Classifications

• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
• • 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
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
  • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
  • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
• • 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
  • H05K3/285—Permanent coating compositions
  • H05K3/287—Photosensitive compositions

Definitions

• the present invention relates to a photocurable resin composition used as, for example, a solder resist for a printed wiring board.
• a solder resist composition that can exhibit high photopolymerization ability has been proposed.
• a photoresist in which acrylic acid is added to an epoxy group-containing polymer such as a copolymer of glycidyl methacrylate and methyl methacrylate, an acid anhydride is further added, and the resulting carboxyl group is reacted with 4-hydroxybutyl glycidyl acrylate.
• Ink is disclosed (see, for example, Patent Document 1).
• the side chain molecules are very long with respect to the main chain and further branched, there is a problem that the dry dryness of the dry coating film is extremely poor.
• solder resist composition using an oxime ester initiator as a photopolymerization initiator is disclosed (see, for example, Patent Documents 2 and 3). According to such a solder resist composition, good dryness to touch can be obtained. However, in an exposure method such as direct exposure, the sensitivity of the composition greatly affects the productivity, and thus further enhancement of ultrasensitivity is required.
• the components of the photopolymerization initiator may volatilize as outgas during exposure, and optical components in the exposure apparatus may be contaminated.
• post-curing is performed by thermal curing or UV exposure, and further, mounting by reflow is performed in a subsequent process.
• the components of the photopolymerization initiator are volatilized as outgas, cooled and solidified, which causes contamination of the work environment.
• the solder resist ink there is an increasing demand for the solder resist ink to be black in order to lower the surface contrast and make it difficult to see the conductor pattern on the printed wiring board (see, for example, Patent Document 5).
• the colorant (black) used in conventional solder resist inks has a light absorption range from the ultraviolet to the infrared range, and assuming that the pigment concentration is necessary to obtain the effect of making the conductor difficult to see, the solder resist is a coating film
• the ultraviolet rays necessary for the curing reaction do not transmit to the deep part of the film, and the resolution is poor. Further, when exposing it at a single wavelength such as laser exposure, the problem becomes more serious, and since a large amount of exposure is required, the time required for exposure becomes extremely long.
• JP 2004-264773 A (Claims) JP 2007-286138 A (Claims) JP 2007-281140 (Claims) Japanese Patent No. 4008273 JP 2005-108896 A
• the present invention is a good black color with high sensitivity, high resolution, excellent dryness to the touch of a dry coating film, and suppresses outgassing during curing and forms a solder resist for a printed wiring board, for example. It is an object of the present invention to provide a black photocurable resin composition capable of combining excellent alignment accuracy with high productivity and reliability.
• the present invention comprises a photopolymerization initiator having two oxime ester groups in the molecule, a colorant, a carboxyl group-containing resin, and a compound having a plurality of ethylenically unsaturated groups in the molecule.
• a black photocurable resin composition is provided. With such a structure, it is a good black color with high sensitivity, excellent resolution, and dry touch of the dry paint film. It suppresses outgassing during curing and forms a solder resist for printed wiring boards. In doing so, it is possible to suppress contamination and combine excellent alignment accuracy with high productivity and reliability.
• the photopolymerization initiator preferably has a carbazole structure.
• a carbazole structure By having a carbazole structure, radical generation (photocleavage) of the oxime ester group by light irradiation results in a large molecular weight of the remaining carbazole dimer, which reduces volatilization and can suppress outgassing. It becomes.
• the photopolymerization initiator is preferably an oxime ester compound represented by the following general formula (I). By using such an oxime ester compound, volatilization is further reduced and contamination by outgas can be suppressed.
• R 1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms)
• R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and an amino group, substituted with an alkylamino group having a C 1-8 alkyl group or a dialkylamino group), C1-C8 alkoxy group, halogen group, phenyl group, phenyl group (having C
• the photocurable resin composition of one embodiment of the present invention preferably further includes a thermosetting resin.
• a thermosetting component By containing a thermosetting component, the heat resistance can be further improved.
• the photocurable resin composition of 1 aspect of this invention can be apply
• the photocurable resin composition of one embodiment of the present invention is applied to a substrate and dried, or a dry film formed by applying the photocurable resin composition on a film is laminated on the substrate, and irradiated with active energy rays.
• photocuring a cured product having good characteristics can be obtained even with low energy irradiation. And it becomes possible to suppress the contamination by generation
• direct exposure or the like it is possible to provide a printed wiring board having excellent alignment accuracy and high productivity.
• the present invention has high sensitivity while having a good black color, excellent resolution, and dry touch of dried coatings, suppresses outgassing during curing, and forms, for example, a solder resist for printed wiring boards.
• a black photocurable resin composition that can suppress contamination and have both excellent alignment accuracy, high productivity, and reliability.
• the photocurable resin composition of this embodiment comprises a photopolymerization initiator having two oxime ester groups in the molecule, a colorant, a carboxyl group-containing resin, and a compound having a plurality of ethylenically unsaturated groups in the molecule. It is characterized by including.
• a highly sensitive photocurable resin composition can be obtained by using a photopolymerization initiator having two oxime ester groups in the molecule. Furthermore, when this is cured, it is possible to suppress the generation of outgas in a subsequent process (heating process) such as reflow.
• outgas generation is suppressed to some extent, but according to the photopolymerization initiator in the present embodiment, generation of outgas can be further suppressed.
• the photopolymerization initiator in the present embodiment has very high sensitivity, so that sensitivity equal to or higher than that can be obtained even with a small addition amount, and having two oxime ester groups in the molecule, ethylene This is considered to be because it is incorporated into the network as a crosslinking point when reacting with the polyunsaturated double bond.
• the photopolymerization initiator in this embodiment is a photocleavable molecule that reacts as a bifunctional functional group between molecules of a carboxyl group-containing resin having an ethylenically unsaturated group or a compound having an ethylenically unsaturated group. It functions as a crosslinkable photopolymerization initiator.
• This intermolecular crosslinking also has an effect on improving the resolution.
• a pigment with good blackness is blended to make the conductor pattern difficult to see, the ultraviolet ray transmission is reduced, and in particular, the photocuring reaction is difficult to occur in the deep part of the composition.
• a photopolymerization initiator having two oxime ester groups in the molecule by using a photopolymerization initiator having two oxime ester groups in the molecule, a cross-linked structure is created even in a portion with less ultraviolet light, and good resolution can be obtained.
• Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (I).
• R 1 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms)
• R 2 and R 3 are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an amino group, substituted with an alkylamino group having a C 1-8 alkyl group or a dialkylamino group), C1-C8 alkoxy group, halogen group, phenyl group, phenyl group (having C
• R 1 and R 2 are each a methyl group or an ethyl group
• R 3 is methyl or phenyl
• Ar is a bond, phenylene, naphthylene or thienylene
• n is 0 It is preferable that
• the blending amount of such a photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount is more than 5 parts by mass, light absorption is increased, the photoreactivity of the resist bottom is reduced, undercutting occurs, and the dryness to the touch is deteriorated. On the other hand, when it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. More preferably, it is 0.1 to 3 parts by mass.
• the carboxyl group-containing resin in the photocurable resin composition of the present embodiment is used for imparting alkali developability, and a known resin containing a carboxyl group in the molecule can be used.
• a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable.
• the unsaturated double bond is more preferably derived from acrylic acid or methacrylic acid or a derivative thereof. Specific examples are shown below.
• a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
• Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid and polycarbonate polyols, poly Carboxyl group-containing urethane by polyaddition reaction of diol compounds such as ether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups resin.
• diol compounds such as ether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups resin.
• Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
• a diol compound such as a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
• diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.
• a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and a polybasic acid is added to the remaining hydroxyl group.
• a carboxyl group-containing photosensitive resin obtained by reacting an anhydride.
• one epoxy group and one or more (meth) acryloyl groups are added in the molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate.
• a carboxyl group-containing photosensitive resin obtained by adding a compound having the same.
• Such a carboxyl group-containing resin can be used without being limited to these, and can be used by mixing one kind or plural kinds.
• (meth) acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
• the acid value of such a carboxyl group-containing resin is preferably 40 to 200 mgKOH / g.
• the acid value is less than 40 mgKOH / g, alkali development becomes difficult.
• the acid value exceeds 200 mgKOH / g, the exposed portion is dissolved by the developer, and the line becomes thinner than necessary. Dissolving and peeling with a developer without distinction between unexposed areas makes it difficult to draw a normal resist pattern. More preferably, it is 45 to 120 mg KOH / g.
• the weight average molecular weight of such a carboxyl group-containing resin is preferably 2,000 to 150,000, although it varies depending on the resin skeleton. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when it exceeds 150,000, the developability may be remarkably deteriorated, and the storage stability tends to deteriorate. More preferably, it is 5,000 to 100,000.
• the blending amount of such a carboxyl group-containing resin is preferably 20 to 80% by mass in the photocurable resin composition.
• the blending amount is less than 20% by mass, the film strength decreases.
• it is more than 80% by mass, the viscosity of the composition is increased, and the coating property and the like are lowered. More preferably, it is 30 to 60% by mass.
• the compound having a plurality of ethylenically unsaturated groups in the molecule is photocured by irradiation with active energy rays to insolubilize the carboxyl group-containing resin in an alkaline aqueous solution, or Used to help insolubilization.
• Examples of the compound having a plurality of ethylenically unsaturated groups in the molecule include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, Polyhydric alcohols such as dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate and ethylene oxide addition of these phenols Or polyvalent acrylates such as propylene oxide adducts; glycerin diglycidyl ether, glycerin triglycidyl Ether, trimethylolpropane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as t
• polyfunctional epoxy resins such as cresol novolac type epoxy resins and epoxy acrylate resins obtained by reacting acrylic acid, and hydroxyl groups of the epoxy acrylate resins, hydroxy acrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate And an epoxy urethane acrylate compound obtained by reacting a half urethane compound.
• an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
• the compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays.
• it exceeds 100 mass parts the solubility with respect to alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 1 to 70 parts by mass.
• a photopolymerization initiator other than the photopolymerization initiator having two oxime ester groups in the molecule can be used.
• a photopolymerization initiator having one oxime ester group in one molecule can be used.
• a photopolymerization initiator can be used.
• oxime ester photopolymerization initiators examples include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles NCI-831.
• oxime ester photopolymerization initiators can be used alone or in combination of two or more.
• the blending amount of such an oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the blending amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated.
• it exceeds 5 parts by mass the effect of reducing outgas cannot be obtained, and light absorption on the surface of the solder resist coating film becomes violent and the deep curability tends to decrease. More preferably, it is 0.1 to 3 parts by mass.
• ⁇ -aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like.
• Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.
• acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
• Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.
• the blending amount of these ⁇ -aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount is less than 0.01 parts by mass, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.
• photopolymerization initiators, photoinitiators and sensitizers that can be suitably used for the photocurable resin composition of the present embodiment include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, A benzophenone compound, a tertiary amine compound, a xanthone compound, etc. can be mentioned.
• benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
• acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
• anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
• thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
• ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
• benzophenone compound examples include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
• the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc.
• 4,4′-dimethylaminobenzophenone Non-dimethylaminobenzophenone
• Dialkylaminobenzophenones such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2
• Dialkylamino group-containing coumarin compounds ethyl 4-dimethylaminobenzoate (Kayacure EPA, Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, International Bio-Synthetics), 4-dimethylamino Nobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid ( Examples include Esolol 507) manufactured by VanDyk and 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).
• thioxanthone compounds and tertiary amine compounds are preferred.
• the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability.
• thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
• the blending amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.
• a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
• the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm and is in the ultraviolet region, so that it is less colored and a colored solder resist film reflecting the color of the colored pigment itself can be provided.
• 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
• the blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the blending amount is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
• the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
• the total amount of such photopolymerization initiator, photoinitiator glaze, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
• these photopolymerization initiators, photoinitiators, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber.
• these are not only used for the purpose of improving the sensitivity of the composition, but if necessary, absorb light of a specific wavelength to increase the photoreactivity of the surface, resist line shape and opening. Can be changed to vertical, tapered, or inversely tapered, and the processing accuracy of the line width and opening diameter can be improved.
• N phenylglycines phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as a chain transfer agent in order to improve sensitivity.
• chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercapto Chain transfer agents having a hydroxyl group such as butanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) Diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanthi Lumpur, cyclohex
• polyfunctional mercaptan compounds can be used. Specifically, for example, aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, and the like.
• Aromatic thiols such as xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercapto) Acetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis Mercaptoacetate), poly (mercaptoacetate) polyhydric alcohols such as dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane
• a heterocyclic compound having a mercapto group can be used.
• mercapto-4-butyrolactone also known as 2-mercapto-4-butanolide
• 2-mercapto-4-methyl-4-butyrolactone 2-mercapto-4-ethyl-4-butyrolactone
• 2-mercapto-4-butyrothiolactone 2-mercapto-4-butyrolactam
• N-methoxy-2-mercapto-4-butyrolactam N-ethoxy-2-mercapto -4-butyrolactam
• N-methyl-2-mercapto-4-butyrolactam N-ethyl-2-mercapto-4-butyrolactam
• N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam N- (2-Ethoxy) ethyl-2-mercapto-4-butyrolactam
• 2-mercapto-5 Valerolactone 2-mercapto-5-vale
• heterocyclic compounds having a mercapto group are preferred because they do not impair the developability of the photocurable resin composition.
• mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred.
• chain transfer agents can be used alone or in combination of two or more.
• the total amount of such chain transfer agents is preferably 5 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If the total amount exceeds 5 parts by mass, not only the sensitivity is not improved by adding more than necessary, but also these and the ethylenically unsaturated group react with each other, and the developability tends to be lowered.
• thermosetting resin can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance.
• a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin, etc., a plurality of cyclic ether groups and / or cyclic thioether groups hereinafter referred to as “cyclic (thio) ether groups”
• polyisocyanate Compounds compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule such as blocked isocyanate compounds, amine resins such as melamine resins and benzoguanamine resins and derivatives thereof, bismaleimide, oxazine, cyclocarbonate compounds, carbodiimide resins, etc.
• a well-known thermosetting resin is mentioned.
• thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule is either a 3,4, or 5-membered cyclic ether group or a cyclic thioether group, or two types of groups in the molecule.
• a compound having at least a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having at least a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, Examples thereof include compounds having a plurality of episulfide groups, that is, episulfide resins.
• polyfunctional epoxy compound examples include commercially available products such as jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Tohto Kasei Co., Ltd. manufactured by DIC. Epototo YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan Co., Ltd.
• A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd.
• glycidylamine type Poxy resin Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Japan; Celoxide 2021 manufactured by Daicel Chemical Industries, Araldide CY175 and CY179 manufactured by Ciba Japan (all are trade names) Alicyclic epoxy resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (both trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000YL-6121 (both trade names) Or bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd.
• Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Japan
• Celoxide 2021 manufactured by Daicel Chemical Industries Araldide CY175 and CY179 manufactured by Ciba Japan
• Alicyclic epoxy resin Y
• EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd. EXA-1514 manufactured by DIC Co., Ltd.
• Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Epoxy Resin; Tetraphenylolethane type such as jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan Co., Ltd. Epoxy resin; A heterocyclic epoxy resin such as Araldide PT810 manufactured by Japan Co., Ltd. or TEPIC manufactured by Nissan Chemical Industries Co., Ltd.
• Diglycidyl phthalate resin such as Bremer DGT (trade name) manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resins such as ZX-1063 (trade name); naphthyl group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by DIC
• An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC (both trade names); and glycidyl methacrylate such as CP-50S and CP-50M manufactured by NOF Corporation (both trade names) Polymerized epoxy resin; cyclohexylmaleimide and grease Copolymerized epoxy resin of gil methacrylate; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy
• polyfunctional epoxy compounds can be used alone or in combination of two or more.
• a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.
• polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyl)
• episulfide resin examples include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
• the blending amount of the thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule is 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. preferable.
• the blending amount is less than 0.6 equivalent, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are deteriorated.
• the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8 to 2.0 equivalents.
• a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
• the compound which has this, ie, a blocked isocyanate compound, etc. are mentioned.
• polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
• aromatic polyisocyanate examples include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and o-xylylene diene. Mention may be made of isocyanates, m-xylylene diisocyanate and 2,4- ⁇ -ylene dimers.
• aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
• alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
• the blocked isocyanate compound having a plurality of blocked isocyanate groups in one molecule an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
• the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with the blocking agent and temporarily deactivated, and such a blocked isocyanate group is heated to a predetermined temperature. Then, the blocking agent is dissociated and an isocyanate group is generated.
• isocyanate compound that can react with the isocyanate blocking agent examples include isocyanurate type, biuret type, and adduct type.
• isocyanurate type a compound that can react with the isocyanate blocking agent
• biuret type a compound that can react with the isocyanate blocking agent
• adduct type a compound that can react with the isocyanate blocking agent
• polyisocyanate compound described above is used.
• isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam and the like.
• Lactam blocking agents active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene Glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diace Alcohol blocking agents such as alcohol, methyl lactate and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl Mercaptan block agents such as mercaptan, thiophenol, methylthio
• the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS- 2117, Desmotherm 2170, Desmotherm 2265 (all from Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (both from Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B -846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals), and the like.
• Sumidules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. These compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used alone or in combination of two or more.
• the compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained.
• the amount exceeds 100 parts by mass, the storage stability decreases. More preferably, it is 2 to 70 parts by mass.
• thermosetting resins include amine resins such as melamine resins and benzoguanamine resins, and derivatives thereof. Specific examples include a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound.
• alkoxymethylated melamine compounds alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds and alkoxymethylated urea compounds obtained by converting these methylol groups to alkoxymethyl groups
• the kind of alkoxymethyl group is not particularly limited, and for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like can be used.
• a melamine derivative having a formalin concentration friendly to the human body and the environment is preferably 0.2% or less.
• thermosetting resins can be used alone or in combination of two or more.
• the compounding amount of such an amine resin and its derivative is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
• the blending amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, while when it exceeds 100 parts by mass, the storage stability is lowered. More preferably, it is 2 to 70 parts by mass.
• thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule
• thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl- Imidazole derivatives such as 2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy
• amine compounds such as —N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine
• hydrazine compounds such as adipic acid dihydrazide and sebacic acid di
• the present invention is not particularly limited thereto, and may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or a thermosetting catalyst that promotes a reaction between an epoxy group and / or an oxetanyl group and a carboxyl group. Two or more kinds can be used in combination.
• thermosetting catalysts is sufficient in the usual quantitative ratio, for example, 0 with respect to 100 parts by mass of the carboxyl group-containing resin or thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule. It is preferably 1 to 20 parts by mass. More preferably, it is 0.5 to 15 parts by mass.
• an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.
• an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.
• a binder polymer can be used in the photo-curable resin composition of the present embodiment for the purpose of improving touch drying properties and handling properties.
• binder polymer examples include polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, and phenoxy polymers. These binder polymers can be used alone or in combination of two or more.
• the photocurable resin composition of the present embodiment can use an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product.
• the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers.
• an elastomer or the like obtained by modifying a part or all of the epoxy groups of epoxy resins having various skeletons with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
• epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or in combination of two or more.
• the photocurable resin composition of the present embodiment is blended with a colorant so as to be black.
• a colorant black pigments, dyes and the like can be used.
• known colorants such as blue, green, yellow, and red can be mixed and used, and any of pigments, dyes, and pigments may be used.
• the color index (C.I .; issued by The Society of Dyers and Colorists) number as shown below can be given.
• Carbon black, graphite, iron oxide, copper oxide, anthraquinone, manganese, antimony oxide, nickel oxide, perylene, molybdenum sulfide, bismuth sulfide, etc. are used as the black colorant.
• phthalocyanine series As the blue colorant, phthalocyanine series, anthraquinone series and the like are used.
• pigment systems include Pigment Blue 15, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15.6, 16, 60, and the like.
• the dye system include Solvent Blue 35, 63, 67, 68, 70, 83 87, 94, 97, 122, and 136.
• metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• phthalocyanine series As the green colorant, phthalocyanine series, anthraquinone series, perylene series, and the like are similarly used. For example, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28 and the like. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like are used. Specific examples include the following. Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183. Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
• Condensed azo type Pigment Yellow 93, 94, 95, 128, 155, 166, 180.
• Benzimidazolone series Pigment Yellow 18, 120, 151, 154, 156, 175.
• Isoindolinone series Pigment Yellow 109, 110, 139, 179, 185.
• Anthraquinone series Pigment Yellow 24, 108, 147, 193, 199, 202, Solvent Yellow 163.
• a monoazo, disazo, monoazo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, or the like can be used. Specific examples include the following. Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269. Disazo: Pigment Red 37, 38, 41.
• Monoazo lakes Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.
• Benzimidazolone Pigment Red 171, 175, 176, 185, 208.
• Perylene series Pigment Red 123, 149, 166, 178, 179, 190, 194, 224, Solvent Red 135, 179.
• Diketopyrrolopyrrole type Pigment Red 254, 255, 264, 270, 272.
• Condensed azo series Pigment Red 144, 166, 214, 220, 221, 242.
• Anthraquinone series Pigment Red 168, 177, 216, Solvent Red 52, l49, 150, 207.
• Quinacridone series Pigment Red 122, 202, 206, 207, 209.
• colorants such as purple, orange, brown and white may be added for the purpose of adjusting the color tone.
• purple colorants for example, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36.
• orange coloring agents include Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 63, 64, 71, 73.
• brown colorant examples include Pigment Brown 23 and 25.
• Examples of the white colorant include zinc oxide shown in Pigment White 4, titanium oxide shown in Pigment White 6, and zinc sulfide shown in Pigment White 7. Particularly preferred in terms of coloring power and non-toxicity.
• Titanium oxide for example, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industrial Co., Ltd., R550, R580, R630, R820, CR50, CR60, CR90 manufactured by Ishihara Sangyo Co., Ltd.
• Rutile type titanium oxide such as KR270, KR310, KR380, TA-100, TA-200, TA-300, TA-500 manufactured by Fuji Titanium Industrial Co., Ltd. A100, A220 manufactured by Ishihara Sangyo Co., Ltd. KA-15, KA manufactured by Titanium Industrial Co., Ltd.
• Anatase type titanium oxide such as -20, KA-35, KA-90 and the like can be mentioned.
• the blending amount of such a colorant is not particularly limited, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin in order to obtain desired coloring without affecting the characteristics. . More preferably, it is 0.1 to 5 parts by mass.
• An antioxidant may be added to the photocurable resin composition of the embodiment to prevent oxidation.
• oxidative degradation occurs one after another in a chain, leading to functional degradation of the polymer material.
• Antioxidants such as peroxide decomposers that break down oxides into harmless substances and prevent the generation of new radicals are effective.
• the radical scavenger may be commercially available, specifically, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (all manufactured by Asahi Denka Co., Ltd., trade names), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 152, TINTINTIN (Both manufactured by Ciba Japan, trade names).
• antioxidant acting as a peroxide decomposer examples include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, and distearyl 3,3. And sulfur compounds such as' -thiodipropionate.
• the peroxide decomposing agent may be a commercially available one. Specifically, for example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Examples thereof include a Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., trade name). These antioxidants can be used alone or in combination of two or more.
• an ultraviolet absorber may be further added. Since polymeric materials absorb light, which causes decomposition and degradation, stabilization measures against ultraviolet rays are effective.
• the ultraviolet absorber examples include a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an anthranilate derivative, a dibenzoylmethane derivative, and a coumarin derivative.
• Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2′-dihydroxy-4. -Methoxybenzophenone and 2,4-dihydroxybenzophenone.
• benzoate derivative examples include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di- Examples include t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
• benzotriazole derivative examples include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5 Mention may be made of chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.
• triazine derivative examples include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
• Such ultraviolet absorbers may be commercially available, specifically, for example, TINUVINPS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400 TINUVIN 405, TINUVIN 460, TINUVIN 479 (all are trade names, manufactured by Ciba Japan).
• ultraviolet absorbers can be used alone or in combination of two or more, and by using in combination with an antioxidant, the cured product obtained from the photocurable resin composition of the present embodiment is stabilized. be able to.
• the photocurable resin composition of the present embodiment can be blended with a filler as necessary.
• a filler a known inorganic or organic filler can be used.
• barium sulfate, spherical silica, talc and the like are particularly preferably used.
• metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
• the amount of such filler is preferably 75% by mass or less of the total amount of the composition.
• the blending amount exceeds 75% by mass, the viscosity of the insulating composition is increased, and the coating and moldability are lowered, or the cured product is brittle. More preferably, the content is 0.1 to 60% by mass.
• the photocurable resin composition of the present embodiment may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary.
• a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc.
• Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics.
• the photo-curable resin composition of the present embodiment may further include a known thermal polymerization inhibitor, an antifoaming agent such as a silicone, fluorine, or polymer, a leveling agent, an imidazole, a thiazole, or a triazole, if necessary.
• Additives such as silane coupling agents and rust preventives can be blended.
• the thermal polymerization inhibitor can be used to prevent thermal polymerization or polymerization with time of the polymerizable compound.
• Specific examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, first chloride.
• the photocurable resin composition of the present embodiment may use an organic solvent for the synthesis of a carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. it can.
• organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
• ketones such as methyl ethyl ketone and cyclohexanone
• aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene
• cellosolve methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol
• propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl
• the photocurable resin composition of the present embodiment is prepared at a predetermined blending ratio, and is adjusted to have a viscosity suitable for the coating method using an organic solvent, for example, and then a dip coating method, a flow coating method, a roll coating method. It is applied onto a substrate by a method such as a bar coater method, a screen printing method, or a curtain coating method.
• Base materials include printed circuit boards and flexible printed circuit boards that have been formed in advance, paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide glass cloth / non-woven cloth-epoxy resin, glass Cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET film, A glass substrate, a ceramic substrate, a wafer plate, or the like can be used. Then, a tack-free dry coating film is formed by volatilizing and drying (preliminary drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C.
• the volatile drying is performed by using a method and a nozzle in which the hot air in the dryer is brought into countercurrent contact with a heat source of an air heating method using steam, such as a hot air circulation drying furnace, an IR furnace, a hot plate, and a convection oven. It can carry out using the method of spraying on a support body. Then, an active energy ray is selectively irradiated on the coating film by direct exposure, divided projection exposure, or the like, and the exposed portion is photocured.
• a heat source of an air heating method using steam such as a hot air circulation drying furnace, an IR furnace, a hot plate, and a convection oven.
• an ultraviolet lamp such as a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) or an (ultra) high pressure mercury lamp is used.
• the direct drawing apparatus can be used.
• a direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used.
• an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, and the like can be used.
• the active energy ray may have a peak wavelength in the range of 300 to 450 nm where the photocurable resin composition of the present embodiment has sufficient light absorption ability.
• a medium such as a gas laser or a solid laser is not particularly limited as long as it oscillates laser light having a wavelength in this range.
• the exposure amount varies depending on the film thickness and the like, in the photocurable resin composition of the present embodiment, particularly high sensitivity can be obtained, and therefore generally 5 to 200 mJ / cm 2 , preferably 5 to 100 mJ / It can be in the range of cm 2 .
• the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern.
• a developing method a dipping method, a shower method, a spray method, a brush method, or the like can be used.
• dilute alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.
• an aqueous sodium carbonate solution of 0.3 to 3% by mass can be used.
• thermosetting the carboxyl group of the carboxyl group-containing resin reacts with a thermosetting component such as a thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule, heat resistance, chemical resistance, moisture absorption resistance, It becomes possible to improve adhesiveness, electrical characteristics, and the like.
• the photocurable resin composition of the present embodiment is not directly applied onto a substrate as described above, for example, a dried coating film previously applied on a film and dried is wound up as a film, as a dry film It may be laminated on a substrate.
• the dry film has a structure in which, for example, a carrier film, a solder resist layer (photocurable resin composition layer), and a peelable cover film used as necessary are laminated in this order. .
• a carrier film a solder resist layer (photocurable resin composition layer)
• a peelable cover film used as necessary are laminated in this order.
• a dry film is obtained.
• a thermoplastic film such as polyethylene terephthalate or polyester film having a thickness of 2 to 150 ⁇ m is used as the carrier film.
• the solder resist layer is formed by uniformly applying a photocurable resin composition to a carrier film or a cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc., and then drying.
• a cover film a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the adhesive force with the solder resist layer is smaller than that of the carrier film.
• a protective film permanent protective film
• the cover film is peeled off, the solder resist layer and the printed circuit board are overlaid, and further laminated by using a laminator or the like, thereby forming a solder resist layer on the printed wiring board.
• a protective film (permanent protective film) is formed by performing exposure, development and heat curing on the solder resist layer.
• the carrier film may be peeled off either before exposure or after exposure.
• the resin solution (B-1) thus obtained had a weight average molecular weight (Mw) of 15,000, a solid content of 57%, and a solid acid value of 79.8 mgKOH / g.
• the weight average molecular weight of the obtained resin was a high-speed liquid consisting of three pumps LC-6AD manufactured by Shimadzu Corporation and three columns ShodeX (registered trademark) KF-804, KF-803, and KF-802 manufactured by Showa Denko K.K. Measured by chromatography.
• the resin solution (B-2) thus obtained had a solid content of 65% and an acid value of the solid content of 91 mgKOH / g.
• Non-volatile content was adjusted to 50% using carbitol acetate to obtain a photosensitive carboxyl group-containing resin solution (B-3).
• the resin solution (B-3) thus obtained had a solid content of 50% and an acid value of the solid content of 47 mgKOH / g.
• resin solution B-8 a commercially available product ZCR-1601H (manufactured by Nippon Kayaku Co., Ltd., oxalic acid value: 96 mgKOH / g, solid content: 65%) was used as it was.
• composition examples 1 to 14 were designated as examples 1 to 14, and composition examples 15 to 17 were designated as comparative examples 1 to 3, and the following evaluations were performed.
• dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer made from Eriksen, it was each 15 micrometers or less.
• composition of each of the above Examples and Comparative Examples is applied to the entire surface of a patterned copper foil substrate having a circuit thickness of 35 ⁇ m by screen printing and allowed to cool to room temperature.
• This substrate can be used for exposure equipment equipped with metal halide lamps (exposure machine with metal halide lamps, manufactured by Oak Manufacturing Co., Ltd.), exposure equipment mounted with high-pressure mercury lamps (exposure machines with mercury short arc lamps), direct exposure equipment for high-pressure mercury lamps (extra-high-pressure mercury lamps) Lamp-mounted direct exposure machine Marlex from Dainippon Screen Co., Ltd.) and direct lithography system (405 nm laser exposure system, manufactured by Hitachi Via Mechanics) are used to expose the solder resist pattern with an optimal exposure machine, and 1% sodium carbonate at 30 ° C.
• the aqueous solution was developed for 60 seconds under the condition of a spray pressure of 2 kg / cm 2 to obtain a line pattern.
• the exposure pattern is a line pattern with a width of 100, 90, 80, 70, 60, 50, 40, 30 ⁇ m and a length of 1 mm.
• the line is evaluated by the width of the remaining line in the exposed portion, no line remains.
• compositions of the above Examples and Comparative Examples are applied to the entire surface of the copper foil substrate by screen printing and allowed to cool to room temperature.
• This substrate is exposed to a solder resist pattern with an optimum exposure machine using an exposure apparatus equipped with a high-pressure mercury lamp (exposure machine manufactured by Oak Manufacturing Co., Ltd.), and a 1% sodium carbonate aqueous solution at 30 ° C. is sprayed to 0.2 MPa.
• Development was performed for 60 seconds under the conditions described above to obtain a resist pattern.
• This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm 2 and then cured by heating at 150 ° C. for 60 minutes.
• the value of the L * a * b * color system of the cured coating film on copper was measured according to JIS Z 8729 using a color difference meter, and the L * value, which is an index representing lightness, was evaluated as an index of blackness. A smaller L * value means better blackness.
• As the colorimeter a 45 ° ring illumination vertical light receiving high-performance colorimeter (CR-221 manufactured by Konica Minolta) was used.
• ⁇ Maximum development live> The photocurable resin composition of each example and comparative example was applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., and the substrate was taken out every 10 minutes from 20 minutes to 80 minutes. And allowed to cool to room temperature. After cooling, the substrate is developed for 60 seconds under the conditions of temperature: 30 ° C., spray pressure: 0.2 MPa, developer: 1% aqueous sodium carbonate solution, and the maximum allowable drying time in which no residue remains is defined as the maximum development life. did.
• ⁇ Electroless gold plating resistance> Using commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under the conditions of nickel 0.5 ⁇ m and gold 0.03 ⁇ m, and the presence or absence of penetration of the plating was evaluated. The presence or absence of peeling was evaluated. The judgment criteria are as follows. ⁇ : No soaking or peeling is observed ⁇ : Slight soaking is confirmed after plating, but no peeling after tape peeling ⁇ : Slight soaking is seen after plating, peeling is also seen after tape peeling ⁇ : After plating There is peeling There is peeling
• a comb-type electrode B coupon of IPCB-25 was used for the copper foil substrate.
• a bias voltage of DC 10 V was applied to this comb-shaped electrode, and 85 ° C., 85% R.D. H.
• the presence or absence of migration after 1,000 hours was confirmed in the constant temperature and humidity chamber.
• the judgment criteria are as follows. A: No change is observed. O: Very slight change. ⁇ : Discoloration is observed. X: Migration occurs. Table 2 shows the evaluation results.
• composition examples 1, 2, 15, and 16 in Table 1 were each diluted with methyl ethyl ketone, applied onto a PET film, and dried at 80 ° C. for 30 minutes to form a resin composition layer having a thickness of 20 ⁇ m. Further, a cover film was laminated thereon to produce a dry film.
• Composition Examples 1 and 2 were designated as Examples 15 and 16, and Composition Examples 15 and 16 were designated as Comparative Examples 4 and 5, respectively. Then, the cover film was peeled off, the film was thermally laminated on the patterned copper foil substrate, and the resin composition layer was adhered to the copper foil substrate.
• the substrate thus obtained was exposed in the same manner as the substrate formed by applying the photocurable resin composition.
• a high-pressure mercury lamp-mounted exposure device (mercury short arc lamp mounted exposure machine manufactured by Oak Manufacturing Co., Ltd.) and a direct drawing apparatus (405 nm laser exposure apparatus manufactured by Hitachi Via Mechanics) were used.
• the substrate was developed for 60 seconds under the conditions of temperature: 30 ° C., spray pressure: 0.2 MPa, developer: 1% aqueous sodium carbonate solution to obtain a resist pattern. Furthermore, after heat-curing for 60 minutes with a 150 degreeC hot-air dryer, the ultraviolet irradiation was similarly performed and the test board
• the photocurable resin composition of the present embodiment As described above, by using the photocurable resin composition of the present embodiment and the dry film thereof, it is possible to perform high-sensitivity, short-time exposure and good solder heat resistance without degrading developability. It can be seen that reliability, such as reliability, electroless gold plating resistance, and electrical insulation characteristics, can be obtained. And by using such a photocurable resin composition, it becomes possible to obtain high productivity even when using an exposure apparatus having high alignment accuracy such as direct exposure.
• Example 17 and Comparative Examples 6 and 7 were designated as Example 17 and Comparative Examples 6 and 7, and applied to a glass substrate by screen printing, and then heated at 80 ° C. using a hot air circulating drying oven. After drying for 30 minutes, exposure was carried out at an appropriate exposure amount using a high pressure mercury lamp exposure apparatus manufactured by Oak Manufacturing Co., Ltd. And about the one part, the coating film was shaved out as it was, and it was set as the sample before thermosetting, after hardening the remainder for 60 minutes at 150 degreeC, the coating film was shaved off and it was set as the sample after thermosetting. 1 mg of each sample was heated in a purge and trap, the sample before thermosetting for 5 minutes at 150 ° C.
• the photocurable resin composition of this embodiment while having high sensitivity, it can be seen that the amount of volatile components (outgas) derived from the photopolymerization initiator can be suppressed in both the pre-thermosetting sample and the post-thermosetting sample. Accordingly, it is possible to suppress contamination during exposure by direct exposure or the like or during mounting by reflow in a later process.

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• 2011
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