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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
  • C08L101/08—Carboxyl groups
• • 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
  • G03F7/0041—Photosensitive materials providing an etching agent upon exposure
• • 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
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • 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
  • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• • 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
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B2038/0052—Other operations not otherwise provided for
  • B32B2038/0076—Curing, vulcanising, cross-linking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

• the present invention is, for example, a photocurable resin composition used as a solder resist of a printed wiring board, a dry film and a cured product obtained therefrom, and a cured film such as a solder resist formed by the dry film or the cured product.
• the present invention relates to a printed wiring board.
• the photocurable resin composition can be finely processed by applying the principle of a photographic method (photolithography). Furthermore, since a cured product having excellent physical properties can be obtained, it is used in electronic devices and printing plates.
• the photocurable resin composition includes a solvent development type and an alkali development type. In recent years, an alkali development type that can be developed with a dilute weak alkaline aqueous solution has become mainstream from the viewpoint of environmental measures.
• alkali-developable photocurable resin compositions are widely used in printed wiring board manufacture, liquid crystal display board manufacture, printing plate making, and the like. As a characteristic required for this, for example, when used as a solder resist in the production of a printed wiring board, the cured product is required to have heat resistance that can withstand processing under high temperature conditions such as soldering.
• a typical example of the conventional photocurable resin composition includes a photocurable resin composition using a carboxyl group-containing epoxy (meth) acrylate resin and a (meth) acrylate monomer together with a photopolymerization initiator.
• a photocurable resin composition using a carboxyl group-containing epoxy (meth) acrylate resin and a (meth) acrylate monomer together with a photopolymerization initiator.
• the present invention has been made in view of the above-described problems of the prior art, and halation and undercutting may occur even when exposed in a state where a film is applied to a dry coating film of a liquid type or a dry film type. It is an object of the present invention to provide a photocurable resin composition that can obtain high resolution and can suppress the occurrence of cracks during a cooling and heating cycle. Furthermore, the object of the present invention is to obtain a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable resin composition, and to cure a solder resist or the like with the dry film or the cured product. It is providing the printed wiring board by which a membrane
• a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof.
• the naphthalene derivative and / or naphthoquinone and its derivative are compounds having a hydroxyl group.
• the carboxyl group-containing resin preferably has a photosensitive group. By having the photosensitive group, the photocurability of the photocurable resin composition increases, and the sensitivity can be improved.
• the photopolymerization initiator is an oxime ester photopolymerization initiator represented by the following general formula (I), represented by the following general formula (II). And a mixture of one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators represented by the following general formula (III): Is preferred.
• R 1 represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more).
• a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R 2 is a phenyl group (substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom).
• an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 -8 cycloalkyl groups,
• R 3 and R 4 are each independently 1 to 12 carbon atoms
• R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded
• R 7 and R 8 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an al
• thermosetting component it is preferable to contain a thermosetting component further.
• a thermosetting component while providing heat resistance, the tensile elongation rate of a cured film can be increased and crack resistance can be improved.
• a coloring agent can be contained further. By containing a colorant, it can be suitably used as a solder resist.
• coating and drying the photocurable resin composition mentioned above on a film is provided.
• a resist layer can be easily formed without applying a photocurable resin composition on a substrate.
• the photocurable resin composition or dry film mentioned above can be used as hardened
• the printed wiring board which has the pattern of the hardened
• the printed wiring board it is possible to improve the heat cycle resistance.
• the photocurable resin composition of the present invention since it contains a naphthalene derivative and / or naphthoquinone and its derivative together with a carboxyl group-containing resin and a photopolymerization initiator, a film is applied to a dry coating film of a liquid type and a dry film type. Even when exposed in the affixed state, halation and undercut do not occur and high resolution can be obtained, and the cured product improves the thermal cycle resistance when used for a printed wiring board or the like. It becomes possible.
• the photocurable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board, and can provide a stable resolution and a thermal cycle resistance (TCT). Resistance) and PCT (pressure cooker test) resistance, and other cured films such as solder resists excellent in various properties can be formed, and a highly reliable printed wiring board can be provided.
• a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board
• the present inventors have found that the above-described object can be achieved by a photocurable resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof.
• the invention has been completed.
• a naphthalene derivative and / or naphthoquinone and its derivatives it is possible to obtain a stable and high resolution without undercut or halation, without generating the starting point of crack generation during a thermal cycle, and crack resistance. Can be improved.
• the photocurable resin composition of the present invention will be described in detail.
• carboxyl group-containing resin constituting the photocurable resin composition of the present invention various known carboxyl group-containing resins having a carboxyl group in the molecule are used for the purpose of imparting alkali developability. be able to.
• a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance.
• the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
• carboxyl group-containing resin examples include the following compounds (any of oligomers and polymers) are preferable.
• 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, polycarbonate polyols, and polyethers
• carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, 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 a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
• 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 a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
• one isocyanate group and one or more (meth) acryl groups in the molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate
• a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.
• a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
• a carboxyl group-containing polyester obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a bifunctional oxetane resin as described later, and adding a dibasic acid anhydride to the resulting primary hydroxyl group. resin.
• Reaction product obtained by reacting a compound obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid.
• a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride.
• a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (10) described above.
• (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
• carboxyl group-containing resins are not limited to those listed, and can be used singly or in combination.
• the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH / g.
• the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
• it exceeds 200 mgKOH / g dissolution of the exposed portion by the developer proceeds, so the line becomes thinner than necessary, and in some cases, dissolution and peeling occur with the developer without distinguishing between the exposed portion and the unexposed portion, It becomes difficult to draw a normal resist pattern. More preferably, it is in the range of 45 to 120 mg KOH / g.
• the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. If the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be inferior, the moisture resistance of the coating 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 the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is in the range of 5,000 to 100,000.
• the blending amount of such a carboxyl group-containing resin is preferably in the range of 20 to 60% by mass of the total composition.
• the blending amount is less than 20% by mass, the film strength is lowered.
• it is more than 60% by mass, the viscosity of the composition becomes high, and the applicability and the like deteriorate. More preferably, it is in the range of 30 to 50% by mass.
• photopolymerization initiator examples include an oxime ester photopolymerization initiator having a group represented by the following general formula (I), and an ⁇ -aminoacetophenone photopolymerization initiator having a group represented by the following general formula (II). Or / and by using one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (III), It is possible to obtain high resolution even in a resist having the same.
• R 1 represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more). Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl.
• R 2 is a phenyl group (substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom).
• an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 -8 cycloalkyl groups,
• R 3 and R 4 are each independently 1 to 12 carbon atoms
• R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded
• R 7 and R 8 Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an al
• the oxime ester photopolymerization initiator having a group represented by the general formula (I) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (IV),
• the compound represented by general formula (V) and the compound represented by the following general formula (VI) are mentioned.
• R 9 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 carbon atoms
• R 10 and R 12 each independently represents a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom may be substituted).
• an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain).
• a cycloalkyl group having 5 to 8 carbon atoms an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)
• R 11 Are a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which is substituted with one or more hydroxyl groups).
• Or may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 may be substituted with 6 alkyl groups or phenyl groups).
• R 13 , R 14 and R 19 each independently represents an alkyl group having 1 to 12 carbon atoms
• R 15 , R 16 , R 17 and R 18 each independently represents a hydrogen atom or a carbon atom.
• Expression 1 represents an alkyl group
• M represents O, S or NH
• x and y each independently represents an integer of 0 to 5).
• oxime ester photopolymerization initiators 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (IV) and a compound represented by the formula (V) are more preferable.
• Commercially available products include CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
• the ⁇ -aminoacetophenone photopolymerization initiator having a group represented by the general formula (II) includes 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, Irgacure 379, and Irgacure 389 manufactured by BASF Japan.
• Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.
• Examples of commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.
• the blending amount of such a photopolymerization initiator is preferably in the range of 0.01 to 30 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, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated.
• it exceeds 30 parts by mass light absorption on the coating film surface of the photopolymerization initiator becomes intense, and the deep curability tends to decrease. More preferably, it is in the range of 0.5 to 15 parts by mass.
• the blending amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 0.01 to 5 parts by mass.
• Photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones.
• a compound, a xanthone compound, a tertiary amine 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-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. It is done.
• an ethanolamine compound a compound having a dialkylaminobenzene structure
• 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.) Dialkylaminobenzophenones such as EAB); dialkylamino group-containing coumarin compounds such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin); Ethyl dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-di
• a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are preferable.
• the dialkylaminobenzophenone compound 4,4'-diethylaminobenzophenone is preferable because of its low toxicity.
• the dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is not colored because the maximum absorption wavelength is in the ultraviolet region, and uses not only a colorless and transparent photosensitive composition but also a colored pigment. A colored solder resist film reflecting the color can be provided.
• 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
• thioxanthone compounds and tertiary amine compounds are preferable.
• the composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
• a compounding quantity of a thioxanthone compound 20 mass parts or less are preferable with respect to 100 mass parts of carboxyl group-containing resin.
• the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis
• the compounding amount of the 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 amount of the tertiary amine compound 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 dried coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
• These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
• the total amount of such photopolymerization initiator, photoinitiator assistant, 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.
• N-phenylglycines phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, etc.
• chain transfer agents include mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof. These chain transfer agents can be used alone or in combination of two or more.
• the photo-curable resin composition of the present invention uses any naphthalene derivative and / or naphthoquinone and its derivatives, so that any exposure apparatus can be used for exposure in a state where a PET film is attached to a dry film of a liquid type and a dry film type. Even in the case of using halation, halation did not occur, and stable resolution was obtained regardless of the time for peeling the PET film.
• naphthalene derivatives and / or naphthoquinone and its derivatives are different from general polymerization inhibitors phenothiazine and hydroquinone, and have an effect of slowing the rate of photoreaction under oxygen evasion (that is, under oxygen evasion). This is considered to be because it acts as a polymerization inhibitor) and suppresses the speed of surface curing and cures uniformly in the thickness direction.
• naphthalene derivatives and / or naphthoquinone and derivatives thereof used in the present invention ammonium 1,4-dihydroxy-2-naphthalenesulfonate, 4-methoxy-1-naphthol and the like can be used as the naphthalene derivative.
• naphthoquinone and its derivatives 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, anthrone and the like can be used.
• naphthalene derivatives examples include Kinopower (registered trademark) WSI, Kinopower MNT (all manufactured by Kawasaki Chemical Industry Co., Ltd.), 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.
• naphthoquinone and its derivatives include, for example, Kinopower (registered trademark) NQI, Kinopower LSN, Kinopower ATR (all manufactured by Kawasaki Kasei Co., Ltd.), 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, anthrone (Both manufactured by Tokyo Chemical Industry Co., Ltd.).
• the blending amount of the naphthalene derivative and / or naphthoquinone and its derivative is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount of the naphthalene derivative and / or naphthoquinone and its derivative is less than 0.01 parts by mass, the resolution will not be stable, and halation and undercut will occur and high resolution will not be obtained. is there. On the other hand, when the amount exceeds 20 parts by mass, the coating properties such as electroless gold plating resistance deteriorate due to the decrease in photocurability. More preferably, it is in the range of 0.05 to 10 parts by mass.
• thermosetting component can be added to the photocurable resin composition of the present invention in order to impart heat resistance.
• thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins.
• the thermosetting resin can be used.
• Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.
• thermosetting component having a plurality of cyclic (thio) ether groups in the molecule has either one of the three-, four- or five-membered cyclic (thio) ether groups or a plurality of two types of groups in the molecule.
• Compound for example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule That is, an episulfide resin etc. are mentioned.
• Examples of the polyfunctional epoxy compound include jER (registered trademark) 828, jER834, jER1001, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron (registered trademark) 840, Epicron 850, Epicron 1050, and Epicron 2055 (all DIC Corporation).
• Epototo registered trademark
• YD-011, YD-013, YD-127, YD-128 all manufactured by Nippon Steel Chemical Co., Ltd.
• Bisphenol A type epoxy resin such as 664 (all manufactured by Asahi Kasei Kogyo Co., Ltd.); jERYL903 (manufactured by Mitsubishi Chemical), Epicron 152, Epicron 165 (all manufactured by DIC), Epototo YDB-400, YDB-500 (all new) Manufactured by Nippon Steel Chemical Co., Ltd.)
• E. R. 542 manufactured by Dow Chemical Company
• Araldite 8011 manufactured by BASF Japan
• Sumiepoxy ESB-400, ESB-700 both manufactured by Sumitomo Chemical Co., Ltd.
• Brominated epoxy resins such as 714 (both manufactured by Asahi Kasei Kogyo Co., Ltd.); jER152, jER154 (both manufactured by Mitsubishi Chemical Co., Ltd.); E. N. 431, D.D. E. N.
• Novolak type epoxy resins such as ECN-235 and ECN-299 (both manufactured by Asahi Kasei Kogyo Co., Ltd.); Epicron 830 (manufactured by DIC), jER807 (manufactured by Mitsubishi Chemical), Epototo YDF-170, YDF-175, YDF-2004 Bisphenol F epoxy resins such as Araldite XPY306 (manufactured by BASF Japan); Epototo ST-2004, ST-2007, ST-3000 (all manufactured by Nippon Steel Chemical Co., Ltd.), etc.
• Hydrogenated bisphenol A type epoxy resin jER604 (Mitsubishi Chemical Co., Ltd.), Epototo YH-434 (Nippon Steel Chemical Co., Ltd.), Araldite MY720 (BASF Japan Co., Ltd.), Sumiepoxy ELM-120 (Sumitomo Chemical Co., Ltd.) Glycidylamine type epoxy resin such as Araldite CY-350 Hydantoin type epoxy resins such as BASF Japan); Cycloside (registered trademark) 2021 (manufactured by Daicel Chemical Industries, Ltd.), Araldite CY175, CY179 (both manufactured by BASF Japan), and other cycloaliphatic epoxy resins; YL-933 ( Manufactured by Mitsubishi Chemical Corporation), T.M.
• E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN (registered trademark) -501 and EPPN-502 (all manufactured by Nippon Kayaku Co., Ltd.); YL-6056, YX-4000, YL-6121 (all manufactured by Mitsubishi Chemical Corporation) Bisylenol type or biphenol type epoxy resins such as bisphenol S type epoxy resins such as EBPS-200 (manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (manufactured by ADEKA), EXA-1514 (manufactured by DIC) Bisphenol A novolac type epoxy resin such as jER157S (Mitsubishi Chemical); tetraphenylolethane type epoxy resin such as jERYL-931 (Mitsubishi Chemical), Araldite 163 (BASF Japan); Araldite PT810 (BASF Japan) ), TEPIC (Nissan Chemical Industry) A heterocyclic epoxy resin such as Blemmer (registered
• CTBN modified epoxy resins e.g., manufactured by Nippon Steel Chemical Co., Ltd. of YR-102, YR-450, etc.
• These epoxy resins 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-ethyl-3- In addition to polyfunctional oxetanes such as 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-hydroxy
• Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin by the sulfur atom using the same synthesis method can also be used.
• the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin.
• the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are lowered.
• the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8 to 2.0 equivalents.
• thermosetting components include amino resins such as melamine derivatives and benzoguanamine derivatives.
• amino resins such as melamine derivatives and benzoguanamine derivatives.
• examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
• the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
• the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
• a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
• thermosetting components can be used alone or in combination of two or more.
• a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the photocurable resin composition of the present invention.
• Examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds.
• the blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces.
• polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
• aromatic polyisocyanate examples include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, Examples thereof include m-xylylene diisocyanate and 2,4-tolylene dimer.
• 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.
• adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.
• the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
• an isocyanate compound which can react with a blocking agent the above-mentioned polyisocyanate compound etc. are mentioned, for example.
• isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; 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, diacetone alcohol, lactic acid And alcohol blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl e
• the blocked isocyanate compound may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062.
• TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals), etc. Can be mentioned.
• Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
• a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly 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 blending amount is less than 1 part by mass, sufficient coating film toughness cannot be obtained.
• it exceeds 100 mass parts storage stability falls. More preferably, it is 2 to 70 parts by mass.
• thermosetting component 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-2-phenylimidazole.
• Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
• Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are trade names of bicyclic amidine compounds and salts thereof), etc. It is done.
• thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
• thermosetting catalysts is sufficient in the usual quantitative ratio.
• 100 parts by mass of the thermosetting component having a carboxyl group-containing resin or a plurality of cyclic (thio) ether groups in the molecule is 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.
• a colorant can be blended in the photocurable resin composition of the present invention.
• known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used.
• red colorants examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. (CI: The Society of Dyers and Colorists) number is given.
• 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 series Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
• Perylene series Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
• Diketopyrrolopyrrole series Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
• Condensed azo series Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
• Anthraquinone series Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
• Kinacridone series Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
• Blue colorants include phthalocyanine and anthraquinone, and pigments include Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15 : 6, Pigment Blue 16, Pigment Blue 60, and dye series Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 97 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, and the like can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• the green colorant there are phthalocyanine series, anthraquinone series, and perylene series.
• Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. may be used. it can.
• metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• yellow colorants examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
• Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
• Isoindolinone type Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
• Condensed azo series Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
• Benzimidazolone series Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
• 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.
• the blending ratio 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. When it exceeds 10 mass parts, deep part sclerosis
• the compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and an ethylenically unsaturated group-containing carboxyl group-containing resin is obtained. It helps insolubilize or insolubilize in dilute alkaline aqueous solution.
• glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like.
• Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols
• Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols
• an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
• the epoxy urethane acrylate compound etc. which made the half urethane compound react are mentioned.
• Such an epoxy acrylate resin can improve the photocurability without deteriorating the touch drying property of the coating film.
• 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 dilute alkaline aqueous solution falls, and a coating film becomes weak. More preferably, it is 1 to 70 parts by mass.
• the photo-curable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film.
• a filler known inorganic or organic fillers can be used.
• barium sulfate, spherical silica, hydrotalcite and talc are preferably used.
• metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
• the blending amount of the filler is preferably 75% by mass or less of the total amount of the composition.
• the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle. More preferably, the content is 0.1 to 60% by mass.
• the photocurable resin composition of the present invention 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.
• organic solvent 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 ether acetate, Esters such as propylene glycol butyl ether acetate; ethanol, propanol Ethylene glycol, or propylene glycol; octane, alipha
• the photo-curable resin composition of the present invention may further include a known thickener such as a known thermal polymerization inhibitor, fine silica, organic bentonite, and montmorillonite, a silicone-based, a fluorine-based, a polymer-based, etc., if necessary.
• a known thickener such as a known thermal polymerization inhibitor, fine silica, organic bentonite, and montmorillonite, a silicone-based, a fluorine-based, a polymer-based, etc., if necessary.
• Known additives such as antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.
• the thermal polymerization inhibitor can be used to prevent thermal polymerization or polymerization with time of the polymerizable compound.
• the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
• an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the formed resin insulation layer and the substrate.
• adhesion promoters include, for example, benzimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione.
• the photocurable resin composition of the present invention configured as described above is prepared to a predetermined composition, it is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a substrate, a dip coating method, a flow
• the coating method is a coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, or the like.
• the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C. to form a tack-free coating film (resin insulating layer).
• the volatile drying is performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a method having a heat source of an air heating method using steam in a countercurrent contact with hot air in the dryer) A method of spraying on a support).
• a resin insulating layer by forming a dry film with a photocurable resin composition and bonding this on a base material.
• the dry film has, for example, a structure in which a carrier film such as polyethylene terephthalate, a resin insulating layer such as a solder resist layer, and a peelable cover film used as necessary are laminated in this order.
• the resin insulation layer is a layer obtained by applying and drying a photocurable resin composition on a carrier film or a cover film.
• the photocurable resin composition of the present invention is uniformly applied to a carrier film with a thickness of 10 to 150 ⁇ m by a blade coater, a lip coater, a comma coater, a film coater, etc., and dried. Formed. And a dry film is formed by laminating
• the carrier film may be laminated after the photocurable resin composition is applied to the cover film and dried.
• the carrier film for example, a thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
• a cover film a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.
• paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy Made of materials such as copper clad laminates for high frequency circuits using fluorine, polyethylene, PPO, cyanate ester, etc., all grades (FR-4 etc.) copper clad laminates, other polyimide films, PET films, glass A substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.
• exposure is selectively performed with an active energy ray or directly with a laser direct exposure machine through a photomask having a pattern formed by a contact method (or non-contact method).
• a direct drawing device for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer
• an exposure device equipped with a metal halide lamp for example, an exposure machine mounted, an exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.
• the active energy ray it is preferable to use laser light having a wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photoinitiator. If a laser beam in this range is used, either a gas laser or a solid laser may be used.
• the exposure amount varies depending on the film thickness and the like, but can be generally in the range of 5 to 200 mJ / cm 2 , preferably 5 to 100 mJ / cm 2 , more preferably 5 to 50 mJ / cm 2 .
• the direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a wavelength of 350 to 410 nm.
• the exposed portion (the portion irradiated with the active energy ray) is cured, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution).
• a dilute alkaline aqueous solution for example, 0.3 to 3 wt% sodium carbonate aqueous solution.
• the developing method can be a dipping method, a shower method, a spray method, a brush method, or the like.
• an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.
• thermosetting component when added, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and, for example, a plurality of cyclic ether groups and / or cyclic groups in the molecule
• a thermosetting component having a thioether group reacts to form a cured product (pattern) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
• an electronic component in the cured product containing a carboxyl group-containing resin, a photopolymerization initiator, a naphthalene derivative and / or naphthoquinone and a derivative thereof, an electronic component It is possible to satisfy the resolution required when used for the above, and to obtain the reliability such as the resistance to the thermal cycle. And it becomes possible by using such hardened
• Examples 1 to 11 and Comparative Examples 1 to 3 The various components and ratios (parts by mass) shown in Table 1 were blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive resin composition for a solder resist. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by an Erichsen company.
• the solder resist pattern was exposed at an optimum exposure amount, and the PET film affixed after 10 minutes was peeled off. Thereafter, a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern.
• This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes.
• the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
• ⁇ Dry film type substrate production> The photosensitive resin compositions of the examples and comparative examples were each appropriately diluted with methyl ethyl ketone, and then applied to a PET film (FB-50: 16 ⁇ m manufactured by Toray Industries Inc.) using an applicator so that the film thickness after drying was 20 ⁇ m. It was applied and dried at 80 ° C. for 30 minutes to obtain a dry film.
• a PET film FB-50: 16 ⁇ m manufactured by Toray Industries Inc.
• the resulting dry film was vacuumed using a vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho), pressure: 0.8 MPa, 70 ° C., 1 minute, vacuum Degree: 133.3 Pa was laminated by heating to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.
• the solder resist pattern was exposed to this substrate with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off after 10 minutes. Thereafter, a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C.
• This substrate was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern.
• This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes.
• the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
• Example 1 and Comparative Example 1 were coated on the entire surface of a patterned copper foil substrate so that the film thickness after drying by screen printing was 20 ⁇ m, and a hot-air circulating drying oven at 80 ° C. For 30 minutes. Exposure is performed at 100 mJ / cm 2 using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the time for removing the PET film is 5 to 60 minutes. Thereafter, development is performed with a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C.
• the opening bottom having an opening design value of 80 ⁇ m is 60 ⁇ m or more and 80 ⁇ m or less, and there is no occurrence of undercut and halation.
• the bottom of the opening is 40 ⁇ m or more and less than 60 ⁇ m.
• ⁇ Electroless gold plating resistance> Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 ⁇ m and gold 0.03 ⁇ m, and the presence or absence of peeling of the resist layer or plating penetration by tape peel After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated. The judgment criteria are as follows. A: No soaking or peeling is observed. ⁇ : Slight penetration is confirmed after plating, but does not peel off after tape peeling. ⁇ : Slight penetration after plating and peeling after tape peel. X: There is peeling after plating.
• ⁇ TCT resistance> A photosensitive resin composition was applied to a substrate on which a 2 mm copper line pattern was formed, exposed and developed, and then thermally cured to produce an evaluation substrate in which a 3 mm square resist pattern was formed on the copper line. .
• This evaluation substrate was put into a thermal cycle machine in which a temperature cycle was performed between ⁇ 65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. And the external appearance at the time of 600 cycles, 800 cycles, and 1000 cycles was observed.
• ⁇ No abnormality at 800 cycles, cracks occurred at 1000 cycles.
• ⁇ No abnormality at 600 cycles, crack occurred at 800 cycles.
• X Cracks occurred at 600 cycles.
• PCT resistance> The evaluation substrate on which the solder resist cured coating film was formed was subjected to PCT (Pressure Cooker Test) for 168, 192 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation). ) And the state of the coating film after PCT was evaluated. Judgment criteria are as follows. A: No swelling, peeling, discoloration or elution from 192 hours. ⁇ : No swelling, peeling, discoloration, or elution from 168 hours. ⁇ : Some swelling, peeling, discoloration, and elution. X: Swelling, peeling, discoloration, and elution are often observed.
• Example 1 As shown in Table 2, in the case of Example 1 using a naphthalene derivative and / or naphthoquinone and its derivative, good resolution was obtained regardless of the time for peeling the PET film as compared with Comparative Example 1. It turns out that it is obtained.
• Example 2 In contrast to Example 1, in the case of Comparative Example 1 in which a naphthalene derivative and / or naphthoquinone and its derivative are not used and in Comparative Example 3 in which phenothiazine is used instead, TCT resistance is similarly inferior, and PCT resistance is inferior. Is marked with ⁇ , but the resolution was not stable, halation occurred, and peeling occurred in PCT after 168 hours.
• the photocurable resin composition of the present invention or its dry film can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

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