1001 manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol A-novolak type epoxy resin (part number EPICLON N-865 manufactured by DIC Corporation), bisphenol F type epoxy resin (particularly Mitsubishi Chemical Corporation) Company product number jER4004P), bisphenol S type epoxy resin (specific example, product number EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl type epoxy resin (specific As a product number YX4000 manufactured by Mitsubishi Chemical Co., Ltd.), biphenyl novolac type epoxy resin (specifically, product number NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (specifically manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Product number ST-4000D), naphthalene type epoxy resin (specific examples: product numbers EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770, manufactured by DIC Corporation), hydroquinone type epoxy resin (specific examples, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Product number YDC-1312), tertiary butyl catechol type epoxy resin (specifically, product number EPICLON HP-820 manufactured by DIC Corporation), dicyclopentadiene type epoxy resin (specific example, product number EPICLON manufactured by DIC) HP-7200), adamantane type epoxy resin (specifically, part number ADAMANATE X-E-201 manufactured by Idemitsu Kosan Co., Ltd.), biphenyl ether type epoxy resin (specific example, part number YSLV-80DE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Bifunctional epoxy resin (specific examples: product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; product numbers EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON manufactured by DIC Corporation) 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. No. YSLV-120TE) and at least one compound selected from the group consisting of bisphenol-based epoxy resins other than those described above.
　エポキシ化合物は、好ましくは、トリグリシジルイソシアヌレートを含有する。トリグリシジルイソシアヌレートは、好ましくは、Ｓ－トリアジン環骨格面に対して３個のエポキシ基が同一方向に結合した構造をもつβ体であり、或いは、このβ体と、Ｓ－トリアジン環骨格面に対し１個のエポキシ基が他の２個のエポキシ基と異なる方向に結合した構造をもつα体と、の混合物である。 The epoxy compound preferably contains triglycidyl isocyanurate. The triglycidyl isocyanurate is preferably a β-form having a structure in which three epoxy groups are bonded in the same direction with respect to the S-triazine ring skeleton plane, or the β-form and the S-triazine ring skeleton plane. On the other hand, it is a mixture of an α-form having a structure in which one epoxy group is bonded to the other two epoxy groups in different directions.
　［着色剤（Ｅ）について］
　ソルダーレジスト組成物は着色剤（Ｅ）を含有する。着色剤（Ｅ）は、ペリレン系黒色着色剤（Ｅ１）、及び黒色以外の一種の着色剤（Ｅ２）を含む。ソルダーレジスト組成物がペリレン系黒色着色剤（Ｅ１）及び着色剤（Ｅ２）を含むことにより、ソルダーレジスト組成物から形成される被膜を露光する際に、被膜を表層から深部まで十分に硬化させることができる。更に、ソルダーレジスト組成物から形成される被膜による導体配線の隠蔽性を十分に確保することができる。 [Colorant (E)]
The solder resist composition contains a colorant (E). The colorant (E) includes a perylene black colorant (E1) and a kind of colorant (E2) other than black. When the solder resist composition contains a perylene-based black colorant (E1) and a colorant (E2), when the film formed from the solder resist composition is exposed, the film is sufficiently cured from the surface layer to the deep part. Can do. Furthermore, the concealability of the conductor wiring by the film formed from the solder resist composition can be sufficiently ensured.
　特に好ましくは、着色剤（Ｅ）がペリレン系黒色着色剤（Ｅ１）及び黒色以外の一種の着色剤（Ｅ２）のみを含む。ペリレン系黒色着色剤（Ｅ１）と着色剤（Ｅ２）とを組み合わせることにより、ソルダーレジスト組成物の光硬化性の低下を抑制できると共に、被膜に高い隠蔽性を付与できる。 Particularly preferably, the colorant (E) contains only a perylene-based black colorant (E1) and one kind of colorant (E2) other than black. By combining the perylene-based black colorant (E1) and the colorant (E2), it is possible to suppress a decrease in photocurability of the solder resist composition and to impart high concealability to the coating.
　［ペリレン系黒色着色剤（Ｅ１）について］
　ペリレン系黒色着色剤（Ｅ１）は、例えば、カラーインデックス（Ｃ．Ｉ．）ピグメントブラック３１、及びカラーインデックス（Ｃ．Ｉ．）ピグメントブラック３２からなる群から選択される少なくとも一種の化合物を含有できる。また、ペリレン系黒色着色剤（Ｅ１）は、上記の成分以外に、カラーインデックスの番号は付されていないが、ペリレン系の近赤外線透過黒色着色剤として知られているＢＡＳＦ社のＬｕｍｏｇｅｎ　Ｂｌａｃｋ　ＦＫ　４２８０及びＬｕｍｏｇｅｎ　Ｂｌａｃｋ　ＦＫ　４２８１からなる群から選択される少なくとも一種の成分を含有できる。 [Perylene black colorant (E1)]
The perylene-based black colorant (E1) can contain, for example, at least one compound selected from the group consisting of a color index (CI) pigment black 31 and a color index (CI) pigment black 32. . In addition to the above components, the perylene-based black colorant (E1) has no color index number, but is known as a perylene-based near-infrared transmitting black colorant, BASF's Lumogen Black FK 4280. And at least one component selected from the group consisting of Lumogen Black FK 4281.
　［黒色以外の一種の着色剤（Ｅ２）について］
　黒色以外の一種の着色剤（Ｅ２）は黒色以外の一種の着色剤である。着色剤（Ｅ２）は、例えば、カラーインデックス（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　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ）発行）番号が付されている公知の着色剤のうち、黒色でない着色剤であり得る。着色剤（Ｅ２）は、例えば、赤色着色剤、青色着色剤、緑色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤、茶色着色剤、及びこれら以外の着色剤からなる群から選択される少なくとも一種の着色剤であり得る。 [About one kind of colorant (E2) other than black]
A kind of colorant (E2) other than black is a kind of colorant other than black. The colorant (E2) is, for example, a non-black colorant among known colorants having a color index (CI; issued by The Society of Dyer's and Colorists) number It can be. The colorant (E2) is selected from the group consisting of, for example, a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, a brown colorant, and other colorants. Can be at least one colorant.
　好ましくは黒色以外の一種の着色剤（Ｅ２）は赤色着色剤である。ソルダーレジスト組成物がペリレン系黒色着色剤（Ｅ１）と赤色着色剤とを含有することにより、ソルダーレジスト組成物から形成される被膜を露光する際に、被膜を表層から深部まで十分に硬化させることができる。更に、ソルダーレジスト組成物から形成される被膜による導体配線の隠蔽性をより十分に確保することができる。赤色着色剤は、例えば、アントラキノン系赤色顔料、アゾ系赤色顔料、レーキ系赤色顔料、キナクリドン系赤色顔料、及びジケトピロール系赤色顔料からなる群から選択される少なくとも一種の顔料を含有できる。 Preferably, the one type of colorant (E2) other than black is a red colorant. When the solder resist composition contains a perylene-based black colorant (E1) and a red colorant, when the film formed from the solder resist composition is exposed, the film is sufficiently cured from the surface layer to the deep part. Can do. Furthermore, the concealability of the conductor wiring by the film formed from the solder resist composition can be more sufficiently ensured. The red colorant can contain, for example, at least one pigment selected from the group consisting of an anthraquinone red pigment, an azo red pigment, a lake red pigment, a quinacridone red pigment, and a diketopyrrole red pigment.
　特に好ましくは、赤色着色剤はアントラキノン系赤色顔料である。アントラキノン系赤色顔料は、例えば、カラーインデックス（Ｃ．Ｉ．）ピグメントレッド８３、カラーインデックス（Ｃ．Ｉ．）ピグメントレッド１６８、カラーインデックス（Ｃ．Ｉ．）ピグメントレッド１７７、及びカラーインデックス（Ｃ．Ｉ．）ピグメントレッド２１６からなる群から選択される少なくとも一種の顔料であり得る。赤色着色剤がアントラキノン系赤色着色剤であることにより、ソルダーレジスト組成物から形成される被膜による導体配線の隠蔽性をより十分に確保することができる。また、アントラキノン系赤色着色剤は、優れた分散性及び耐候性を有する。 Particularly preferably, the red colorant is an anthraquinone red pigment. Anthraquinone red pigments include, for example, Color Index (CI) Pigment Red 83, Color Index (CI) Pigment Red 168, Color Index (CI) Pigment Red 177, and Color Index (C.I.). I.) It may be at least one pigment selected from the group consisting of Pigment Red 216. When the red colorant is an anthraquinone red colorant, the concealability of the conductor wiring by the film formed from the solder resist composition can be more sufficiently ensured. An anthraquinone red colorant has excellent dispersibility and weather resistance.
　［着色剤（Ｅ３）について］
　着色剤（Ｅ）は、着色剤（Ｅ１）及び黒色以外の一種の着色剤（Ｅ２）以外の着色剤（Ｅ３）を更に含有してもよい。すなわち、ソルダーレジスト組成物は着色剤（Ｅ３）を含有してもよい。 [About Colorant (E3)]
The colorant (E) may further contain a colorant (E3) other than the colorant (E1) and one kind of colorant (E2) other than black. That is, the solder resist composition may contain a colorant (E3).
　着色剤（Ｅ３）は、例えば、赤色着色剤、青色着色剤、緑色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤、茶色着色剤、及び前記以外の色の着色剤からなる群から選択される少なくとも一種の着色剤である。好ましくは、着色剤（Ｅ３）は、赤色着色剤、紫色着色剤、オレンジ色着色剤、及び茶色着色剤からなる群から選択される少なくとも一種の着色剤である。 The colorant (E3) is, for example, from the group consisting of a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, a brown colorant, and a colorant of a color other than those described above. At least one colorant selected. Preferably, the colorant (E3) is at least one colorant selected from the group consisting of a red colorant, a purple colorant, an orange colorant, and a brown colorant.
　［その他の成分について］
　ソルダーレジスト組成物は、有機溶剤を含有してもよい。有機溶剤は、ソルダーレジスト組成物の液状化又はワニス化、粘度調整、塗布性の調整、造膜性の調整などを行うために使用される。 [Other ingredients]
The solder resist composition may contain an organic solvent. The organic solvent is used for liquefying or varnishing the solder resist composition, adjusting the viscosity, adjusting the coating property, adjusting the film forming property, and the like.
　有機溶剤は、例えばエタノール、プロピルアルコール、イソプロピルアルコール、ヘキサノール、エチレングリコール等の直鎖、分岐、２級或いは多価のアルコール類；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、キシレン等の芳香族炭化水素類；スワゾールシリーズ（丸善石油化学社製）、ソルベッソシリーズ（エクソン・ケミカル社製）等の石油系芳香族系混合溶剤；セロソルブ、ブチルセロソルブ等のセロソルブ類；カルビトール、ブチルカルビトール等のカルビトール類；プロピレングリコールメチルエーテル等のプロピレングリコールアルキルエーテル類；ジプロピレングリコールメチルエーテル等のポリプロピレングリコールアルキルエーテル類；酢酸エチル、酢酸ブチル、セロソルブアセテート、カルビトールアセテート等の酢酸エステル類；並びにジアルキルグリコールエーテル類からなる群から選択される少なくとも一種の化合物を含有できる。 Organic solvents include, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, hexanol and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene Petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.) and Solvesso series (manufactured by Exxon Chemical Co.); cellosolves such as cellosolve and butylcellosolve; Tolls; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, cal Acetic acid esters such as tall acetate; as well as containing at least one compound selected from the group consisting of dialkyl glycol ethers.
　ソルダーレジスト組成物に含まれる有機溶剤の割合は、ソルダーレジスト組成物から形成される塗膜を乾燥させる際に有機溶剤が速やかに揮散するように、すなわち有機溶剤が乾燥塗膜に残存しないように、調整されることが好ましい。特に、ソルダーレジスト組成物全体に対する有機溶剤の割合は、好ましくは５～９９．５質量％の範囲内であり、より好ましくは１５～８０質量％の範囲内である。尚、有機溶剤の好ましい割合は、塗布方法に応じて異なる。このため、有機溶剤の割合が、塗布方法に応じて、適宜調節されることが好ましい。 The proportion of the organic solvent contained in the solder resist composition is such that when the coating film formed from the solder resist composition is dried, the organic solvent is volatilized quickly, that is, the organic solvent does not remain in the dry coating film. It is preferable to be adjusted. In particular, the ratio of the organic solvent to the entire solder resist composition is preferably in the range of 5 to 99.5% by mass, more preferably in the range of 15 to 80% by mass. In addition, the preferable ratio of an organic solvent changes with coating methods. For this reason, it is preferable that the ratio of the organic solvent is appropriately adjusted according to the coating method.
　本発明の主旨を逸脱しない限りにおいて、ソルダーレジスト組成物は、上記成分以外の成分を更に含有してもよい。 Unless departing from the gist of the present invention, the solder resist composition may further contain components other than the above components.
　例えば、ソルダーレジスト組成物は、カプロラクタム、オキシム、マロン酸エステル等でブロックされたトリレンジイソシアネート系、モルホリンジイソシアネート系、イソホロンジイソシアネート系及びヘキサメチレンジイソシアネート系のブロックドイソシアネート；メラミン樹脂、ｎ－ブチル化メラミン樹脂、イソブチル化メラミン樹脂、ブチル化尿素樹脂、ブチル化メラミン尿素共縮合樹脂、ベンゾグアナミン系共縮合樹脂等のアミノ樹脂；前記以外の各種熱硬化性樹脂；紫外線硬化性エポキシ（メタ）アクリレート；ビスフェノールＡ型、フェノールノボラック型、クレゾールノボラック型、脂環型等のエポキシ樹脂に（メタ）アクリル酸を付加して得られる樹脂；並びにジアリルフタレート樹脂、フェノキシ樹脂、ウレタン樹脂、フッ素樹脂等の高分子化合物からなる群から選択される少なくとも一種の樹脂を含有してもよい。 For example, the solder resist composition includes tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanates blocked with caprolactam, oxime, malonic acid ester, etc .; melamine resin, n-butylated melamine Resins, isobutylated melamine resins, butylated urea resins, butylated melamine urea cocondensation resins, benzoguanamine-based cocondensation resins, and other amino resins; various other thermosetting resins; ultraviolet curable epoxy (meth) acrylates; bisphenol A Resin obtained by adding (meth) acrylic acid to epoxy resin such as epoxy, phenol novolac, cresol novolac, alicyclic, etc .; and diallyl phthalate resin, phenoxy resin, urethane resin It may contain at least one resin selected from the group consisting of a polymer compound such as a fluorine resin.
　ソルダーレジスト組成物がエポキシ化合物を含有する場合、ソルダーレジスト組成物は、エポキシ化合物を硬化させるための硬化剤を含有してもよい。硬化剤は、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；アジピン酸ヒドラジド、セバシン酸ヒドラジド等のヒドラジン化合物；トリフェニルホスフィン等のリン化合物；酸無水物；フェノール；メルカプタン；ルイス酸アミン錯体；及びオニウム塩からなる群から選択される少なくとも一種の化合物を含有できる。市販されているこれらの化合物の例は、例えば、四国化成株式会社製の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－ＣＡＴ３５０３Ｎ、Ｕ－ＣＡＴ３５０２Ｔ（いずれもジメチルアミンのブロックイソシアネート化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ－ＣＡＴＳＡ１０２、Ｕ－ＣＡＴ５００２（いずれも二環式アミジン化合物及びその塩）を含み得る。 When the solder resist composition contains an epoxy compound, the solder resist composition may contain a curing agent for curing the epoxy compound. Examples of the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; Lewis acid amine complexes; Oni It can contain at least one compound selected from the group consisting of unsalted. Examples of these commercially available compounds include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U- CAT3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof).
　ソルダーレジスト組成物は、密着性を付与する添加剤を含有してもよい。この添加剤は、例えばグアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、並びに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－４，６－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－トリアジン誘導体からなる群から選択される少なくとも一種の化合物を含有できる。 The solder resist composition may contain an additive that imparts adhesion. Examples of the additive include guanamine, acetoguanamine, benzoguanamine, melamine, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl- At least one selected from the group consisting of S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct These compounds can be contained.
　ソルダーレジスト組成物は、硬化促進剤；シリコーン、アクリレート等の共重合体；レベリング剤；シランカップリング剤等の密着性付与剤；チクソトロピー剤；重合禁止剤；ハレーション防止剤；難燃剤；消泡剤；酸化防止剤；界面活性剤；高分子分散剤；並びに硫酸バリウム、結晶性シリカ、ナノシリカ、カーボンナノチューブ、タルク、ベントナイト、水酸化アルミニウム、水酸化マグネシウム、酸化マグネシウム、炭酸カルシウム等の無機フィラーからなる群から選択される一種以上の成分を含有してもよい。 Solder resist composition includes curing accelerator; copolymer such as silicone and acrylate; leveling agent; adhesion imparting agent such as silane coupling agent; thixotropic agent; polymerization inhibitor; antihalation agent; flame retardant; An antioxidant; a surfactant; a polymer dispersant; and an inorganic filler such as barium sulfate, crystalline silica, nanosilica, carbon nanotube, talc, bentonite, aluminum hydroxide, magnesium hydroxide, magnesium oxide, and calcium carbonate. You may contain the 1 or more types of component selected from a group.
　ソルダーレジスト組成物は、更に公知の光重合促進剤、増感剤等を含有してもよい。例えばソルダーレジスト組成物は、ｐ－ジメチル安息香酸エチルエステル、ｐ－ジメチルアミノ安息香酸イソアミルエステル、２－ジメチルアミノエチルベンゾエート等を含有してもよい。 The solder resist composition may further contain a known photopolymerization accelerator, sensitizer and the like. For example, the solder resist composition may contain p-dimethylbenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate and the like.
　［ソルダーレジスト組成物に含まれる各成分の配合量及び調製方法について］
　ソルダーレジスト組成物中の各成分の量は、ソルダーレジスト組成物が光硬化性を有しアルカリ性溶液で現像可能であるように、適宜調整される。 [About the compounding quantity and preparation method of each component contained in a soldering resist composition]
The amount of each component in the solder resist composition is appropriately adjusted so that the solder resist composition has photocurability and can be developed with an alkaline solution.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）、光重合性化合物（Ｂ）、光重合開始剤（Ｃ）、及び熱硬化性成分（Ｄ）の合計に対するカルボキシル基含有樹脂（Ａ）の割合は、好ましくは４０～８０質量％の範囲内であり、より好ましくは４５～７５質量％の範囲内であり、特に好ましくは５０～７０質量％の範囲内である。 Of the carboxyl group-containing resin (A) with respect to the total of the carboxyl group-containing resin (A), photopolymerizable compound (B), photopolymerization initiator (C), and thermosetting component (D) contained in the solder resist composition. The ratio is preferably in the range of 40 to 80% by mass, more preferably in the range of 45 to 75% by mass, and particularly preferably in the range of 50 to 70% by mass.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する光重合性化合物（Ｂ）の割合は、好ましくは５～６０質量％の範囲内であり、より好ましくは１０～５０質量％の範囲内であり、特に好ましくは１５～４０質量％の範囲内である。 The ratio of the photopolymerizable compound (B) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass. Particularly preferably, it is in the range of 15 to 40% by mass.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する光重合開始剤（Ｃ）はの割合は、好ましくは１～５０質量％の範囲内であり、より好ましくは３～４０質量％の範囲内であり、特に好ましくは５～２５質量％の範囲内である。 The ratio of the photopolymerization initiator (C) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass. And particularly preferably in the range of 5 to 25% by mass.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する熱硬化性成分（Ｄ）の割合は、好ましくは５～８５質量％の範囲内であり、より好ましくは１０～６０質量％の範囲内であり、特に好ましくは１５～４５質量％の範囲内である。 The ratio of the thermosetting component (D) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 60% by mass. Particularly preferably, it is in the range of 15 to 45% by mass.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する着色剤（Ｅ）の割合は、好ましくは０．２～１５質量％の範囲内であり、より好ましくは０．５～１０質量％の範囲内であり、特に好ましくは１～８質量％の範囲内である。ソルダーレジスト組成物がこれらの割合の着色剤（Ｅ）を含む場合、ソルダーレジスト組成物で形成されるソルダーレジスト層の解像性を確保しやすい。ソルダーレジスト組成物に含まれる着色剤（Ｅ）の割合が多すぎると、ソルダーレジスト組成物から形成されるソルダーレジスト層の解像性が低下し得る。 The ratio of the colorant (E) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.2 to 15% by mass, more preferably 0.5 to 10% by mass. It is within the range, and particularly preferably within the range of 1 to 8% by mass. When a soldering resist composition contains the coloring agent (E) of these ratios, it is easy to ensure the resolution of the soldering resist layer formed with a soldering resist composition. When there are too many ratios of the coloring agent (E) contained in a soldering resist composition, the resolution of the soldering resist layer formed from a soldering resist composition may fall.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対するペリレン系黒色着色剤（Ｅ１）の割合は、好ましくは０．１～１４質量％の範囲内であり、より好ましくは０．５～７質量％の範囲内である。 The ratio of the perylene-based black colorant (E1) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.1 to 14% by mass, more preferably 0.5 to 7 It is in the range of mass%.
　ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する黒色以外の一種の着色剤（Ｅ２）の割合は、好ましくは０．１～１２質量％の範囲内であり、より好ましくは０．５～７質量％の範囲内である。特に、着色剤（Ｅ２）が赤色着色剤である場合、ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する着色剤（Ｅ２）の割合は、好ましくは０．５～７質量％の範囲内である。 The ratio of one kind of colorant (E2) other than black to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.1 to 12% by mass, more preferably 0.5. It is in the range of ˜7% by mass. In particular, when the colorant (E2) is a red colorant, the ratio of the colorant (E2) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably in the range of 0.5 to 7% by mass. Is within.
　ソルダーレジスト組成物に含まれるペリレン系黒色着色剤（Ｅ１）及び着色剤（Ｅ２）の割合が上記の範囲内であることにより、ソルダーレジスト組成物の被膜を硬化させる際に、被膜の表層から深部まで特に十分に硬化させることができると共に、ソルダーレジスト組成物から形成されるソルダーレジスト層の導体配線の隠蔽性を特に向上させることができる。 When the ratio of the perylene-based black colorant (E1) and the colorant (E2) contained in the solder resist composition is within the above range, when the film of the solder resist composition is cured, the depth from the surface layer of the film In particular, the concealability of the conductor wiring of the solder resist layer formed from the solder resist composition can be particularly improved.
　また、ソルダージスト組成物中に着色剤（Ｅ３）が含まれる場合、ソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）に対する着色剤（Ｅ３）の割合は、好ましくは０．１～７質量％の範囲内である。 In addition, when the colorant (E3) is included in the solder resist composition, the ratio of the colorant (E3) to the carboxyl group-containing resin (A) contained in the solder resist composition is preferably 0.1 to 7 mass. %.
　ソルダーレジスト組成物は、例えば、上記のソルダーレジスト組成物の成分を、三本ロール、ボールミル、サンドミル等によって混練することにより、得られる。 The solder resist composition can be obtained, for example, by kneading the components of the solder resist composition with a three roll, ball mill, sand mill or the like.
　このソルダーレジスト組成物を、銅板上で、光硬化させてから熱硬化させることで皮膜を形成し、この被膜の厚みが１８～２２μｍの範囲内のいずれかである場合、この被膜のＬ＊値が４０以下であり、ａ＊値が５．１～５５の範囲内であり、且つｂ＊値が－１５～１５の範囲内である。尚、厚みが１８～２２μｍの範囲内のいずれかである被膜のＬ＊値、ａ＊値、及びｂ＊値が、上記の条件を満たしているなら、その他の厚みを有する被膜は、上記の条件を満たさなくてもよい。例えば、厚みが２０μｍである被膜が上記の条件を満たしていれば、厚みが１８μｍである被膜が上記の条件を備えていなくてもよい。この場合、ソルダーレジスト組成物から形成されるソルダーレジスト層による導体配線の隠蔽性を十分に確保できる。尚、被膜のＬ＊値、ａ＊値、及びｂ＊値は、例えば、分光測色計によって測定できる。この分光測色計は、例えば、コニカミノルタセンシング株式会社製の型番ＣＭ－６００ｄである。 When this solder resist composition is photocured on a copper plate and then thermally cured to form a film, and the thickness of this film is in the range of 18 to 22 μm, the L * value of this film Is 40 or less, the a * value is in the range of 5.1 to 55, and the b * value is in the range of −15 to 15. If the L * value, a * value, and b * value of the coating having a thickness in the range of 18 to 22 μm satisfy the above conditions, the coating having other thicknesses is It is not necessary to satisfy the conditions. For example, if the film having a thickness of 20 μm satisfies the above conditions, the film having a thickness of 18 μm may not have the above conditions. In this case, the concealability of the conductor wiring by the solder resist layer formed from the solder resist composition can be sufficiently ensured. The L * value, a * value, and b * value of the coating can be measured by, for example, a spectrocolorimeter. This spectrocolorimeter is, for example, model number CM-600d manufactured by Konica Minolta Sensing Co., Ltd.
　保存安定性等の観点から、ソルダーレジスト組成物の原料の一部を混合することで第一剤を調製し、原料の残部を混合することで第二剤を調製してもよい。すなわち、ソルダーレジスト組成物は、第一剤と第二剤とを含んでもよい。例えば、原料のうち光重合性化合物（Ｂ）、有機溶剤の一部、及び熱硬化性成分（Ｄ）を予め混合して分散させることで第一剤を調製し、原料のうち残部を混合して分散させることで第二剤を調製してもよい。この場合、適時必要量の第一剤と第二剤とを混合し混合液を調製し、この混合液からソルダーレジスト層を形成することができる。 From the viewpoint of storage stability and the like, the first agent may be prepared by mixing a part of the raw material of the solder resist composition, and the second agent may be prepared by mixing the rest of the raw material. That is, the solder resist composition may include a first agent and a second agent. For example, the first agent is prepared by previously mixing and dispersing the photopolymerizable compound (B), a part of the organic solvent, and the thermosetting component (D) among the raw materials, and the remaining part of the raw materials is mixed. The second agent may be prepared by dispersing it. In this case, the required amount of the first agent and the second agent can be mixed to prepare a mixed solution, and the solder resist layer can be formed from this mixed solution.
　［被覆プリント配線板について］
　一実施形態のソルダーレジスト組成物は、例えばプリント配線板にソルダーレジスト層を形成するために適用される。これにより、被覆プリント配線板が製造される。 [About coated printed wiring boards]
The solder resist composition of one embodiment is applied, for example, to form a solder resist layer on a printed wiring board. Thereby, a covering printed wiring board is manufactured.
　以下に、一実施形態のソルダーレジスト組成物を用いてプリント配線板上にソルダーレジスト層を形成する方法の一例を、図１Ａ～図１Ｃを参照しながら説明する。本例では、光硬化性及び熱硬化性の両方を備えるソルダーレジスト組成物からソルダーレジスト層を形成する。 Hereinafter, an example of a method for forming a solder resist layer on a printed wiring board using the solder resist composition of one embodiment will be described with reference to FIGS. 1A to 1C. In this example, a solder resist layer is formed from a solder resist composition having both photocuring properties and thermosetting properties.
　まず、プリント配線板１００を用意し、このプリント配線板上にソルダーレジスト組成物を用いて塗膜１を形成する。例えばプリント配線板１００の表面上にソルダーレジスト組成物を塗布して湿潤状態の塗膜（湿潤塗膜）を形成する。ソルダーレジスト組成物の塗布方法は、公知の方法、例えば浸漬法、スプレー法、スピンコート法、ロールコート法、カーテンコート法、及びスクリーン印刷法からなる群から選択される。続いて、必要に応じてソルダーレジスト組成物中の有機溶剤を揮発させるために、例えば６０～１２０℃の範囲内の温度下で湿潤塗膜を乾燥させて、図１Ａに示すように、乾燥後の塗膜１（乾燥塗膜）を得る。 First, a printed wiring board 100 is prepared, and a coating film 1 is formed on the printed wiring board using a solder resist composition. For example, a solder resist composition is applied on the surface of the printed wiring board 100 to form a wet paint film (wet paint film). The method for applying the solder resist composition is selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing. Subsequently, in order to volatilize the organic solvent in the solder resist composition, if necessary, the wet coating film is dried at a temperature in the range of 60 to 120 ° C., for example, as shown in FIG. 1A. The coating film 1 (dry coating film) is obtained.
　尚、プリント配線板上に塗膜１を形成する場合には、予め適宜の支持体上にソルダーレジスト組成物を塗布してから乾燥することで塗膜１を形成し、この塗膜１をプリント配線板１００に重ねた状態で塗膜１とプリント配線板１００に圧力をかけることで、プリント配線板１００上に塗膜１を設けてもよい（ドライフィルム法）。 In addition, when forming the coating film 1 on a printed wiring board, the coating film 1 is formed by applying a solder resist composition on an appropriate support in advance and then drying, and printing the coating film 1 The coating film 1 may be provided on the printed wiring board 100 by applying pressure to the coating film 1 and the printed wiring board 100 in a state of being overlaid on the wiring board 100 (dry film method).
　続いて、図１Ｂに示すように、塗膜１にマスク３を直接又は間接的に当てがってから、マスク３へ向けて活性エネルギー線を照射することで、マスク３を介して塗膜１を露光する。 Subsequently, as shown in FIG. 1B, the mask 3 is applied directly or indirectly to the coating film 1, and then the active energy ray is irradiated toward the mask 3, whereby the coating film 1 is passed through the mask 3. To expose.
　活性エネルギー線は、ソルダーレジスト組成物の組成に応じて選択される。一実施形態では活性エネルギー線は紫外線である。紫外線の光源は、例えばケミカルランプ、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ及びメタルハライドランプからなる群から選択される光源である。 The active energy ray is selected according to the composition of the solder resist composition. In one embodiment, the active energy ray is ultraviolet light. The ultraviolet light source is, for example, a light source selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, and metal halide lamps.
　マスク３は、活性エネルギー線が透過される露光部３１と、活性エネルギー線が遮蔽される非露光部３２とを備える。露光部３１の形状はソルダーレジスト層のパターン形状と合致する。このマスクは、例えばマスクフィルム、乾板等のフォトツールである。このマスク３を介して塗膜１が露光されると、塗膜１における露光部３１に対応する部分に光が照射され、塗膜１における非露光部３２に対応する部分に光が照射されない。 The mask 3 includes an exposure part 31 through which active energy rays are transmitted and a non-exposure part 32 through which active energy rays are shielded. The shape of the exposed portion 31 matches the pattern shape of the solder resist layer. This mask is, for example, a photo tool such as a mask film or a dry plate. When the coating film 1 is exposed through the mask 3, light is irradiated to a portion corresponding to the exposed portion 31 in the coating film 1, and light is not irradiated to a portion corresponding to the non-exposed portion 32 in the coating film 1.
　尚、露光方法として、マスクを用いる方法以外の方法が採用されてもよい。例えばレーザ露光等による直接描画法が採用されてもよい。 It should be noted that a method other than the method using a mask may be adopted as the exposure method. For example, a direct drawing method such as laser exposure may be employed.
　一実施形態では、塗膜１が露光されると、上述の通り、塗膜１の表層から深部にわたって効率良く光硬化反応が進む。 In one embodiment, when the coating film 1 is exposed, the photocuring reaction proceeds efficiently from the surface layer to the deep part of the coating film 1 as described above.
　塗膜１の露光後、プリント配線板１００からマスク３を取り外し、そして塗膜１に現像処理を施すことで、塗膜１の露光されていない部分を除去する。その結果、図１Ｃに示すように、プリント配線板１００の表面上に塗膜１の露光された部分であるソルダーレジスト層１０が残存する。 After the coating film 1 is exposed, the mask 3 is removed from the printed wiring board 100, and the coating film 1 is developed to remove the unexposed portion of the coating film 1. As a result, as shown in FIG. 1C, the solder resist layer 10 that is the exposed portion of the coating film 1 remains on the surface of the printed wiring board 100.
　現像処理では、ソルダーレジスト組成物の組成に応じた適宜の現像液が使用され得る。現像液の具体例は、炭酸ナトリウム水溶液、炭酸カリウム水溶液、炭酸アンモニウム水溶液、炭酸水素ナトリウム水溶液、炭酸水素カリウム水溶液、炭酸水素アンモニウム水溶液、水酸化ナトリウム水溶液、水酸化カリウム水溶液、水酸化アンモニウム水溶液、水酸化テトラメチルアンモニウム水溶液、水酸化リチウム水溶液などのアルカリ性溶液を含み得る。現像液の具体例は、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン等の有機アミンを含み得る。これらの現像液のうち一種のみが用いられてもよく、複数種が併用されてもよい。現像液がアルカリ性溶液である場合、現像液の溶媒は、水のみであってもよく、水と低級アルコール類等の親水性有機溶媒との混合物であってもよい。 In the development treatment, an appropriate developer according to the composition of the solder resist composition can be used. Specific examples of the developer include an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous ammonium carbonate solution, an aqueous sodium hydrogen carbonate solution, an aqueous potassium hydrogen carbonate solution, an aqueous ammonium hydrogen carbonate solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, water An alkaline solution such as an aqueous tetramethylammonium oxide solution or an aqueous lithium hydroxide solution may be included. Specific examples of the developer may include organic amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine. Of these developing solutions, only one type may be used, or a plurality of types may be used in combination. When the developer is an alkaline solution, the solvent of the developer may be water alone or a mixture of water and a hydrophilic organic solvent such as lower alcohols.
　ソルダーレジスト組成物は熱硬化性成分（Ｄ）を含有するため、ソルダーレジスト層に加熱処理を施すことでソルダーレジスト層は硬化できる。加熱処理において、例えば、加熱温度は１２０～１８０℃の範囲内であり、加熱時間は３０～９０分間の範囲内である。これにより、ソルダーレジスト層の強度、硬度、耐薬品性等の性能を向上させることができる。 Since the solder resist composition contains a thermosetting component (D), the solder resist layer can be cured by subjecting the solder resist layer to a heat treatment. In the heat treatment, for example, the heating temperature is in the range of 120 to 180 ° C., and the heating time is in the range of 30 to 90 minutes. Thereby, performance, such as intensity | strength of a soldering resist layer, hardness, and chemical resistance, can be improved.
　また、ソルダーレジスト層を加熱処理した後、更にソルダーレジスト層に活性エネルギー線を照射してもよい。この場合、ソルダーレジスト層の光硬化反応を更に進行させることができる。これにより、ソルダーレジスト層のマイグレーション耐性を更に向上させることができる。 Further, after the solder resist layer is heat-treated, the solder resist layer may be further irradiated with active energy rays. In this case, the photocuring reaction of the solder resist layer can be further advanced. Thereby, the migration tolerance of a soldering resist layer can further be improved.
　上述の方法により、プリント配線板と、このプリント配線板を部分的に覆うソルダーレジスト層と、を備える被覆プリント配線板が得られる。この被覆プリント配線板において、ソルダーレジスト層は表層から深部に亘って充分に硬化されている。 By the above-described method, a coated printed wiring board including a printed wiring board and a solder resist layer that partially covers the printed wiring board is obtained. In this coated printed wiring board, the solder resist layer is sufficiently cured from the surface layer to the deep part.
　このソルダーレジスト層の膜厚は、例えば、好ましくは５～６０μｍの範囲内であり、より好ましくは１０～４０μｍの範囲内である。この場合、ソルダーレジスト層による導体配線の隠蔽性を向上させることができる。 The film thickness of the solder resist layer is, for example, preferably in the range of 5 to 60 μm, more preferably in the range of 10 to 40 μm. In this case, the concealability of the conductor wiring by the solder resist layer can be improved.
　このソルダーレジスト層が、更に別のソルダーレジスト層（第二レジスト層）によって覆われていることも好ましい。この第二レジスト層は、プリント配線板上のソルダーレジスト層を保護できる。 It is also preferable that this solder resist layer is covered with another solder resist layer (second resist layer). This second resist layer can protect the solder resist layer on the printed wiring board.
　すなわち、他の実施形態に係る被覆プリント配線板は、ソルダーレジスト層を覆う第二レジスト層を含むことが好ましい。 In other words, the coated printed wiring board according to another embodiment preferably includes a second resist layer that covers the solder resist layer.
　更に、この第二レジスト層が第一の領域と、第一の領域よりも高い光透過率を有する第二の領域と、を含むことが好ましい。第二レジスト層が光透過率の異なる複数の領域を備えることにより、互いに色が異なる領域を形成することができる。この場合、第二レジスト層に容易にマーキングを施すことができる。例えば、第一の領域の形状が適宜の図形、文字等の形状であることにより、第一の領域のマーキングが形成される。また、第二の領域の形状が適宜の図形、文字等の形状であることで、第二の領域のマーキングが形成されてもよい。このため、第二レジスト層の形成と同時にマーキングを施すことができる。 Furthermore, it is preferable that the second resist layer includes a first region and a second region having a light transmittance higher than that of the first region. When the second resist layer includes a plurality of regions having different light transmittances, regions having different colors can be formed. In this case, it is possible to easily mark the second resist layer. For example, the marking of the first region is formed when the shape of the first region is an appropriate figure, character, or the like. Moreover, the marking of a 2nd area | region may be formed because the shape of a 2nd area | region is shapes, such as a suitable figure and a character. For this reason, marking can be performed simultaneously with the formation of the second resist layer.
　以下、第二レジスト層を形成するためのソルダーレジスト組成物（以下、第二レジスト組成物という）について説明する。 Hereinafter, a solder resist composition (hereinafter referred to as a second resist composition) for forming the second resist layer will be described.
　第二レジスト組成物は、カルボキシル基含有樹脂（Ｆ）、光重合性化合物（Ｇ）、光重合開始剤（Ｈ）、着色剤（Ｉ）、及び明確な融点を有し且つ光重合性を有しない有機化合物（Ｊ）（以下、特定有機化合物（Ｊ）ともいう）を含有する。 The second resist composition has a carboxyl group-containing resin (F), a photopolymerizable compound (G), a photopolymerization initiator (H), a colorant (I), a clear melting point, and has photopolymerizability. The organic compound (J) which does not carry out (it is also hereafter called a specific organic compound (J)).
　上記のソルダーレジスト層及び第二レジスト層を備える被覆プリント配線板の製造においては、ソルダーレジスト組成物の乾燥塗膜（以下、第一塗膜という）上に、第二レジスト組成物を塗布して乾燥させることで第二塗膜を形成した後、この第二塗膜を露光する。続いて露光後の第一塗膜及び第二塗膜をアルカリ性溶液で現像した後、第一塗膜及び第二塗膜を加熱する。これにより、ソルダーレジスト層及び第二レジスト層を備えた被覆プリント配線板が製造される。 In the production of a coated printed wiring board provided with the solder resist layer and the second resist layer, a second resist composition is applied onto a dried coating film (hereinafter referred to as a first coating film) of the solder resist composition. After the second coating film is formed by drying, the second coating film is exposed. Then, after developing the 1st coating film and 2nd coating film after exposure with an alkaline solution, a 1st coating film and a 2nd coating film are heated. Thereby, the covering printed wiring board provided with the soldering resist layer and the 2nd resist layer is manufactured.
　特に、第二塗膜が露光される際、第二塗膜の第一の部分に活性エネルギー線が照射され、第二塗膜の第一の部分とは異なる第二の部分に、第一の部分よりも低い露光量の活性エネルギー線が照射され、第二塗膜における第一の部分及び第二の部分とは異なる第三領域に活性エネルギー線が照射されない。 In particular, when the second coating film is exposed, the first part of the second coating film is irradiated with active energy rays, and the second part different from the first part of the second coating film is exposed to the first part. An active energy ray having an exposure amount lower than that of the portion is irradiated, and the first region and the third region different from the second portion in the second coating film are not irradiated with the active energy ray.
　尚、第一の部分の露光量は均一であってもよく、第一の部分が互いに露光量の異なる複数の部分を含んでいてもよい。また、第二の部分に活性エネルギー線が照射される場合、第二の部の露光量は均一であってもよく、第二の部分が互いに露光量の異なる複数の部分を含んでいてもよい。 Note that the exposure amount of the first portion may be uniform, or the first portion may include a plurality of portions having different exposure amounts. When the active energy ray is irradiated to the second part, the exposure amount of the second part may be uniform, or the second part may include a plurality of parts having different exposure amounts. .
　特に、第二塗膜が加熱される際、第二塗膜の加熱温度はＴh≧Ｔm－３０（但し、Ｔh（℃）は第二塗膜の前記加熱温度、Ｔmは、特定有機化合物（Ｊ）の融点である）の関係を満たす。すなわち、第二塗膜が加熱される際の加熱温度は、特定有機化合物（Ｊ）の融点かよりも３０℃低い温度以上である。換言すれば、特定有機化合物（Ｊ）の融点は、第二塗膜を加熱する際の加熱温度よりも３０℃高い温度以下である。 In particular, when a second coating is heated, the heating temperature of the second coating T h ≧ T m -30 (where, T h (° C.) is the heating temperature of the second coating film, T m, the specific The relationship of the melting point of the organic compound (J) is satisfied. That is, the heating temperature when the second coating film is heated is equal to or higher than the temperature 30 ° C. lower than the melting point of the specific organic compound (J). In other words, the melting point of the specific organic compound (J) is not more than 30 ° C. higher than the heating temperature when heating the second coating film.
　第二レジスト層が形成される際、上記の条件が適用されると、第一の部分内に気泡が形成される。一方、第二の部分内には、加熱されても気泡は形成されず、或いは、第一の部分よりも低い割合の気泡が形成される。このため、第二塗膜の第一の部分の硬化物（第一の領域）の光透過率は、第二の部分の硬化物（第二の領域）よりも低い。また、第一の領域では、第二の領域よりも光の散乱が生じやすい。 When the above-mentioned conditions are applied when the second resist layer is formed, bubbles are formed in the first portion. On the other hand, bubbles are not formed in the second portion even when heated, or bubbles at a lower rate than the first portion are formed. For this reason, the light transmittance of the hardened | cured material (1st area | region) of the 1st part of a 2nd coating film is lower than the hardened | cured material (2nd area | region) of a 2nd part. Also, light scattering is more likely to occur in the first region than in the second region.
　このため、第一の領域の外観の色は、第二レジスト組成物に含まれる着色剤（Ｉ）の色である。これに対して、第二の領域の外観の色は、第二レジスト組成物に含まれる着色剤（Ｉ）の色と、ソルダーレジスト層の表面の色との混合色である。この効果は、次の理由により生じると推察される。 Therefore, the color of the appearance of the first region is the color of the colorant (I) contained in the second resist composition. On the other hand, the color of the appearance of the second region is a mixed color of the color of the colorant (I) contained in the second resist composition and the color of the surface of the solder resist layer. This effect is presumed to occur for the following reason.
　第一の部分は第二塗膜が露光された時に活性エネルギー線が照射されているため、第一の部分は光重合性化合物（Ｇ）の光重合反応により生成した重合体を含んでいる。この状態で第二塗膜が加熱されると、第二塗膜内の特定有機化合物（Ｊ）が溶融して、第二塗膜が変形しようとする。しかし、第一の部分は重合体を含むため、特定有機化合物（Ｊ）の溶融に追随して変形しにくい。このため、第一の部分内に気泡が生じ得る。一方、第二の部分は、光重合性化合物（Ｇ）の重合体を含まず、或いは、この重合体の割合が第一の部分よりも低い。このため、第二塗膜が加熱されると、第二の部分は第一の部分よりも特定有機化合物（Ｊ）の溶融に追随して変形しやすい。このため、第二の部分内に気泡が生じず、或いは第二の部分内の気泡の割合が第一の部分よりも低くなり得る。 Since the first part is irradiated with active energy rays when the second coating film is exposed, the first part contains a polymer produced by the photopolymerization reaction of the photopolymerizable compound (G). When the second coating film is heated in this state, the specific organic compound (J) in the second coating film melts and the second coating film tends to be deformed. However, since the first portion contains a polymer, it hardly deforms following the melting of the specific organic compound (J). For this reason, bubbles may be generated in the first portion. On the other hand, the second part does not contain the polymer of the photopolymerizable compound (G), or the ratio of this polymer is lower than that of the first part. For this reason, when the second coating film is heated, the second part is more likely to deform following the melting of the specific organic compound (J) than the first part. For this reason, bubbles may not be generated in the second portion, or the ratio of bubbles in the second portion may be lower than that of the first portion.
　尚、本実施形態では、第二塗膜を加熱する際の加熱温度が、特定有機化合物（Ｊ）の融点よりも低く、特定有機化合物（Ｊ）の融点よりも３０℃低い温度以上である場合、第一の部分内に気泡が生じる。その理由は明確には解明されていない。理由の一つは、第二塗膜内の特定有機化合物（Ｊ）に別の化合物が混入することによる、特定有機化合物（Ｊ）の融点降下（凝固点降下）であり得る。 In the present embodiment, the heating temperature at the time of heating the second coating film is lower than the melting point of the specific organic compound (J) and not less than 30 ° C. lower than the melting point of the specific organic compound (J). , Bubbles are generated in the first part. The reason is not clearly understood. One of the reasons may be a melting point drop (freezing point depression) of the specific organic compound (J) due to the mixing of another compound with the specific organic compound (J) in the second coating film.
　露光及び現像後の第二塗膜の加熱温度は、好ましくはＴm＋１００≧Ｔh≧Ｔm－３０の関係を満たす。この場合、第二レジスト組成物中の成分の熱による劣化が抑制される。 The heating temperature of the second coating film after exposure and development preferably satisfies the relationship of T m + 100 ≧ T h ≧ T m −30. In this case, deterioration of the components in the second resist composition due to heat is suppressed.
　第一塗膜上に第二塗膜を形成した時点から、第二塗膜の露光が完了する時点までの間、第二塗膜の温度を、特定有機化合物（Ｊ）の融点よりも低い温度に維持することがより好ましい。この場合、第一の領域内の気泡の割合がより高くなり、第一の領域の外観色と第二の領域の外観色との間の相違がより顕著になる。これは、第一の部分内の光重合性化合物（Ｇ）が重合する前に、第一の部分内で特定有機化合物（Ｊ）が溶融し、第一の部分内で特定有機化合物（Ｊ）が安定になり、このため、第二塗膜の露光後に第一の部分が加熱されても、第一の部分が変形しにくいためであると、推察される。更に好ましくは、第二レジスト組成物を配線板上に配置する時点から、第二塗膜の露光が完了する時点までの間、第二塗膜の温度を、特定有機化合物（Ｊ）の融点よりも３０℃低い温度よりも低い温度に維持する。 The temperature of the second coating film is lower than the melting point of the specific organic compound (J) from the time when the second coating film is formed on the first coating film to the time when the exposure of the second coating film is completed. It is more preferable to maintain it. In this case, the ratio of bubbles in the first region becomes higher, and the difference between the appearance color of the first region and the appearance color of the second region becomes more remarkable. This is because the specific organic compound (J) melts in the first portion before the photopolymerizable compound (G) in the first portion is polymerized, and the specific organic compound (J) in the first portion. Therefore, even if the first part is heated after the exposure of the second coating film, it is assumed that the first part is not easily deformed. More preferably, the temperature of the second coating film is determined from the melting point of the specific organic compound (J) between the time when the second resist composition is placed on the wiring board and the time when the exposure of the second coating film is completed. Is maintained at a temperature lower than the temperature 30 ° C. lower.
　この第二レジスト組成物について、更に詳しく説明する。 This second resist composition will be described in more detail.
　［カルボキシル基含有樹脂（Ｆ）について］
　カルボキシル基含有樹脂（Ｆ）は、第二レジスト組成物から形成される塗膜に、アルカリ性溶液による現像性を付与できる。カルボキシル基含有樹脂（Ｆ）は、例えば、上記のソルダーレジスト組成物に含まれるカルボキシル基含有樹脂（Ａ）と同じであり得る。 [Carboxyl group-containing resin (F)]
The carboxyl group-containing resin (F) can impart developability with an alkaline solution to a coating film formed from the second resist composition. The carboxyl group-containing resin (F) can be, for example, the same as the carboxyl group-containing resin (A) contained in the solder resist composition.
　［光重合性化合物（Ｇ）について］
　光重合性化合物（Ｇ）は、第二レジスト組成物に光硬化性を付与できる。光重合性化合物（Ｇ）は、例えば、上記のソルダーレジスト組成物に含まれる光重合性化合物（Ｂ）と同じであり得る。 [About Photopolymerizable Compound (G)]
The photopolymerizable compound (G) can impart photocurability to the second resist composition. The photopolymerizable compound (G) can be, for example, the same as the photopolymerizable compound (B) contained in the solder resist composition.
　［光重合開始剤（Ｈ）について］
　光重合開始剤（Ｈ）は、例えば、上記のソルダーレジスト組成物に含まれる光重合開示剤（Ｃ）と同じであり得る。第二レジスト組成物に含まれる光重合開始剤（Ｈ）は、好ましくはα-ヒドロキシアルキルフェノン類、α-アミノアルキルフェノン類、チオキサントン類、及びアシルホスフィンオキサイド系光重合開始剤からなる群から選択される少なくとも２種の成分を含む。 [About Photoinitiator (H)]
The photopolymerization initiator (H) can be, for example, the same as the photopolymerization disclosure agent (C) contained in the solder resist composition. The photopolymerization initiator (H) contained in the second resist composition is preferably selected from the group consisting of α-hydroxyalkylphenones, α-aminoalkylphenones, thioxanthones, and acylphosphine oxide photopolymerization initiators. Containing at least two components.
　［着色剤（Ｉ）について］
　着色剤（Ｉ）は、例えば、顔料、染料、及び色素からなる群から選択される少なくとも一種の材料を含む。尚、着色剤は、被膜形成用組成物から形成される被膜を着色する物質である。着色剤は、顔料と染料のいずれも含み得る。但し、着色剤（Ｉ）は、有色ではあるが被膜形成用組成物から被膜を形成する過程において加熱されることにより無色になる物質は、被膜を着色させないため、含まない。 [Colorant (I)]
The colorant (I) includes, for example, at least one material selected from the group consisting of pigments, dyes, and pigments. In addition, a coloring agent is a substance which colors the film formed from the composition for film formation. The colorant can include both pigments and dyes. However, the colorant (I) is not a substance that is colored but becomes colorless when heated in the process of forming a film from the film-forming composition because it does not color the film.
　着色剤（Ｉ）は、例えば赤色着色剤、青色着色剤、緑色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤、茶色着色剤、及び前記以外の色の着色剤からなる群から選択される少なくとも一種の材料を含有できる。 The colorant (I) is selected from the group consisting of, for example, a red colorant, a blue colorant, a green colorant, a yellow colorant, a purple colorant, an orange colorant, a brown colorant, and a colorant having a color other than those described above. At least one kind of material.
　特に着色剤（Ｉ）は、好ましくは緑色着色剤、あるいは青色着色剤と黄色着色剤の混合物を含む。この場合、第二レジスト層の第一の領域の外観の色が主として緑色になると共に、第二レジスト層の第二の領域の外観の色が、緑色着色剤の色とソルダーレジスト層の表面の色との混合色になる。このような第一領域と第二領域とは外観色が明確に異なるため、第一の領域及び第二の領域によって形成されるマーキングが判別されやすい。特に、ソルダーレジスト組成物に含まれる着色剤（Ｅ２）が赤色顔料であって、ソルダーレジスト層の表面の色が赤みがかった黒色である場合、第二の領域の外観の色は深い黒色である。この場合、第二レジスト層の第一の領域の外観の色と第二の領域の外観の色とは、特に明確に異なる。このため、第一の領域及び第二の領域によって形成されるマーキングが特に判別されやすい。 Particularly, the colorant (I) preferably contains a green colorant or a mixture of a blue colorant and a yellow colorant. In this case, the color of the appearance of the first region of the second resist layer is mainly green, and the color of the appearance of the second region of the second resist layer is the color of the green colorant and the surface of the solder resist layer. It becomes a mixed color with the color. Since the first region and the second region have distinctly different appearance colors, the marking formed by the first region and the second region can be easily distinguished. In particular, when the colorant (E2) contained in the solder resist composition is a red pigment and the surface color of the solder resist layer is reddish black, the color of the appearance of the second region is deep black. In this case, the color of the appearance of the first region of the second resist layer and the color of the appearance of the second region are particularly distinct. For this reason, the marking formed by the first region and the second region is particularly easily distinguished.
　緑色着色剤は、例えば、フタロシアニン系緑色着色剤、アントラキノン系緑色着色剤、ペリレン系緑色着色剤、及び金属置換もしくは無置換のフタロシアニン化合物からなる群から選択される少なくとも一種の着色剤を含有できる。緑色着色剤の具体的は、ピグメントグリーン７及びピグメントグリーン３６で表される着色剤が挙げられる。 The green colorant can contain, for example, at least one colorant selected from the group consisting of phthalocyanine green colorants, anthraquinone green colorants, perylene green colorants, and metal-substituted or unsubstituted phthalocyanine compounds. Specific examples of the green colorant include colorants represented by Pigment Green 7 and Pigment Green 36.
　［特定有機化合物（Ｊ）について］
　特定有機化合物（Ｊ）は、明確な融点を有し、この融点以上の温度で低粘度の液体であることが好ましい。特定有機化合物（Ｊ）の融点は、好ましくは１００～２３０℃の範囲内である。この場合、第二レジスト組成物が充分に露光されてから加熱されると、第二レジスト組成物の硬化物中で気泡が特に生成しやすく、且つ第二レジスト組成物の硬化物全体に対する気泡の割合が高くなる傾向がある。特定有機化合物（Ｊ）は、例えば結晶性エポキシ化合物及びジカルボン酸からなる群から選択される少なくとも一種の成分を含有できる。 [Specific organic compound (J)]
The specific organic compound (J) has a clear melting point, and is preferably a low-viscosity liquid at a temperature equal to or higher than this melting point. The melting point of the specific organic compound (J) is preferably in the range of 100 to 230 ° C. In this case, when the second resist composition is sufficiently exposed and then heated, bubbles are particularly likely to be generated in the cured product of the second resist composition, and the bubbles are formed on the entire cured product of the second resist composition. The ratio tends to be high. The specific organic compound (J) can contain, for example, at least one component selected from the group consisting of a crystalline epoxy compound and a dicarboxylic acid.
　結晶性エポキシ化合物は、エポキシ基を有し且つ結晶性を有するモノマー、プレポリマー及びポリマーからなる群から選択される少なくとも一種の成分を含有できる。このような成分は市販され、容易に入手可能である。例えば結晶性エポキシ化合物は、１，３，５－トリス（２，３－エポキシプロピル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン（高融点タイプ）、新日鉄住金化学株式会社製の品名ＹＤＣ－１３１２（ハイドロキノン型結晶性エポキシ樹脂）、新日鉄住金化学株式会社製の品名ＹＳＬＶ－１２０ＴＥ（チオエーテル型結晶性エポキシ樹脂）、日本化薬株式会社製の品名ＧＴＲ－１８００（テトラキスフェノールエタン型結晶性エポキシ樹脂）、ビスフェノールフルオレン型結晶性エポキシ樹脂、三菱化学株式会社製の品名ＹＸ－４０００（ビフェニル型結晶性エポキシ樹脂）、及び１，３，５－トリス（２，３－エポキシプロピル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン（低融点タイプ）からなる群から選択される少なくとも一種の成分を含有できる。 The crystalline epoxy compound can contain at least one component selected from the group consisting of a monomer, a prepolymer and a polymer having an epoxy group and crystallinity. Such components are commercially available and are readily available. For example, the crystalline epoxy compound is 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (high melting type) Product name YDC-1312 (hydroquinone type crystalline epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Product name YSLV-120TE (thioether type crystalline epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Product name GTR manufactured by Nippon Kayaku Co., Ltd. -1800 (tetrakisphenolethane type crystalline epoxy resin), bisphenolfluorene type crystalline epoxy resin, product name YX-4000 (biphenyl type crystalline epoxy resin) manufactured by Mitsubishi Chemical Corporation, and 1,3,5-tris (2 , 3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (low It can contain at least one component selected from the group consisting of a point type).
　ジカルボン酸は、例えばマロン酸、コハク酸、アジピン酸、シュウ酸、ピメリン酸、スベリン酸、セバシン酸、フタル酸、及び４－シクロヘキセン－１，２－ジカルボン酸からなる群から選択される少なくとも一種の成分を含有できる。 The dicarboxylic acid is, for example, at least one selected from the group consisting of malonic acid, succinic acid, adipic acid, oxalic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, and 4-cyclohexene-1,2-dicarboxylic acid. It can contain ingredients.
　特定有機化合物（Ｊ）は、光重合開始剤（Ｈ）に含まれる化合物であってもよい。このような化合物は、例えば、例えばビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、及びエタノン，１－〔９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾールー３－イル〕―１－（０－アセチルオキシム）からなる群から選択される少なくとも一種の成分を含有できる。 The specific organic compound (J) may be a compound contained in the photopolymerization initiator (H). Such compounds include, for example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and ethanone, It may contain at least one component selected from the group consisting of 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime).
　［第二レジスト組成物に含まれるその他の成分について］
　第二レジスト組成物はエポキシ化合物を含有してもよい。エポキシ化合物は、例えば、特定有機化合物（Ｊ）に含まれる結晶性エポキシ化合物、及び非結晶性エポキシ化合物からなる群から選択される少なくとも一種の成分を含有できる。 [Other components contained in the second resist composition]
The second resist composition may contain an epoxy compound. The epoxy compound can contain, for example, at least one component selected from the group consisting of a crystalline epoxy compound contained in the specific organic compound (J) and an amorphous epoxy compound.
　非結晶性エポキシ化合物は、例えば、非結晶性のクレゾールノボラック型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品名ＥＰＩＣＬＯＮ　Ｎ－６９５）、非結晶性のフェノールノボラック型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品名ＥＰＩＣＬＯＮ　Ｎ－７７５）、非結晶性のビスフェノールＡノボラック型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品名ＥＰＩＣＬＯＮ　Ｎ－８６５）、非結晶性のビスフェノールＡ型エポキシ樹脂（具体例として三菱化学株式会社製の品名ｊＥＲ１００１）、非結晶性のビスフェノールＦ型エポキシ樹脂（具体例として三菱化学株式会社製の品名ｊＥＲ４００４Ｐ）、非結晶性のビスフェノールＳ型エポキシ樹脂（具体例としてＤＩＣ株式会社製の品名ＥＰＩＣＬＯＮ　ＥＸＡ－１５１４）、非結晶性のビスフェノールＡＤ型エポキシ樹脂、非結晶性の水添ビスフェノールＡ型エポキシ樹脂、非結晶性のビフェニルノボラック型エポキシ樹脂、及び非結晶性の特殊二官能型エポキシ樹脂（具体例として、三菱化学株式会社製の品番ＹＬ７１７５－５００、及びＹＬ７１７５－１０００；ＤＩＣ株式会社製の品名ＥＰＩＣＬＯＮ　ＴＳＲ－９６０、ＥＰＩＣＬＯＮ　ＴＥＲ－６０１、ＥＰＩＣＬＯＮ　ＴＳＲ－２５０－８０ＢＸ、ＥＰＩＣＬＯＮ　１６５０－７５ＭＰＸ、ＥＰＩＣＬＯＮ　ＥＸＡ－４８５０、ＥＰＩＣＬＯＮ　ＥＸＡ－４８１６、ＥＰＩＣＬＯＮ　ＥＸＡ－４８２２、及びＥＰＩＣＬＯＮ　ＥＸＡ－９７２６；新日鉄住金化学株式会社製の品名ＹＳＬＶ－１２０Ｔ）、及び前記以外の非結晶性のビスフェノール系エポキシ樹脂からなる群から選択される少なくとも一種の成分を含有できる。 Non-crystalline epoxy compounds include, for example, non-crystalline cresol novolac type epoxy resin (specifically, product name EPICLON N-695 manufactured by DIC Corporation), non-crystalline phenol novolac type epoxy resin (specific example is DIC Corporation). Product name EPICLON N-775), amorphous bisphenol A novolak type epoxy resin (specifically, product name EPICLON N-865 manufactured by DIC Corporation), amorphous bisphenol A type epoxy resin (specifically Mitsubishi Chemical) Product name jER1001), non-crystalline bisphenol F type epoxy resin (specifically, product name jER4004P manufactured by Mitsubishi Chemical Corporation), non-crystalline bisphenol S type epoxy resin (specifically, product name manufactured by DIC Corporation) EPICLON EXA- 514), non-crystalline bisphenol AD type epoxy resin, non-crystalline hydrogenated bisphenol A type epoxy resin, non-crystalline biphenyl novolac type epoxy resin, and non-crystalline special bifunctional type epoxy resin (as specific examples) Product numbers YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Corporation; product names EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, manufactured by DIC Corporation EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; product name YSLV-120T manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and other non-crystalline bisfees It can contain at least one component selected from the group consisting Lumpur epoxy resin.
　第二レジスト組成物がエポキシ化合物を含有する場合、第二レジスト組成物は好ましくはエポキシ化合物を硬化させるための硬化剤を含有する。硬化剤は、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；アジピン酸ヒドラジド、セバシン酸ヒドラジド等のヒドラジン化合物；トリフェニルホスフィン等のリン化合物；酸無水物；フェノール；メルカプタン；ルイス酸アミン錯体；及びオニウム塩からなる群から選択される少なくとも一種以上の成分を含有できる。これらの化合物の市販品の例は、四国化成株式会社製の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－ＣＡＴ３５０３Ｎ、Ｕ－ＣＡＴ３５０２Ｔ（いずれもジメチルアミンのブロックイソシアネート化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ－ＣＡＴＳＡ１０２、Ｕ－ＣＡＴ５００２（いずれも二環式アミジン化合物及びその塩）を含む。また、硬化剤は、密着性付与剤としても機能するグアナミン、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－４，６－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含有してもよい。 When the second resist composition contains an epoxy compound, the second resist composition preferably contains a curing agent for curing the epoxy compound. Examples of the curing agent include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; Lewis acid amine complexes; Oni It can contain at least one or more components selected from the group consisting of unsalted. Examples of commercially available products of these compounds are 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof). Curing agents include guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S, which also function as an adhesion-imparting agent. -Contains S-triazine derivatives such as triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct May be.
　第二レジスト組成物は、更に安息香酸系又はｐ－ジメチルアミノ安息香酸エチルエステル、ｐ－ジメチルアミノ安息香酸イソアミルエステル、２－ジメチルアミノエチルベンゾエート等の第三級アミン系等の公知の光重合促進剤、増感剤等を含有してもよい。また、第二レジスト組成物は、レーザ露光法用増感剤として、７－ジエチルアミノ－４－メチルクマリン、４，６－ジエチル－７－エチルアミノクマリン等のクマリン誘導体、その他カルボシアニン色素系、キサンテン色素系等を含有してもよい。 The second resist composition is a known photopolymerization accelerator such as benzoic acid or tertiary amines such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester and 2-dimethylaminoethylbenzoate. An agent, a sensitizer and the like may be contained. In addition, the second resist composition is a sensitizer for laser exposure methods, such as coumarin derivatives such as 7-diethylamino-4-methylcoumarin and 4,6-diethyl-7-ethylaminocoumarin, other carbocyanine dyes, xanthene. It may contain a pigment system or the like.
　第二レジスト組成物は充填材を含有してもよい。この場合、第二塗膜の硬化収縮が低減する。充填材は、例えばシリカ、硫酸バリウム、カーボンナノチューブ、水酸化アルミニウム、及び水酸化マグネシウムからなる群から選択される少なくとも一種の成分を含有できる。 The second resist composition may contain a filler. In this case, the curing shrinkage of the second coating film is reduced. The filler can contain, for example, at least one component selected from the group consisting of silica, barium sulfate, carbon nanotubes, aluminum hydroxide, and magnesium hydroxide.
　第二レジスト組成物は、更に必要に応じて適宜の添加剤を含有してもよい。例えば第二レジスト組成物は、シリコーン、アクリレート等の共重合体；レベリング剤；シランカップリング剤等の密着性付与剤；チクソトロピー剤；重合禁止剤；ハレーション防止剤；難燃剤；消泡剤；酸化防止剤；界面活性剤；並びに高分子分散剤からなる群から選択される少なくとも一種の成分を含有してもよい。 The second resist composition may further contain appropriate additives as necessary. For example, the second resist composition includes a copolymer such as silicone and acrylate; a leveling agent; an adhesion-imparting agent such as a silane coupling agent; a thixotropic agent; a polymerization inhibitor; an antihalation agent; a flame retardant; It may contain at least one component selected from the group consisting of an inhibitor; a surfactant; and a polymer dispersant.
　第二レジスト組成物は有機溶剤を含有してもよい。有機溶剤は、第二レジスト組成物の液状化又はワニス化、粘度調整、塗布性の調整、造膜性の調整などの目的で使用される。この有機溶剤は、例えば、上記のソルダーレジスト組成物に含まれる有機溶剤と同じであってもよい。 The second resist composition may contain an organic solvent. The organic solvent is used for the purpose of liquefaction or varnishing of the second resist composition, viscosity adjustment, coating property adjustment, film forming property adjustment, and the like. This organic solvent may be the same as the organic solvent contained in the solder resist composition, for example.
　第二レジスト組成物中の有機溶剤の割合は、第二塗膜の予備乾燥時に有機溶剤が速やかに揮散するように、すなわち第二レジスト組成物中の有機溶剤の割合は、有機溶剤が乾燥後の第二塗膜に残存しないように、調整されることが好ましい。特に、第二レジスト組成物中の有機溶剤の割合は、好ましくは５～９９．５質量％の範囲内である。この場合、第二レジスト組成物の良好な塗布性が得られる。尚、有機溶剤の好適な割合は、塗布方法などによって異なるので、塗布方法に応じて割合が適宜調節されることが好ましい。 The ratio of the organic solvent in the second resist composition is such that the organic solvent is volatilized quickly during the preliminary drying of the second coating film, that is, the ratio of the organic solvent in the second resist composition is after the organic solvent is dried. It is preferable to adjust so that it may not remain in the second coating film. In particular, the proportion of the organic solvent in the second resist composition is preferably in the range of 5 to 99.5% by mass. In this case, good applicability of the second resist composition can be obtained. In addition, since the suitable ratio of an organic solvent changes with application methods etc., it is preferable that a ratio is suitably adjusted according to the application method.
　［第二レジスト組成物に含まれる各成分の配合量及び調製方法について］
　第二レジスト組成物に含まれる各成分の量は、第二レジスト組成物が光硬化性を有すると共にアルカリ性溶液で現像可能であるように、適宜調整される。 [About the amount and preparation method of each component contained in the second resist composition]
The amount of each component contained in the second resist composition is appropriately adjusted so that the second resist composition has photocurability and can be developed with an alkaline solution.
　第二レジスト組成物の固形分量に対するカルボキシル基含有樹脂（Ｆ）の割合は、好ましくは１５～５５質量％の範囲内であり、より好ましくは２０～５０質量％の範囲内であり、更に好ましくは２５～４５質量％の範囲内である。 The ratio of the carboxyl group-containing resin (F) to the solid content of the second resist composition is preferably in the range of 15 to 55% by mass, more preferably in the range of 20 to 50% by mass, and still more preferably. It is in the range of 25 to 45% by mass.
　第二レジスト組成物に含まれるカルボキシル基含有樹脂（Ｆ）に対する光重合性化合物（Ｇ）の割合は、好ましくは５～６０質量％の範囲内であり、より好ましくは１０～５０質量％の範囲内であり、更に好ましくは１５～４０質量％の範囲内である。 The ratio of the photopolymerizable compound (G) to the carboxyl group-containing resin (F) contained in the second resist composition is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass. More preferably, it is in the range of 15 to 40% by mass.
　第二レジスト組成物に含まれるカルボキシル基含有樹脂（Ｆ）に対する光重合開始剤（Ｈ）の割合は、１～５０質量％の範囲内であり、より好ましくは３～４０質量％の範囲内であり、更に好ましくは５～２５質量％の範囲内である。 The ratio of the photopolymerization initiator (H) to the carboxyl group-containing resin (F) contained in the second resist composition is in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass. More preferably, it is in the range of 5 to 25% by mass.
　第二レジスト組成物に含まれるカルボキシル基含有樹脂（Ｆ）に対する着色剤（Ｉ）の割合は、好ましくは０．２～１５質量％の範囲内であり、より好ましくは０．５～１０質量％の範囲内である。第二レジスト組成物の固形分量に対する緑色着色剤の割合は、好ましくは０．２～１５質量％の範囲内であり、より好ましくは０．５～１０質量％の範囲内である。 The ratio of the colorant (I) to the carboxyl group-containing resin (F) contained in the second resist composition is preferably in the range of 0.2 to 15% by mass, more preferably 0.5 to 10% by mass. Is within the range. The ratio of the green colorant to the solid content of the second resist composition is preferably in the range of 0.2 to 15% by mass, and more preferably in the range of 0.5 to 10% by mass.
　第二レジスト組成物に含まれるカルボキシル基含有樹脂（Ｆ）に対する特定有機化合物（Ｊ）の割合は、好ましくは１５～２００質量％の範囲内であり、より好ましくは２０～１００質量％の範囲内であり、更に好ましくは２５～８０質量％の範囲内であり、特に好ましくは３０～６０質量％の範囲内である。 The ratio of the specific organic compound (J) to the carboxyl group-containing resin (F) contained in the second resist composition is preferably in the range of 15 to 200% by mass, more preferably in the range of 20 to 100% by mass. More preferably, it is in the range of 25 to 80% by mass, and particularly preferably in the range of 30 to 60% by mass.
　尚、ここでいう固形分量とは、第二レジスト組成物から第二レジスト層を形成する過程において揮発する溶剤などの成分を除いた、全成分の合計量のことである。 The solid content here is the total amount of all components excluding components such as a solvent that volatilizes in the process of forming the second resist layer from the second resist composition.
　第二レジスト組成物は、例えば、上記の第二レジスト組成物の原料を、三本ロール、ボールミル、サンドミル等によって混練することにより、得られる。 The second resist composition can be obtained, for example, by kneading the above-mentioned second resist composition raw materials with a three-roll, ball mill, sand mill or the like.
　保存安定性等を考慮して、第二レジスト組成物の原料の一部を混合することで第一剤を調製し、第二レジスト組成物の原料の残部を混合することで第二剤を調製してもよい。例えば、第二レジスト組成物の原料のうち、光重合性化合物（Ｇ）と、有機溶剤の一部と、特定有機化合物（Ｊ）とを予め混合して分散させることで第一剤を調製し、第二レジスト組成物の原料のうち残部を混合して分散させることで第二剤を調製してもよい。この場合、適時必要量の第一剤と第二剤とを混合することで、第二レジスト組成物が調製することができる。 In consideration of storage stability, etc., the first agent is prepared by mixing a part of the raw material of the second resist composition, and the second agent is prepared by mixing the remainder of the raw material of the second resist composition. May be. For example, among the raw materials of the second resist composition, the first agent is prepared by previously mixing and dispersing the photopolymerizable compound (G), a part of the organic solvent, and the specific organic compound (J). The second agent may be prepared by mixing and dispersing the remainder of the raw material of the second resist composition. In this case, the second resist composition can be prepared by mixing the necessary amount of the first agent and the second agent in a timely manner.
　以下、第二レジスト組成物を用いてソルダーレジスト層上に第二レジスト層を形成する方法を、図２Ａ～図２Ｃを参照して説明する。 Hereinafter, a method of forming the second resist layer on the solder resist layer using the second resist composition will be described with reference to FIGS. 2A to 2C.
　まず、プリント配線板１００を用意し、このプリント配線板１００上に、上述の方法により、ソルダーレジスト組成物から第一塗膜１を形成する。更に、必要に応じてソルダーレジスト組成物中の有機溶剤を揮発させるために、湿潤塗膜を乾燥する。これにより乾燥された第一塗膜１（乾燥塗膜）が得られる。 First, the printed wiring board 100 is prepared, and the first coating film 1 is formed on the printed wiring board 100 from the solder resist composition by the method described above. Further, the wet coating film is dried to volatilize the organic solvent in the solder resist composition as necessary. Thereby, the dried 1st coating film 1 (dry coating film) is obtained.
　次に、図２Ａに示すように、第一塗膜１の上に第二レジスト組成物を塗布することで、第二塗膜２を形成する。第二レジスト組成物の塗布方法は、公知の方法、例えば浸漬法、スプレー法、スピンコート法、ロールコート法、カーテンコート法、及びスクリーン印刷法からなる群から選択される方法である。 Next, as shown in FIG. 2A, the second coating film 2 is formed by applying a second resist composition onto the first coating film 1. The coating method of the second resist composition is a method selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating, and screen printing.
　続いて、必要に応じて第二レジスト組成物中の有機溶剤を揮発させるために、第二塗膜２を加熱する（予備乾燥）。この場合の加熱温度は、好ましくは第二レジスト組成物中の特定有機化合物（Ｊ）の融点よりも低い温度であり、より好ましくは第二レジスト組成物中の特定有機化合物（Ｊ）の融点よりも３０℃低い温度よりも低い温度である。この加熱温度は、例えば６０～１００℃の範囲内である。 Subsequently, the second coating film 2 is heated (preliminary drying) in order to volatilize the organic solvent in the second resist composition as necessary. In this case, the heating temperature is preferably lower than the melting point of the specific organic compound (J) in the second resist composition, more preferably from the melting point of the specific organic compound (J) in the second resist composition. Also, the temperature is lower than the temperature 30 ° C. lower. This heating temperature is in the range of 60 to 100 ° C., for example.
　第一塗膜１上に第二塗膜２を形成する場合、予め適宜の支持体上に第二レジスト組成物を塗布して乾燥することで第二塗膜２（ドライフィルム）を形成し、このドライフィルムを第一塗膜１の上に重ねた状態でドライフィルムと第一塗膜１に圧力をかけることで、第一塗膜１の上にドライフィルムを転着させてもよい（ドライフィルム法）。この場合、予備乾燥が省略されてもよい。 When forming the 2nd coating film 2 on the 1st coating film 1, the 2nd coating composition 2 (dry film) is formed by apply | coating and drying a 2nd resist composition on a suitable support body beforehand, The dry film may be transferred onto the first coating film 1 by applying pressure to the dry film and the first coating film 1 while the dry film is stacked on the first coating film 1 (dry Film method). In this case, preliminary drying may be omitted.
　あるいは、予め適宜の支持体上に第二レジスト組成物を塗布した後に第一レジスト組成物を塗布してから乾燥させることで第二塗膜２と第一塗膜１の２層からなる塗膜（ドライフィルム）を形成し、このドライフィルムをプリント配線板１００上に重ねた状態でドライフィルムとプリント配線板１００に圧力をかけることで、プリント配線板１００上にドライフィルムを転着させてもよい（ドライフィルム法）。この場合、予備乾燥が省略されてもよい。 Or the coating film which consists of two layers of the 2nd coating film 2 and the 1st coating film 1 by apply | coating a 1st resist composition after apply | coating a 2nd resist composition previously on a suitable support body, and making it dry. Even if the dry film is transferred onto the printed wiring board 100 by applying pressure on the dry film and the printed wiring board 100 in a state where the dry film is formed on the printed wiring board 100 Good (dry film method). In this case, preliminary drying may be omitted.
　続いて、図２Ｂに示すように、第二塗膜２にマスク４を直接又は間接的にあてがってから、マスク４に活性エネルギー線を照射することで、マスク４を介して第二塗膜２及び第一塗膜１を露光する。 Subsequently, as shown in FIG. 2B, the mask 4 is directly or indirectly applied to the second coating film 2, and then the active energy rays are applied to the mask 4, thereby allowing the second coating film 2 to pass through the mask 4. And the 1st coating film 1 is exposed.
　活性エネルギー線は、ソルダーレジスト組成物及び第二レジスト組成物の組成に応じて選択されるが、例えば紫外線である。紫外線の光源は、例えばケミカルランプ、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ及びメタルハライドランプからなる群から選択される。 The active energy ray is selected according to the composition of the solder resist composition and the second resist composition, and is, for example, ultraviolet rays. The ultraviolet light source is selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps, for example.
　マスク４は、それぞれ異なる光透過性を有する三種類の部分を備える。例えばマスク４は、光透過性を有する部分（以下、透過性部４１という）と、透過性部４１よりも低い光透過性を有する部分（以下、低透過性部４２という）と、光透過性を有しない部分（以下、非透過性部４３という）とを備える。 The mask 4 includes three types of portions each having different light transmittance. For example, the mask 4 includes a light transmissive portion (hereinafter referred to as a transmissive portion 41), a light transmissive portion lower than the transmissive portion 41 (hereinafter referred to as a low transmissive portion 42), and a light transmissive property. A portion (hereinafter referred to as a non-permeable portion 43).
　このマスク４を介して第二塗膜２が露光されると、第二塗膜２における透過性部４１に対応する部分（第一の部分２１）には光が照射され、第二塗膜２における低透過性部４２に対応する部分（第二の部分２２）には、第一の部分２１よりも低い露光量の光が照射され、第二塗膜２の非透過性部４３に対応する部分（第三の部分２３）には光が照射されない。尚、第一の部分２１は露光時に光が照射される部分であり、第二の部分２２は露光時に第一の部分２１よりも低い露光量で光が照射される部分であり、第三の部分２３は露光時に光が照射されない部分であり得る。マスク４の第一の部分２１、第二の部分２２及び第三の部分２３は、それぞれ第二塗膜２の所定の箇所に位置する。 When the second coating film 2 is exposed through this mask 4, the portion corresponding to the transmissive part 41 (first portion 21) in the second coating film 2 is irradiated with light, and the second coating film 2 is exposed. The portion corresponding to the low-permeability portion 42 (second portion 22) is irradiated with light having an exposure amount lower than that of the first portion 21, and corresponds to the non-permeable portion 43 of the second coating film 2. The portion (third portion 23) is not irradiated with light. The first portion 21 is a portion irradiated with light at the time of exposure, and the second portion 22 is a portion irradiated with light at an exposure amount lower than that of the first portion 21 at the time of exposure. The portion 23 may be a portion that is not irradiated with light during exposure. The first portion 21, the second portion 22, and the third portion 23 of the mask 4 are respectively located at predetermined locations on the second coating film 2.
　このように第二塗膜２が露光されると、第二塗膜２の第一の部分２１では光重合性化合物（Ｇ）の光重合反応が進行し、第二の部分２２でも、第一の部分２１よりも程度が低いものの、光重合性化合物（Ｇ）の光重合反応が進行する。一方、第三の部分２３では、光重合性化合物（Ｇ）の光重合反応は進行しない。 When the second coating film 2 is thus exposed, the photopolymerization reaction of the photopolymerizable compound (G) proceeds in the first portion 21 of the second coating film 2, and even in the second portion 22, Although the degree is lower than that of the portion 21, the photopolymerization reaction of the photopolymerizable compound (G) proceeds. On the other hand, in the third portion 23, the photopolymerization reaction of the photopolymerizable compound (G) does not proceed.
　尚、第一の部分２１、第二の部分２２及び第三の部分２３に対する露光量を、所望の値にコントロールできるならば、上記のマスク４が用いられなくてもよい。例えば、第二塗膜２に、第三の部分２３を遮蔽すると共に第一の部分２１及び第二の部分２２を遮蔽しないマスク（第一のマスク）を介して、光を照射し、続いて第一のマスクに、第二の部分２２を遮蔽すると共に第一の部分２１は遮蔽しないマスク（第二のマスク）を重ね、この第一のマスクと第二のマスクを介して、更に光を照射してもよい。この場合でも、第一の部分２１には光が照射され、第二の部分２２には、第一の部分２１よりも低い露光量で光が照射され、第三の部分２３には、光が照射されない。 In addition, if the exposure amount with respect to the 1st part 21, the 2nd part 22, and the 3rd part 23 can be controlled to a desired value, said mask 4 may not be used. For example, the second coating 2 is irradiated with light through a mask (first mask) that shields the third portion 23 and does not shield the first portion 21 and the second portion 22, and subsequently A mask (second mask) that shields the second portion 22 and does not shield the first portion 21 is superimposed on the first mask, and further light is transmitted through the first mask and the second mask. It may be irradiated. Even in this case, the first portion 21 is irradiated with light, the second portion 22 is irradiated with light at a lower exposure amount than the first portion 21, and the third portion 23 is irradiated with light. Not irradiated.
　例えば、第一の部分２１の露光量に対する第二の部分２２の露光量の割合は、好ましくは１～７５％の範囲内であり、より好ましくは１．２～６０％の範囲内である。例えば、第一の部分２１の露光量は、好ましくは１００～５０００ｍＪ／ｃｍ2の範囲内である。例えば、第二の部分２２の露光量は、好ましくは２０～５００ｍＪ／ｃｍ2の範囲内である。 For example, the ratio of the exposure amount of the second portion 22 to the exposure amount of the first portion 21 is preferably in the range of 1 to 75%, more preferably in the range of 1.2 to 60%. For example, the exposure amount of the first portion 21 is preferably in the range of 100 to 5000 mJ / cm 2 . For example, the exposure amount of the second portion 22 is preferably in the range of 20 to 500 mJ / cm 2 .
　第二塗膜２が露光されるのと同時に、第一塗膜１が露光される。第一塗膜１における透過性部４１及び低透過性部４２に対応する部分は、光が照射されることにより、硬化する。一方、第一塗膜１における非透過性部４３に対応する部分には、光が照射されない。 The first coating film 1 is exposed simultaneously with the second coating film 2 being exposed. The portions corresponding to the transmissive portion 41 and the low permeable portion 42 in the first coating film 1 are cured when irradiated with light. On the other hand, the portion corresponding to the non-permeable portion 43 in the first coating film 1 is not irradiated with light.
　第二塗膜２及び第一塗膜１に対する露光後、第二塗膜２及び第一塗膜１をアルカリ性現像液で現像する。その結果、第二塗膜２の第三の部分２３がプリント配線板１００上から除去されると共に、第一塗膜１における非透過性部４３に対応する部分も、プリント配線板１００上から除去される。第二塗膜２の第一の部分２１及び第二の部分２２は、プリント配線板１００上に残存する。 After the exposure to the second coating film 2 and the first coating film 1, the second coating film 2 and the first coating film 1 are developed with an alkaline developer. As a result, the third portion 23 of the second coating film 2 is removed from the printed wiring board 100, and the portion corresponding to the non-permeable portion 43 in the first coating film 1 is also removed from the printed wiring board 100. Is done. The first portion 21 and the second portion 22 of the second coating film 2 remain on the printed wiring board 100.
　第二塗膜２及び第一塗膜１に対する露光後、第二塗膜２（第一の部分２１及び第二の部分２２）を加熱する。この場合、第二塗膜２の加熱温度Ｔｈは、Ｔh≧Ｔm－３０の関係を満たし、好ましくはＴm＋１００≧Ｔh≧Ｔm－３０の関係を満たす。この式において、Ｔh（℃）は第二塗膜２の加熱温度であり、Ｔm（℃）は、特定有機化合物（Ｊ）の融点である。第二塗膜２の加熱温度は、例えば１００～２００℃の範囲内である。第二塗膜２の加熱時間は例えば２０分～５時間の範囲内である。 After the exposure to the second coating film 2 and the first coating film 1, the second coating film 2 (first portion 21 and second portion 22) is heated. In this case, the heating temperature T h of the second coating film 2 satisfies the relation of T h ≧ T m -30, preferably satisfies the relation T m + 100 ≧ T h ≧ T m -30. In this formula, T h (° C.) is the heating temperature of the second coating film 2, and T m (° C.) is the melting point of the specific organic compound (J). The heating temperature of the second coating film 2 is, for example, in the range of 100 to 200 ° C. The heating time of the second coating film 2 is, for example, in the range of 20 minutes to 5 hours.
　このように第二塗膜２を加熱温度Ｔｈで加熱した後、更に１５０℃～３００℃の範囲内、１～１０分間の範囲内の条件で第二塗膜２を加熱しても良い。更に、第二塗膜２を加熱温度Ｔｈで加熱した後、１００～５０００ｍＪ／ｃｍ2の範囲内の条件で紫外線を照射しても良い。 Thus after heating the second coating film 2 at a heating temperature T h, further in the range of 150 ℃ ~ 300 ℃, it may be heated second coating 2 at conditions within the range of 1 to 10 minutes. Further, after heating the second coating film 2 at a heating temperature T h, it may be irradiated with ultraviolet light under conditions in the range of 100 ~ 5000mJ / cm 2.
　このように第二塗膜２が加熱されることにより、第一の部分２１内で気泡が発生する。一方、第二の部分２２内には気泡は発生せず、或いは第一の部分２１よりも低い割合で気泡が発生する。また、第二レジスト組成物がエポキシ化合物を含有する場合、第二塗膜２を加熱することにより、エポキシ化合物の熱硬化反応が進行する。 In this way, when the second coating film 2 is heated, bubbles are generated in the first portion 21. On the other hand, no bubbles are generated in the second portion 22 or bubbles are generated at a lower rate than the first portion 21. Moreover, when the 2nd resist composition contains an epoxy compound, the thermosetting reaction of an epoxy compound advances by heating the 2nd coating film 2. FIG.
　第一の部分２１及び第二の部分２２が加熱された後、第一の部分２１及び第二の部分２２の全体に光が照射されてもよい。この場合、第一の部分２１及び第二の部分２２内に未反応のまま残存する光重合性化合物（Ｇ）の光重合反応が進行する。 After the first portion 21 and the second portion 22 are heated, the entire first portion 21 and the second portion 22 may be irradiated with light. In this case, the photopolymerization reaction of the photopolymerizable compound (G) remaining unreacted in the first portion 21 and the second portion 22 proceeds.
　上記の方法により、図２Ｃに示すように、プリント配線板１００上に、第一塗膜１の硬化物からなるソルダーレジスト層１０が形成され、ソルダーレジスト層１０の上に、第二塗膜２の硬化物からなる第二レジスト層２０が形成される。これにより、被覆プリント配線板が得られる。 2C, a solder resist layer 10 made of a cured product of the first coating film 1 is formed on the printed wiring board 100, and the second coating film 2 is formed on the solder resist layer 10. A second resist layer 20 made of the cured product is formed. Thereby, a covering printed wiring board is obtained.
　この被覆プリント配線板の第二レジスト層２０は、第一の部分２１の硬化物である第一の領域２４と、第二の部分２２の硬化物である第二の領域２５とを備える。第一の領域２４は気泡を含有する。一方、第二の領域２５は気泡を含有せず、或いは、第二の領域２５は第一の領域２４よりも低い密度で気泡を含有する。このため、第一の領域２４の光透過率と第二の領域２５の光透過率との間に差異があり、第二の領域２５の光透過率は、第一の領域２４の光透過率よりも高い。 The second resist layer 20 of the coated printed wiring board includes a first region 24 that is a cured product of the first portion 21 and a second region 25 that is a cured product of the second portion 22. The first region 24 contains bubbles. On the other hand, the second region 25 does not contain bubbles, or the second region 25 contains bubbles at a lower density than the first region 24. For this reason, there is a difference between the light transmittance of the first region 24 and the light transmittance of the second region 25, and the light transmittance of the second region 25 is the light transmittance of the first region 24. Higher than.
　第一の領域２４に含まれる気泡の割合は、好ましくは３～７０％の範囲内であり、より好ましくは５～６０％の範囲内である。また、第一の領域２４に含まれる気泡の割合に対する第二の領域２５に含まれる気泡の割合は、好ましくは０～５％の範囲内である。 The ratio of bubbles contained in the first region 24 is preferably in the range of 3 to 70%, more preferably in the range of 5 to 60%. Further, the ratio of the bubbles contained in the second area 25 to the ratio of the bubbles contained in the first area 24 is preferably in the range of 0 to 5%.
　尚、これらの気泡の割合は、第二レジスト層２０の表面を研磨することで現れる面（すなわち、第二レジスト層２０の表面に沿った第二レジスト層２０の断面）における、長径０．５μｍ以上の気泡の面積割合である。この面積割合は、例えば第二レジスト層２０の２０μｍ2の表面積を有する面における長径０．５μｍ以上の気泡の面積に基づいて導出される。 In addition, the ratio of these bubbles is a major axis of 0.5 μm on the surface appearing by polishing the surface of the second resist layer 20 (that is, the cross section of the second resist layer 20 along the surface of the second resist layer 20). This is the area ratio of the bubbles. This area ratio is derived based on the area of bubbles having a major axis of 0.5 μm or more on the surface of the second resist layer 20 having a surface area of 20 μm 2 , for example.
　これらの気泡の割合は、第一の部分２１に対する露光量、及び第二の部分２２に対する露光量を適宜調整することで、制御され得る。 The ratio of these bubbles can be controlled by appropriately adjusting the exposure amount for the first portion 21 and the exposure amount for the second portion 22.
　第二レジスト層２０の厚みは、例えば１０～４０μｍの範囲内であることが好ましい。この場合、第一の領域２４及び第二の領域２５によって形成されるマーキングを容易に判別することができる。第二レジスト層２０の厚みがこの範囲内である場合、第一の領域２４の気泡の割合は５～７０％の範囲内であることが好ましく、第二の領域２５における気泡の割合の割合は０～５％の範囲内であることが好ましい。 The thickness of the second resist layer 20 is preferably in the range of 10 to 40 μm, for example. In this case, the marking formed by the first region 24 and the second region 25 can be easily determined. When the thickness of the second resist layer 20 is within this range, the ratio of bubbles in the first region 24 is preferably within a range of 5 to 70%, and the ratio of the ratio of bubbles in the second region 25 is It is preferably in the range of 0 to 5%.
　ソルダーレジスト層１０上に形成されている第二レジスト層２０において、第一の領域２４のＬ＊値が３５以上、ａ＊値が－１５以下、且つｂ＊値が－５～５の範囲内であることが好ましく、第二の領域２５のＬ＊値が３２以下、ａ＊値が－１０～１０の範囲内、ｂ＊値が－５～５の範囲内であることが好ましい。この場合、第一の領域２４及び第二の領域２５によって形成されるマーキングを特に容易に判別することができる。 In the second resist layer 20 formed on the solder resist layer 10, the L * value of the first region 24 is 35 or more, the a * value is -15 or less, and the b * value is within the range of -5 to 5. Preferably, the second region 25 has an L * value of 32 or less, an a * value in the range of −10 to 10, and a b * value in the range of −5 to 5. In this case, the marking formed by the first region 24 and the second region 25 can be distinguished particularly easily.
　ソルダーレジスト層１０上の第二レジスト層２０の第一の領域２４のＬ＊値が３５以上、ａ＊値が－１５以下、ｂ＊値が－５～５の範囲内であり、且つ、第二の領域２５のＬ＊値が３２以下、ａ＊値が－１０～１０の範囲内、ｂ＊値が－５～５の範囲内であるためには、ソルダーレジスト組成物中の着色剤（Ｅ２）が赤色着色剤であると共に、第二レジスト組成物中の着色剤（Ｉ）が緑色着色剤であることが好ましい。この場合、着色剤（Ｅ２）の色と着色剤（Ｉ）の色とが補色の関係であることから、第二の領域２５の色を深い黒色にすることが容易になる。特に、ソルダーレジスト層１０のみを銅板上に設けた場合のソルダーレジスト層１０のＬ＊値が４０以下、ａ＊値が５．１～５５の範囲内、ｂ＊値が－１５～１５の範囲内であることが好ましい。また、第二レジスト層２０のみを銅板上に設けた場合の第二レジスト層２０における第二の領域２５のＬ＊値が３５以上、ａ＊値が－１００～－１５の範囲内、ｂ＊値が－２０～２０の範囲内であることが好ましい。 The L * value of the first region 24 of the second resist layer 20 on the solder resist layer 10 is 35 or more, the a * value is −15 or less, the b * value is in the range of −5 to 5, and In order that the L * value of the second region 25 is 32 or less, the a * value is in the range of −10 to 10 and the b * value is in the range of −5 to 5, the colorant (in the solder resist composition) It is preferable that E2) is a red colorant and the colorant (I) in the second resist composition is a green colorant. In this case, since the color of the colorant (E2) and the colorant (I) have a complementary relationship, it is easy to make the color of the second region 25 deep black. In particular, when only the solder resist layer 10 is provided on a copper plate, the L * value of the solder resist layer 10 is 40 or less, the a * value is in the range of 5.1 to 55, and the b * value is in the range of −15 to 15. It is preferable to be within. Further, when only the second resist layer 20 is provided on the copper plate, the L * value of the second region 25 in the second resist layer 20 is 35 or more, the a * value is in the range of −100 to −15, b * The value is preferably in the range of −20 to 20.
　［ソルダーレジスト層を備える被覆プリント配線板について］
　実施例１～５及び比較例１～３で用いるカルボキシル基含有不飽和樹脂溶液を、次のようにして調製した。 [Coated printed wiring board with solder resist layer]
The carboxyl group-containing unsaturated resin solutions used in Examples 1 to 5 and Comparative Examples 1 to 3 were prepared as follows.
　まず、還流冷却管、温度計、空気吹き込み管及び攪拌機が取り付けられている四つ口フラスコ内に、クレゾールノボラック型エポキシ樹脂（新日鉄住金化学株式会社製、品番ＹＤＣＮ－７００－５、エポキシ当量２０３）２０３質量部、ジエチレングリコールモノエチルエーテルアセテート１６０．１質量部、メチルハイドロキノン０．２質量部、アクリル酸７２．７質量部、及びジメチルベンジルアミン０．６質量部を入れることで、混合物を調製した。この混合物をフラスコ内で、加熱温度１１０℃、加熱時間１０時間の条件で加熱することで、付加反応を進行させた。 First, a cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YDCN-700-5, epoxy equivalent 203) is placed in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer. A mixture was prepared by adding 203 parts by mass, 160.1 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72.7 parts by mass of acrylic acid, and 0.6 parts by mass of dimethylbenzylamine. This mixture was heated in a flask under the conditions of a heating temperature of 110 ° C. and a heating time of 10 hours, thereby causing the addition reaction to proceed.
　続いて、フラスコ内の混合物にテトラヒドロ無水フタル酸６０．８質量部、及びジエチレングリコールモノエチルエーテルアセテート７８．９質量部を投入し、加熱温度１１５℃、加熱時間３時間の条件で加熱した。これにより、カルボキシル基含有樹脂の濃度６５質量％溶液を得た。 Subsequently, 60.8 parts by mass of tetrahydrophthalic anhydride and 78.9 parts by mass of diethylene glycol monoethyl ether acetate were added to the mixture in the flask and heated under the conditions of a heating temperature of 115 ° C. and a heating time of 3 hours. Thereby, a 65 mass% concentration solution of the carboxyl group-containing resin was obtained.
　また、表１に示す実施例１～５及び比較例１～３で用いるカルボキシル基含有不飽和樹脂溶液以外の原料の詳細は、次の通りである。
・エポキシ樹脂：１，３，５－トリグリシジルイソシアヌレート（日産化学工業社製、ＴＥＰＩＣ－ＨＰ）。
・エポキシ樹脂溶液：クレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製、品名ＥＰＩＣＬＯＮ　Ｎ－６９５）を固形分７０％でジエチレングリコールモノエチルエーテルアセテートに溶解した溶液。
・光重合開始剤Ａ：２－メチル－１－（４－メチルチオフェニル）―２－モルフォリノプロパンー１－オン（ＢＡＳＦ社製，品名Ｉｒｇａｃｕｒｅ　９０７）。
・光重合開始剤Ｂ：２，４－ジエチルチオキサンテン－９－オン（ＤＥＴＸ）。
・光重合開始剤Ｃ：２，４，６－トリメチルベンゾイルージフェニルーホスフィンオキサイド、ＢＡＳＦ社製の品名Ｉｒｇａｃｕｒｅ　ＴＰＯ。
・光重合開始剤Ｄ：１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、ＢＡＳＦ社製の品名Ｉｒｇａｃｕｒｅ　１８４。
・光重合性モノマー：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）。
・メラミン：日産化学工業株式会社製の微粉メラミン。
・硫酸バリウム：堺化学工業株式会社製の品名バリエースＢ３０。
・微粉シリカ：株式会社トクヤマ製の品名レオロシールＭＴ－１０。
・消泡剤：信越化学工業株式会社製の品名ＫＳ－６６。
・ペリレンブラックＡ：ＢＡＳＦ社製の品名Ｐａｌｉｏｇｅｎ　Ｂｌａｃｋ　Ｓ　００８４。
・ペリレンブラックＢ：ＢＡＳＦ社製の品名Ｌｕｍｏｇｅｎ　Ｂｌａｃｋ　ＦＫ　４２８０。
・カーボンブラック：三菱化学株式会社製の品名ＭＡ７。
・アントラキノン系赤色顔料Ａ：クラリアントジャパン株式会社製の品名ＨＯＳＴＡＰＥＲＭ　ＳＣＡＲＬＥＴ　ＧＯ（カラーインデックスは、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１６８）。
・アントラキノン系赤色顔料Ｂ：ＢＡＳＦ社製の品名Ｐａｌｉｏｇｅｎ　Ｒｅｄ　Ｌ　４０４５（カラーインデックス　Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７７）。
・アゾ系赤色顔料：大日精化株式会社製の品名セイカファースト　レッド　１５３１Ｂ。
・溶剤：ジエチレングリコールモノエチルエーテルアセテート。 Details of raw materials other than the carboxyl group-containing unsaturated resin solutions used in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 are as follows.
Epoxy resin: 1,3,5-triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, TEPIC-HP).
Epoxy resin solution: A solution obtained by dissolving cresol novolac type epoxy resin (manufactured by DIC Corporation, product name EPICLON N-695) in diethylene glycol monoethyl ether acetate at a solid content of 70%.
Photopolymerization initiator A: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, product name Irgacure 907).
Photopolymerization initiator B: 2,4-diethylthioxanthen-9-one (DETX).
Photopolymerization initiator C: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, product name Irgacure TPO manufactured by BASF.
Photopolymerization initiator D: 1-hydroxy-cyclohexyl-phenyl-ketone, product name Irgacure 184 manufactured by BASF.
Photopolymerizable monomer: dipentaerythritol hexaacrylate (DPHA).
Melamine: Fine melamine manufactured by Nissan Chemical Industries, Ltd.
Barium sulfate: Product name Variace B30 manufactured by Sakai Chemical Industry Co., Ltd.
・ Fine silica: Product name Leoroseal MT-10 manufactured by Tokuyama Corporation.
Antifoaming agent: Product name KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.
Perylene Black A: Product name Palogen Black S 0084 manufactured by BASF.
Perylene Black B: Product name Lumogen Black FK 4280 manufactured by BASF.
Carbon black: Product name MA7 manufactured by Mitsubishi Chemical Corporation.
Anthraquinone red pigment A: product name HOSTAPERSM SCARLET GO manufactured by Clariant Japan Ltd. (color index is Pigment Red 168).
Anthraquinone red pigment B: Product name Palogen Red L 4045 (Color Index Pigment Red 177) manufactured by BASF Corporation.
-Azo-based red pigment: Product name Seika First Red 1531B manufactured by Dainichi Seika Co., Ltd.
Solvent: diethylene glycol monoethyl ether acetate.
　（実施例１～５、比較例１～３）
　これらの成分を、表１に示す割合で混合することで、ソルダーレジスト組成物を調製した。 (Examples 1 to 5, Comparative Examples 1 to 3)
A solder resist composition was prepared by mixing these components at a ratio shown in Table 1.
　また、線幅／線間が０．２ｍｍ／０．３ｍｍ、厚みが３５μｍの銅の導体配線を備える配線基板を用意した。この配線基板の表面上に、ソルダーレジスト組成物をスクリーン印刷法で塗布することにより湿潤塗膜を形成した。この湿潤塗膜を８０℃で２０分間加熱することで予備乾燥し、厚みが２０μｍである乾燥塗膜を形成した。 Moreover, a wiring board provided with copper conductor wiring having a line width / line spacing of 0.2 mm / 0.3 mm and a thickness of 35 μm was prepared. A wet coating film was formed on the surface of the wiring board by applying the solder resist composition by screen printing. This wet coating film was pre-dried by heating at 80 ° C. for 20 minutes to form a dry coating film having a thickness of 20 μm.
　この乾燥塗膜に、幅２５μｍ、５０μｍ、７５μｍ、及び１００μｍのソルダーダムが形成されるようなマスクをあてがうと共に、照射エネルギー密度が４００ｍＪ／ｃｍ２の条件で紫外線を照射して、配線基板上の乾燥塗膜を選択的に露光した。 The dried coating film is applied with a mask on which solder dams having a width of 25 μm, 50 μm, 75 μm, and 100 μm are formed and irradiated with ultraviolet rays under a condition of an irradiation energy density of 400 mJ / cm 2 to dry the wiring substrate. The coating was selectively exposed.
　露光後の乾燥塗膜に炭酸ナトリウム水溶液で現像処理を施して、配線基板上の乾燥塗膜における、露光によって硬化した部分を残存させ、硬化しなかった部分を除去した。 The exposed dried coating film was developed with an aqueous sodium carbonate solution to leave a portion cured by exposure in the dried coating film on the wiring board, and an uncured portion was removed.
　続いて、配線基板上の残存した乾燥塗膜を、１５０℃で６０分間加熱することにより硬化させた。これにより、配線基板上に厚み４０μｍのソルダーダムを含むソルダーレジスト層を形成した。 Subsequently, the remaining dry coating film on the wiring board was cured by heating at 150 ° C. for 60 minutes. As a result, a solder resist layer including a solder dam having a thickness of 40 μm was formed on the wiring board.
　（色評価）
　実施例１～５、及び比較例１～３のソルダーレジスト層について、分光測色計（コニカミノルタセンシング株式会社製、型番ＣＭ－６００ｄ）を用いて、Ｌ＊ａ＊ｂ＊表色系におけるＬ＊値、ａ＊値、及びｂ＊値を測定し、下記のように判定した。
Ａ：Ｌ＊値が４０以下、ａ＊値が５．１～５５の範囲内、ｂ＊値が－１５～１５の範囲内である場合
Ｂ：Ｌ＊値、ａ＊値、及びｂ＊値のいずれか一つが、上記「Ａ」の範囲から外れる場合
Ｃ：Ｌ＊値、ａ＊値、及びｂ＊値のうち二つ以上が、上記「Ａ」の範囲から外れる場合。 (Color evaluation)
For the solder resist layers of Examples 1 to 5 and Comparative Examples 1 to 3, using a spectrocolorimeter (manufactured by Konica Minolta Sensing Co., Ltd., model number CM-600d), L in the L * a * b * color system The * value, a * value, and b * value were measured and judged as follows.
A: L * value is 40 or less, a * value is in the range of 5.1 to 55, and b * value is in the range of -15 to 15. B: L * value, a * value, and b * value When any one of the above is out of the range of “A” C: When two or more of the L * value, a * value, and b * value are out of the range of “A”.
　（剥離試験）
　実施例１～５、及び比較例１～３のソルダーダムに対して、セロハン粘着テープを貼り付けた後、これを剥離する剥離試験（テープテスト）を行った。この剥離試験の結果、残存したソルダーダムのうち、最も線幅の細いものの幅を測定し、下記のように判定した。
Ａ：最も細いソルダーダムの線幅が、２５μｍであるもの。
Ｂ：最も細いソルダーダムの線幅が、５０μｍであるもの。 (Peel test)
After the cellophane adhesive tape was applied to the solder dams of Examples 1 to 5 and Comparative Examples 1 to 3, a peel test (tape test) was performed to peel the cellophane adhesive tape. As a result of the peeling test, the width of the narrowest solder dam among the remaining solder dams was measured and determined as follows.
A: The line width of the thinnest solder dam is 25 μm.
B: The narrowest solder dam has a line width of 50 μm.
　これらの評価の結果を、下記の表１に示す。 The results of these evaluations are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１によると、黒色顔料としてペリレンブラックが使用されている実施例１～５では剥離試験が「Ａ」と評価されている。これに対して、ソルダーレジスト組成物中に黒色顔料としてカーボンブラックが含まれている比較例３では剥離試験が「Ｂ」と評価されている。これは、実施例１～５では、比較例３よりも、ソルダーレジスト層が深部まで十分に硬化されているためであると考えられる。 According to Table 1, in Examples 1 to 5 where perylene black is used as the black pigment, the peel test is evaluated as “A”. On the other hand, in Comparative Example 3 in which carbon black is contained as a black pigment in the solder resist composition, the peel test is evaluated as “B”. This is presumably because the solder resist layer in Examples 1 to 5 was sufficiently hardened to a deeper portion than in Comparative Example 3.
　表１によると、ソルダーレジスト組成物中にペリレン系黒色顔料、及び黒色以外の顔料が含まれている実施例１～５では、色評価が「Ａ」と判定されている。これに対して、ソルダーレジスト組成物中にペリレンブラックのみが含まれ、黒色以外の顔料が含まれていない比較例１では、色評価が「Ｂ」と判定され、ソルダーレジスト組成物中にアントラキノン系赤色顔料のみが含まれ、ペリレンブラックが含まれていない比較例２では、低露光領域における黒発色が「Ｃ」と判定されている。比較例１では黒色以外の顔料が含まれておらず、比較例２ではペリレンブラック等の黒色顔料が含まれていないため、比較例１、２のソルダーレジスト層は、所要のＬ＊値、ａ＊値、及びｂ＊値を満たすことができなかったと考えられる。 According to Table 1, in Examples 1 to 5 in which a perylene-based black pigment and a pigment other than black are contained in the solder resist composition, the color evaluation is determined as “A”. On the other hand, in Comparative Example 1 in which only the perylene black is contained in the solder resist composition and no pigment other than black is contained, the color evaluation is determined as “B”, and the anthraquinone type is contained in the solder resist composition. In Comparative Example 2 that contains only a red pigment and no perylene black, the black color development in the low-exposure region is determined as “C”. Since Comparative Example 1 does not contain a pigment other than black, and Comparative Example 2 does not contain a black pigment such as perylene black, the solder resist layers of Comparative Examples 1 and 2 have the required L * value, a * value, and b * is considered that the value could not be satisfied.
　［ソルダーレジスト層及び第二レジスト層を備えた被覆プリント配線板について］
　実施例６～１０及び比較例４～６で用いるカルボキシル基含有不飽和樹脂溶液を、次のようにして調製した。 [About a coated printed wiring board provided with a solder resist layer and a second resist layer]
The carboxyl group-containing unsaturated resin solutions used in Examples 6 to 10 and Comparative Examples 4 to 6 were prepared as follows.
　まず、還流冷却管、温度計、空気吹き込み管及び攪拌機が取り付けられている四つ口フラスコ内に、クレゾールノボラック型エポキシ樹脂（新日鉄住金化学株式会社製、品番ＹＤＣＮ－７００－５、エポキシ当量２０３）２０３質量部、ジエチレングリコールモノエチルエーテルアセテート１０３質量部、メチルハイドロキノン０．２質量部、アクリル酸７２質量部、及びトリフェニルホスフィン１．５質量部を入れることで、混合物を調製した。この混合物を加熱温度１１０℃、加熱時間１０時間の条件で加熱することで、付加反応を進行させた。続いて、混合物にテトラヒドロ無水フタル酸６０．８質量部、及びジエチレングリコールモノエチルエーテルアセテート７８．９質量部を加えてから、更に混合物を加熱温度８０℃、加熱時間３時間の条件で加熱した。これにより、カルボキシル基含有不飽和樹脂の濃度６５質量％溶液を得た。 First, a cresol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product number YDCN-700-5, epoxy equivalent 203) is placed in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube and a stirrer. A mixture was prepared by adding 203 parts by mass, 103 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 1.5 parts by mass of triphenylphosphine. This mixture was heated under the conditions of a heating temperature of 110 ° C. and a heating time of 10 hours, thereby allowing the addition reaction to proceed. Subsequently, 60.8 parts by mass of tetrahydrophthalic anhydride and 78.9 parts by mass of diethylene glycol monoethyl ether acetate were added to the mixture, and the mixture was further heated under the conditions of a heating temperature of 80 ° C. and a heating time of 3 hours. Thereby, a 65 mass% concentration solution of the carboxyl group-containing unsaturated resin was obtained.
　また、実施例６～１０及び比較例４～６で用いるカルボキシル基含有不飽和樹脂溶液以外の原料の詳細は、次の通りである。
・光重合性モノマー：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）。
・結晶性エポキシ化合物：１，３，５－トリグリシジルイソシアヌレート（日産化学工業社製、ＴＥＰＩＣ－ＨＰ）。
・光重合開始剤Ａ：２，４，６－トリメチルベンゾイルージフェニルーホスフィンオキサイド、ＢＡＳＦ社製の品名Ｉｒｇａｃｕｒｅ　ＴＰＯ。
・光重合開始剤Ｂ：１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、ＢＡＳＦ社製の品名Ｉｒｇａｃｕｒｅ　１８４。
・硫酸バリウム：堺化学工業株式会社製の品名バリエースＢ３０。
・微粉シリカ：株式会社トクヤマ製の品名レオロシールＭＴ－１０。
・メラミン：日産化学工業株式会社製の微粉メラミン。
・緑色着色剤：フタロシアニングリーン。
・消泡剤：信越化学工業株式会社製の品名ＫＳ－６６。
・溶剤：ジエチレングリコールモノエチルエーテルアセテート。 Details of raw materials other than the carboxyl group-containing unsaturated resin solutions used in Examples 6 to 10 and Comparative Examples 4 to 6 are as follows.
Photopolymerizable monomer: dipentaerythritol hexaacrylate (DPHA).
Crystalline epoxy compound: 1,3,5-triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, TEPIC-HP).
Photopolymerization initiator A: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, product name Irgacure TPO manufactured by BASF.
Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, product name Irgacure 184 manufactured by BASF.
Barium sulfate: Product name Variace B30 manufactured by Sakai Chemical Industry Co., Ltd.
・ Fine silica: Product name Leoroseal MT-10 manufactured by Tokuyama Corporation.
Melamine: Fine melamine manufactured by Nissan Chemical Industries, Ltd.
Green colorant: phthalocyanine green.
Antifoaming agent: Product name KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.
Solvent: diethylene glycol monoethyl ether acetate.
　（実施例６～１０、比較例４～６）
　これらの成分を下記の表２に示す割合で混合することにより、第二レジスト組成物を調整した。 (Examples 6 to 10, Comparative Examples 4 to 6)
The second resist composition was prepared by mixing these components in the proportions shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　また、線幅／線間が０．２ｍｍ／０．３ｍｍ、厚みが３５μｍの銅の導体配線を備える配線基板を用意した。この配線基板の表面上に、実施例１～５及び比較例１～３で用いたソルダーレジスト組成物をスクリーン印刷法で塗布することにより、第一塗膜を形成した。この第一塗膜を８０℃で２０分間加熱することで予備乾燥し、厚みが２０μｍであった。 Moreover, a wiring board provided with copper conductor wiring having a line width / line spacing of 0.2 mm / 0.3 mm and a thickness of 35 μm was prepared. On the surface of this wiring board, the first coating film was formed by applying the solder resist composition used in Examples 1 to 5 and Comparative Examples 1 to 3 by screen printing. This first coating film was pre-dried by heating at 80 ° C. for 20 minutes, and the thickness was 20 μm.
　この第一塗膜の上に、第二レジスト組成物をスクリーン印刷法により塗布することで、第一塗膜上に、第二塗膜を形成した。この第二塗膜を８０℃で、２０分間加熱することで予備乾燥した。乾燥後の第二塗膜の厚みは４０μｍであった。 The second coating film was formed on the first coating film by applying the second resist composition on the first coating film by a screen printing method. This second coating film was pre-dried by heating at 80 ° C. for 20 minutes. The thickness of the second coating film after drying was 40 μm.
　この第二塗膜に、幅２５μｍ、５０μｍ、７５μｍ、及び１００μｍのソルダーダムが形成されるようなマスクをあてがうと共に、このマスクを介して紫外線を照射して、第一塗膜及び第二塗膜を選択的に露光した。この紫外線の照射にあたり、第一の部分及び第二の部分を設定し、それぞれ照射エネルギー密度が異なる二種類の紫外線を照射した。第一の部分に照射した紫外線の照射エネルギー密度は６００ｍＪ／ｃｍ２であり、第二の部分に照射した紫外線の照射エネルギー密度は７０ｍＪ／ｃｍ２である。 The second coating film is applied with a mask on which solder dams having a width of 25 μm, 50 μm, 75 μm, and 100 μm are formed, and the first coating film and the second coating film are irradiated with ultraviolet rays through the mask. Selective exposure. In this ultraviolet irradiation, a first portion and a second portion were set, and two types of ultraviolet rays having different irradiation energy densities were irradiated. The irradiation energy density of the ultraviolet rays irradiated to the first portion is 600 mJ / cm 2 , and the irradiation energy density of the ultraviolet rays irradiated to the second portion is 70 mJ / cm 2 .
　露光後、炭酸ナトリウム水溶液で現像処理を施して、配線基板上の第一塗膜及び第二塗膜における、露光によって硬化した部分を残存させ、硬化しなかった部分を除去した。 After the exposure, development treatment was performed with an aqueous sodium carbonate solution to leave the portions cured by the exposure in the first coating film and the second coating film on the wiring board, and the uncured portions were removed.
　続いて、配線基板上に残存した第一塗膜及び第二塗膜を、１５０℃で６０分間加熱することにより硬化させた。これにより、ソルダーレジスト層及び第二レジスト層を形成した。ソルダーレジスト層及び第二レジスト層を合わせた厚みは、６０μｍであった。 Subsequently, the first coating film and the second coating film remaining on the wiring board were cured by heating at 150 ° C. for 60 minutes. Thereby, a solder resist layer and a second resist layer were formed. The total thickness of the solder resist layer and the second resist layer was 60 μm.
　第二レジスト層において、照射された紫外線の照射エネルギー密度が小さい第二の部分に対応する領域が低露光領域であり、照射された紫外線の照射エネルギー密度が大きい第一の部分に対応する領域が高露光領域であった。 In the second resist layer, a region corresponding to the second portion where the irradiation energy density of the irradiated ultraviolet light is small is a low exposure region, and a region corresponding to the first portion where the irradiation energy density of the irradiated ultraviolet light is large. It was a high exposure area.
　（剥離試験）
　実施例６～１０、及び比較例４～６のソルダーダムに対して、セロハン粘着テープを貼り付けた後、これを剥離する剥離試験（テープテスト）を行った。この剥離試験の結果、残存したソルダーダムのうち、最も線幅の細いもの（ダム残り）を測定して、下記のように判定した。
Ａ：最も細いソルダーダムの線幅が、５０μｍ以上であるもの。
Ｂ：ソルダーダムが全て剥離してしまったもの。 (Peel test)
After the cellophane adhesive tape was applied to the solder dams of Examples 6 to 10 and Comparative Examples 4 to 6, a peeling test (tape test) was performed to peel the cellophane adhesive tape. As a result of this peeling test, the remaining solder dam having the narrowest line width (dam remaining) was measured and determined as follows.
A: The line width of the thinnest solder dam is 50 μm or more.
B: All the solder dams have been peeled off.
　（低露光領域の発色評価について）
　実施例６～１０及び比較例４～６の第二レジスト層における低露光領域に対応する部分について、分光測色計（コニカミノルタセンシング株式会社製、型番ＣＭ－６００ｄ）を用いて、Ｌ＊ａ＊ｂ＊表色系におけるＬ＊値、ａ＊値、及びｂ＊値を測定し、下記のように判定した。
Ａ：Ｌ＊値が３２以下、ａ＊値が－１０～１０の範囲内、ｂ＊値が－５～５の範囲内である場合。
Ｂ：Ｌ＊値、ａ＊値、及びｂ＊値のいずれか一つが、上記「Ａ」の範囲から外れる場合
Ｃ：Ｌ＊値、ａ＊値、及びｂ＊値のうち二つ以上が、上記「Ａ」の範囲から外れる場合。 (About color evaluation in low exposure areas)
For the portions corresponding to the low exposure areas in the second resist layers of Examples 6 to 10 and Comparative Examples 4 to 6, using a spectrocolorimeter (manufactured by Konica Minolta Sensing Co., Ltd., model number CM-600d), L * a The L * value, a * value, and b * value in the * b * color system were measured and judged as follows.
A: When the L * value is 32 or less, the a * value is in the range of −10 to 10, and the b * value is in the range of −5 to 5.
B: L * value, a * value, and one of the b * value, when departing from the scope of the "A" C: L * value, a * value, and two or more of the b * values, When out of the range of “A”.
　（高露光領域の発色評価について）
　実施例６～１０、及び比較例４～６の第二レジスト層における高露光領域に対応する部分について、分光測色計（コニカミノルタセンシング株式会社製、型番ＣＭ－６００ｄ）を用いて、Ｌ＊ａ＊ｂ＊表色系におけるＬ＊値、ａ＊値、及びｂ＊値を測定し、下記のように判定した。
Ａ：Ｌ＊値が３５以上、ａ＊値が－１５以下、ｂ＊値が－５～５の範囲内である場合。
Ｂ：Ｌ＊値、ａ＊値、及びｂ＊値のいずれか一つが、上記「Ａ」の範囲から外れる場合
Ｃ：Ｌ＊値、ａ＊値、及びｂ＊値のうち二つ以上が、上記「Ａ」の範囲から外れる場合。 (About color evaluation in high exposure areas)
For the portions corresponding to the high exposure areas in the second resist layers of Examples 6 to 10 and Comparative Examples 4 to 6, using a spectrocolorimeter (manufactured by Konica Minolta Sensing Co., Ltd., model number CM-600d), L * The L * value, a * value, and b * value in the a * b * color system were measured and judged as follows.
A: When the L * value is 35 or more, the a * value is −15 or less, and the b * value is in the range of −5 to 5.
B: L * value, a * value, and one of the b * value, when departing from the scope of the "A" C: L * value, a * value, and two or more of the b * values, When out of the range of “A”.
　これらの評価の結果について、下記の表３に示す。 The results of these evaluations are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３によると、黒色顔料としてペリレンブラックが使用されている実施例６～１０では剥離試験が「Ａ」と評価されている。これに対して、ソルダーレジスト組成物中に黒色顔料としてカーボンブラックが含まれている比較例６では剥離試験が「Ｂ」と評価されている。 According to Table 3, in Examples 6 to 10 where perylene black is used as the black pigment, the peel test is evaluated as “A”. On the other hand, in Comparative Example 6 in which carbon black is included as a black pigment in the solder resist composition, the peel test is evaluated as “B”.
　これは、ソルダーレジスト層及び第二レジスト層を一回の露光によって形成した場合に、比較例６ではソルダーレジスト層の表層から深部まで十分に硬化することができていないためであると考えられる。 This is considered to be because, in the case of forming the solder resist layer and the second resist layer by one exposure, in Comparative Example 6, the solder resist layer was not sufficiently cured from the surface layer to the deep part.
　表３によると、ソルダーレジスト組成物中にペリレンブラックと黒色以外の顔料が含まれている実施例６～１０では、低露光領域における黒発色、及び高露光領域における緑発色が「Ａ」と評価されている。これに対して、ソルダーレジスト組成物中にペリレンブラックのみが含まれ、黒色以外の顔料が含まれていない比較例４では、低露光領域における黒発色が「Ｂ」と評価されている。また、ソルダーレジスト組成物中にアントラキノン系赤色顔料のみが含まれ、ペリレンブラックが含まれていない比較例５では、低露光領域における黒発色が「Ｃ」、高露光領域における緑発色が「Ｂ」と評価されている。 According to Table 3, in Examples 6 to 10 in which pigments other than perylene black and black are contained in the solder resist composition, the black color development in the low exposure region and the green color development in the high exposure region are evaluated as “A”. Has been. On the other hand, in the comparative example 4 in which only the perylene black is contained in the solder resist composition and no pigment other than black is contained, the black color development in the low exposure region is evaluated as “B”. Further, in Comparative Example 5 in which only the anthraquinone red pigment is contained in the solder resist composition and no perylene black is contained, the black color development in the low exposure region is “C”, and the green color development in the high exposure region is “B”. It is evaluated.
　これは、第二レジスト層の外観色は、高露光領域では緑色、低露光領域では緑色とソルダーレジスト層の表面の色との混合色になるが、比較例４ではソルダーレジスト組成物に黒色以外の着色剤が含まれておらず、比較例５ではソルダーレジスト組成物に黒色着色剤が含まれていないため、所要のＬ＊値、ａ＊値、及びｂ＊値を有する第一の領域及び第二の領域を含む第二レジスト層を形成することができていないためであると考えられる。 This is because the appearance color of the second resist layer is green in the high-exposure area, and mixed color of green and the surface color of the solder resist layer in the low-exposure area. In Comparative Example 4, the solder resist composition is other than black. In Comparative Example 5, since the solder resist composition does not contain a black colorant, the first region having the required L * value, a * value, and b * value This is probably because the second resist layer including the second region could not be formed.
　以上述べた実施形態から明らかなように、第一の態様に係るソルダーレジスト組成物は、カルボキシル基含有樹脂（Ａ）と、光重合性モノマー及び光重合性プレポリマーからなる群から選択される少なくとも一種を含有する光重合性化合物（Ｂ）と、光重合開始剤（Ｃ）と、熱硬化性成分（Ｄ）と、ペリレン系黒色着色剤（Ｅ１）と、黒色以外の一種の着色剤（Ｅ２）と、を含有し、前記ソルダーレジスト組成物を銅板上で光硬化させてから熱硬化させて、１８～２２μｍの範囲内のいずれかの厚みになる前記ソルダーレジスト組成物の皮膜が、Ｌ＊値が４０以下であり、ａ＊値が５．１～５５の範囲内であり、ｂ＊値が－１５～１５の範囲内であるような性質を有する。 As is clear from the embodiment described above, the solder resist composition according to the first aspect is at least selected from the group consisting of a carboxyl group-containing resin (A), a photopolymerizable monomer, and a photopolymerizable prepolymer. A photopolymerizable compound (B) containing one kind, a photopolymerization initiator (C), a thermosetting component (D), a perylene black colorant (E1), and a kind of colorant other than black (E2 And a film of the solder resist composition having a thickness within the range of 18 to 22 μm when the solder resist composition is photocured on a copper plate and then thermally cured . The properties are such that the value is 40 or less, the a * value is in the range of 5.1 to 55, and the b * value is in the range of −15 to 15.
　第二の態様に係るソルダーレジスト組成物は、第一の態様において、前記着色剤（Ｅ２）は赤色着色剤である。 In the solder resist composition according to the second aspect, in the first aspect, the colorant (E2) is a red colorant.
　第三の態様に係るソルダーレジスト組成物は、第一又は第二の態様において、前記着色剤（Ｅ２）はアントラキノン系赤色着色剤である。 In the solder resist composition according to the third aspect, the colorant (E2) is an anthraquinone red colorant in the first or second aspect.
　第四の態様に係るソルダーレジスト組成物は、第一から第三のいずれか一の態様において、前記熱硬化性成分（Ｄ）は環状エーテル骨格を有する化合物を含む。 In the solder resist composition according to the fourth aspect, in any one of the first to third aspects, the thermosetting component (D) includes a compound having a cyclic ether skeleton.
　第五の態様に係るソルダーレジスト組成物は、第一から第四のいずれか一の態様において、前記カルボキシル基含有樹脂（Ａ）は光重合性官能基を有するカルボキシル基含有樹脂（Ａ２）を含む。 In the solder resist composition according to the fifth aspect, in any one of the first to fourth aspects, the carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A2) having a photopolymerizable functional group. .
　第六の態様に係る被覆プリント配線板は、プリント配線板と、第一から第五のいずれか一の態様に係るソルダーレジスト組成物から形成され、前記プリント配線板を覆うソルダーレジスト層と、を含む。 A coated printed wiring board according to a sixth aspect includes a printed wiring board and a solder resist layer formed from the solder resist composition according to any one of the first to fifth aspects, and covering the printed wiring board. Including.
　第七の態様に係る被覆プリント配線板は、第六の態様において、前記ソルダーレジスト層を覆う第二レジスト層を含む。 The coated printed wiring board according to the seventh aspect includes a second resist layer covering the solder resist layer in the sixth aspect.
　第八の態様に係る被覆プリント配線板は、第七の態様において、前記第二レジスト層は、第一の領域と、前記第一の領域よりも高い光透過率を有する第二の領域を含む。 In the coated printed wiring board according to an eighth aspect, in the seventh aspect, the second resist layer includes a first region and a second region having a higher light transmittance than the first region. .
　第九の態様に係る被覆プリント配線板は、第八の態様において、前記第一の領域のＬ＊値が３５以上、ａ＊値が－１５以下、ｂ＊値が－５～５の範囲内であり、前記第二の領域のＬ＊値が３２以下、ａ＊値が－１０～１０の範囲内、ｂ＊値が－５～５の範囲内である。 The coated printed wiring board according to the ninth aspect is the eighth aspect, wherein the L * value of the first region is 35 or more, the a * value is −15 or less, and the b * value is within the range of −5 to 5. The second region has an L * value of 32 or less, an a * value in the range of −10 to 10, and a b * value in the range of −5 to 5.
　第十の態様に係る被覆プリント配線板は、第七から九のいずれかの一の態様において、前記第二レジスト層は緑色着色剤を含有する。 In the coated printed wiring board according to the tenth aspect, in any one of the seventh to ninth aspects, the second resist layer contains a green colorant.

Claims (10)

  1. 　ソルダーレジスト組成物であって、
    　カルボキシル基含有樹脂（Ａ）と、
    　光重合性モノマー及び光重合性プレポリマーからなる群から選択される少なくとも一種を含有する光重合性化合物（Ｂ）と、
    　光重合開始剤（Ｃ）と、
    　熱硬化性成分（Ｄ）と、
    　ペリレン系黒色着色剤（Ｅ１）と、
    　黒色以外の一種の着色剤（Ｅ２）と、
    　を含有し、
    前記ソルダーレジスト組成物を銅板上で光硬化させてから熱硬化させて、１８～２２μｍの範囲内のいずれかの厚みになる前記ソルダーレジスト組成物の皮膜が、Ｌ＊値が４０以下であり、ａ＊値が５．１～５５の範囲内であり、ｂ＊値が－１５～１５の範囲内であるような性質を有する。     A solder resist composition comprising:
    A carboxyl group-containing resin (A);
    A photopolymerizable compound (B) containing at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerizable prepolymer;
    A photopolymerization initiator (C);
    A thermosetting component (D);
    A perylene-based black colorant (E1);
    A kind of colorant (E2) other than black;
    Containing
    When the solder resist composition is photocured on a copper plate and then thermally cured, the solder resist composition film having any thickness within the range of 18 to 22 μm has an L * value of 40 or less, The a * value is in the range of 5.1 to 55, and the b * value is in the range of −15 to 15.
  2. 　前記着色剤（Ｅ２）は赤色着色剤である
    　請求項１に記載のソルダーレジスト組成物。     The solder resist composition according to claim 1, wherein the colorant (E2) is a red colorant.
  3. 　前記着色剤（Ｅ２）はアントラキノン系赤色着色剤である
    　請求項１又は２に記載のソルダーレジスト組成物。     The solder resist composition according to claim 1, wherein the colorant (E2) is an anthraquinone red colorant.
  4. 　前記熱硬化性成分（Ｄ）は環状エーテル骨格を有する化合物を含む
    　請求項１乃至３のいずれか一項に記載のソルダーレジスト組成物。     The soldering resist composition according to any one of claims 1 to 3, wherein the thermosetting component (D) includes a compound having a cyclic ether skeleton.
  5. 　前記カルボキシル基含有樹脂（Ａ）は光重合性官能基を有するカルボキシル基含有樹脂（Ａ２）を含む
    　請求項１乃至４のいずれか一項に記載のソルダーレジスト組成物。     The solder resist composition according to any one of claims 1 to 4, wherein the carboxyl group-containing resin (A) includes a carboxyl group-containing resin (A2) having a photopolymerizable functional group.
  6. 　プリント配線板と、
    　請求項１乃至５のいずれか一項に記載のソルダーレジスト組成物から形成され、前記プリント配線板を覆うソルダーレジスト層と、
    を含む
    　被覆プリント配線板。     A printed wiring board;
    A solder resist layer formed from the solder resist composition according to any one of claims 1 to 5, and covering the printed wiring board;
    Insulated printed wiring board.
  7. 　前記ソルダーレジスト層を覆う第二レジスト層を含む
    　請求項６に記載の被覆プリント配線板。     The coated printed wiring board according to claim 6, further comprising a second resist layer that covers the solder resist layer.
  8. 　前記第二レジスト層は、第一の領域と、前記第一の領域よりも高い光透過率を有する第二の領域を含む
    　請求項７に記載の被覆プリント配線板。     The coated printed wiring board according to claim 7, wherein the second resist layer includes a first region and a second region having a light transmittance higher than that of the first region.
  9. 　前記第一の領域のＬ＊値が３５以上、ａ＊値が－１５以下、ｂ＊値が－５～５の範囲内であり、
    　前記第二の領域のＬ＊値が３２以下、ａ＊値が－１０～１０の範囲内、ｂ＊値が－５～５の範囲内である
    　請求項８に記載の被覆プリント配線板。     The L * value of the first region is 35 or more, the a * value is −15 or less, and the b * value is in the range of −5 to 5,
    The coated printed wiring board according to claim 8, wherein the L * value of the second region is 32 or less, the a * value is in the range of -10 to 10, and the b * value is in the range of -5 to 5.
  10. 　前記第二レジスト層は緑色着色剤を含有する
    　請求項７乃至９のいずれか一項に記載の被覆プリント配線板。     The coated printed wiring board according to any one of claims 7 to 9, wherein the second resist layer contains a green colorant.
PCT/JP2016/000649 2015-02-10 2016-02-09 Solder resist composition, and coated printed wiring board WO2016129265A1 (en)

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KR1020177000382A KR101856579B1 (en) 2015-02-10 2016-02-09 Solder resist composition, and coated printed wiring board
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JP2015024355A JP6185943B2 (en) 2015-02-10 2015-02-10 Solder resist composition, coated printed wiring board
JP2015-024355 2015-02-10

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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
JP6986340B2 (en) * 2016-08-29 2021-12-22 株式会社タムラ製作所 Manufacturing method of printed wiring board and printed wiring board
JP7170420B2 (en) * 2017-06-27 2022-11-14 太陽インキ製造株式会社 Photosensitive film laminate and cured product thereof
WO2019058964A1 (en) * 2017-09-25 2019-03-28 富士フイルム株式会社 Curable composition, film, infrared transmitting filter, solid-state imaging element and optical sensor
WO2023233894A1 (en) * 2022-05-30 2023-12-07 コニカミノルタ株式会社 Actinic radiation-curable inkjet resist ink, method for forming cured film, cured film, printed wiring board, and electronic device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011039984A1 (en) * 2009-09-29 2011-04-07 太陽ホールディングス株式会社 Photosensitive resin composition, cured product thereof, and printed wiring board
JP2013050562A (en) * 2011-08-31 2013-03-14 Tamura Seisakusho Co Ltd Black curable resin composition
JP2014052430A (en) * 2012-09-05 2014-03-20 Tamura Seisakusho Co Ltd Black curable resin composition and printed wiring board using the same
JP2014130173A (en) * 2012-12-27 2014-07-10 Fujifilm Corp Color filter composition, infrared transmitting filter, manufacturing method therefor, and infrared sensor
JP2014202846A (en) * 2013-04-03 2014-10-27 株式会社カネカ Black photosensitive resin composition and application of the same
JP5643416B1 (en) * 2013-12-24 2014-12-17 互応化学工業株式会社 Manufacturing method of coated wiring board

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4994923B2 (en) * 2007-04-06 2012-08-08 太陽ホールディングス株式会社 Black solder resist composition and cured product thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011039984A1 (en) * 2009-09-29 2011-04-07 太陽ホールディングス株式会社 Photosensitive resin composition, cured product thereof, and printed wiring board
JP2013050562A (en) * 2011-08-31 2013-03-14 Tamura Seisakusho Co Ltd Black curable resin composition
JP2014052430A (en) * 2012-09-05 2014-03-20 Tamura Seisakusho Co Ltd Black curable resin composition and printed wiring board using the same
JP2014130173A (en) * 2012-12-27 2014-07-10 Fujifilm Corp Color filter composition, infrared transmitting filter, manufacturing method therefor, and infrared sensor
JP2014202846A (en) * 2013-04-03 2014-10-27 株式会社カネカ Black photosensitive resin composition and application of the same
JP5643416B1 (en) * 2013-12-24 2014-12-17 互応化学工業株式会社 Manufacturing method of coated wiring board

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JP6185943B2 (en) 2017-08-23
TWI596429B (en) 2017-08-21

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