WO2011096206A1 - 光硬化性樹脂組成物、ドライフィルム、硬化物及びプリント配線板 - Google Patents
光硬化性樹脂組成物、ドライフィルム、硬化物及びプリント配線板 Download PDFInfo
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- WO2011096206A1 WO2011096206A1 PCT/JP2011/000568 JP2011000568W WO2011096206A1 WO 2011096206 A1 WO2011096206 A1 WO 2011096206A1 JP 2011000568 W JP2011000568 W JP 2011000568W WO 2011096206 A1 WO2011096206 A1 WO 2011096206A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- 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 for, for example, a solder resist, a dry film, a cured product thereof, and a printed wiring board using the cured product.
- alkali development type photo solder resists using an aqueous alkali solution as a developing solution are mainly used.
- an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used.
- Patent Document 1 discloses a solder resist composition
- a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. It has been reported.
- (meth) acrylic acid is added to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin, and a polybasic carboxylic acid or
- a solder resist composition comprising a photosensitive resin obtained by reacting the anhydride, a photopolymerization initiator, an organic solvent and the like is disclosed.
- the current alkali development type photo solder resist is not sufficient in terms of durability, such as alkali resistance, water resistance and heat resistance, as compared with conventional thermosetting type and solvent development type.
- the alkali-developable photo solder resist is mainly composed of a hydrophilic group in order to enable alkali development, and chemicals, water, water vapor, etc. are easy to permeate. This is considered to decrease the adhesiveness and adhesion between the resist film and copper.
- CTE coefficient of linear expansion
- the present invention has been made in view of such problems of the prior art, and can form a cured product that can be alkali-developed, has excellent resolution, and has excellent (wet) heat resistance and thermal shock resistance.
- the present invention provides a photocurable resin composition, a dry film, a cured product thereof, and a printed wiring board using the cured product.
- the photocurable resin composition of one embodiment of the present invention is characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, and Neuburg silica particles. With such a configuration, it is possible to form a cured product that can be alkali-developed and has excellent resolution, and is excellent in (wet) heat resistance and thermal shock resistance.
- the Neuburg silica particles are preferably subjected to a surface treatment.
- the surface treatment By performing the surface treatment, the wettability with the resin can be improved.
- the photocurable resin composition of one embodiment of the present invention preferably further contains a silane coupling agent.
- a silane coupling agent By containing a silane coupling agent, it becomes possible to improve wettability with resin.
- the dry film of one embodiment of the present invention is characterized by including a dry coating film obtained by applying and drying the photocurable resin composition having the above-described configuration on a film. With such a configuration, it is possible to form a cured product that can be alkali-developed and has excellent resolution, and is excellent in (wet) heat resistance and thermal shock resistance.
- the cured product of one embodiment of the present invention is the active energy ray after the photocurable resin composition having the above-described configuration is applied on the base material or the dry film having the above-described configuration is attached onto the base material. It is obtained by curing by irradiation. With such a configuration, it is possible to obtain heat resistance (wet) and heat shock resistance.
- the printed wiring board of one embodiment of the present invention is characterized by including such a cured product.
- it has heat resistance (wet) and heat shock resistance, and it is possible to suppress deterioration and modification due to thermal history.
- a photocurable resin composition capable of forming a cured product that is alkali developable and has excellent resolution, and is excellent in (wet) heat resistance and thermal shock resistance, It becomes possible to obtain a dry film, these hardened
- the photocurable resin composition of one embodiment of the present invention is characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, and Neuburg silica particles.
- the carboxyl group-containing resin a known resin containing a carboxyl group can be used. Among these, it is desirable to use a carboxyl group-containing resin that does not use an epoxy resin as a starting material. Such a carboxyl group-containing resin has a very low halide ion content, and can suppress deterioration of insulation reliability.
- 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.
- (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain.
- 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 the resulting hydroxyl group is dibasic acid anhydride.
- a carboxyl group-containing photosensitive resin to which a product is added.
- An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like.
- Polybasic such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the reaction product obtained by reacting with a saturated carboxylic acid containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting an acid anhydride.
- a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid.
- Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
- 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 an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- a carboxyl group-containing urethane resin by a polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate
- a carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.
- a carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups and then terminally (meth) acrylating.
- 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.
- an unsaturated carboxylic acid such as (meth) acrylic acid
- an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- a carboxyl group formed by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate to the polyester resin Contains photosensitive resin.
- (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
- carboxyl group-containing resins as described above, a carboxyl group-containing resin that does not use an epoxy resin as a starting material can be suitably used. Therefore, among the specific examples of the carboxyl group-containing resin described above, (4) to (8) can be particularly preferably used.
- the amount of chlorine ion impurities can be suppressed to a very low value, for example, 100 ppm or less.
- the chloride ion content of the carboxyl group-containing resin suitably used in this embodiment is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.
- a resin containing no hydroxyl group can be easily obtained.
- the presence of hydroxyl groups has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance.
- the moisture resistance is improved. It becomes possible.
- a carboxyl group-containing resin not containing hydroxyl groups can obtain excellent PCT resistance when treated or added with Neuburg silica particles and a silane coupling agent. .
- the silanol groups of the silane coupling agent react with the hydroxyl groups of the resin, not the filler surface, and do not act effectively on the bond between the filler and the resin.
- a carboxyl group-containing resin containing no hydroxyl group is stable with respect to the silane coupling agent and is effective from the viewpoint of storage stability.
- a phenol resin obtained by alkyl oxide-modifying a phenol novolac resin containing no chloride ion impurities is partially acrylated, and an acid anhydride is introduced, thereby providing double bond equivalents of 300 to 550, an acid value of 40 In the range of ⁇ 120 mg KOH / g, it is possible to obtain a resin that theoretically has no hydroxyl group.
- the phenol novolak resin which does not contain a chlorine ion impurity can be obtained easily.
- a carboxyl group-containing urethane resin synthesized from an isocyanate compound not using phosgene as a starting material and a raw material not using epihalohydrin and having a chlorine ion impurity amount of 0 to 30 ppm is also preferably used.
- a resin containing no hydroxyl group can be easily synthesized by combining the equivalents of the hydroxyl group and the isocyanate group.
- an epoxy acrylate-modified raw material can be used as a diol compound in the synthesis of a urethane resin.
- chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.
- the above-mentioned carboxyl group-containing resins (4) to (8) can be used more suitably.
- the carboxyl group-containing resin (9) is obtained by reacting glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or copolymerizing glycidyl methacrylate as an unsaturated group-containing compound.
- glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule
- copolymerizing glycidyl methacrylate as an unsaturated group-containing compound.
- Such a carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer, and thus can be developed with an alkaline aqueous solution.
- the acid value of such a carboxyl group-containing resin is preferably 40 to 150 mgKOH / g.
- the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
- it exceeds 150 mgKOH / g dissolution of the exposed portion by the developer proceeds, so that 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 0 to 130 mgKOH / g.
- the weight average molecular weight of such a 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 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 the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is 5,000 to 100,000.
- the blending amount of such a carboxyl group-containing resin is preferably 20 to 60% by mass in the entire composition. When it is less than 20% by mass, the coating film strength is lowered. On the other hand, when it is more than 60% by mass, the viscosity becomes high, and the coating property and the like are lowered. More preferably, it is 30 to 50% by mass.
- an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator can be used. Of these, it is preferable to use at least one of them.
- oxime ester photopolymerization initiators commercially available products include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, Adeka Arcles (registered trademark), manufactured by Ciba Specialty Chemicals. ) NCI-831 and the like.
- numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
- X is 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 alkoxy group having 1 to 8 carbon atoms).
- Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group.
- X and Y are each a methyl group or an ethyl group
- Z is methyl or phenyl
- n is 0, and Ar is preferably phenylene, naphthylene, thiophene or thienylene.
- the blending amount of such 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 of such 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.
- 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.
- it exceeds 5 parts by mass light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.
- ⁇ -aminoacetophenone photopolymerization initiator examples 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 can be mentioned.
- Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
- acylphosphine oxide photopolymerization initiators 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.
- examples of commercially available products include Lucillin (registered trademark) TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.
- 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 it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, if it exceeds 15 parts by mass, a sufficient effect of reducing the 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 0.5 to 10 parts by mass.
- a photopolymerization initiator a photoinitiator assistant and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment
- a benzoin compound an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound
- examples include benzophenone compounds, tertiary amine compounds, and xanthone compounds.
- 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.
- tertiary amine compound examples include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure (registered trademark) manufactured by Nippon Soda Co., Ltd.).
- thioxanthone compounds and tertiary amine compounds are preferred.
- a thioxanthone compound it is possible to improve deep curability.
- the compounding 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.
- the blending amount of the thioxanthone compound 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.
- dialkylaminobenzophenone compound 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.
- the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to obtain a solder resist film.
- 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 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 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.
- photopolymerization initiators 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.
- these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.
- the Neuburgh siliceous particles used in the present embodiment are natural bound substances called silitin and silicolloid, and have a structure in which spherical silica and plate-shaped kaolinite are loosely bound to each other. Such a structure makes it possible to impart excellent cured product properties that cannot be obtained with fillers such as barium sulfate, crushing, or fused silica.
- Neuburgh siliceous particles are composed of silica and kaolinite, a silane coupling agent described later works very effectively, and sufficient wettability with respect to resins can be obtained.
- Neuburg silica particles are readily available, but are relatively large in size because they are minerals. However, since it can be easily reduced in size by pulverization, it can be used more suitably by appropriately setting the particle size appropriately when used in an electronic material.
- the particle diameter D 50 is preferably 2.0 ⁇ m or less.
- a disperser such as a jet mill or a bead mill, further classify or form a slurry, and filter it.
- the maximum particle size is preferably 5.0 ⁇ m or less.
- the compounding amount of the Neuburg silica particle is 5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If the amount is less than 5 parts by mass, the effect is not confirmed. On the other hand, if the amount exceeds 300 parts by mass, the photocurable resin composition may cause poor dispersion and markedly improved thixotropy. More preferably, it is 20 to 250 parts by mass.
- Neuburg silica particles include, for example, Siritin V85, Siritin V88, Siritin N82, Siritin N85, Siritin N87, Siritin Z86, Siritin Z89, Siricolin P87, Siritin N85 Puris, Siritin Z86 Puris, Siritin Z89 Puris, Siricolloid P87 Puris, ( Any of these may include trade names; manufactured by Hoffmann-mineral). These can be used alone or in combination of two or more.
- Neuburg silica particles are preferably subjected to a surface treatment in order to obtain sufficient wettability to resins.
- surface treatment silane coupling treatment
- silane coupling treatment can be performed using aminosilane, mercaptosilane, vinyl silane, methacryl silane, epoxy silane, alkyl silane, or the like.
- Neuburg silica particles that have been surface-treated include Actidyl VM56, Actidyl MAM, Actidyl MAM-R, Actidyl EM, Actidyl AM, Actidyl MM, Actidyl PF777 (all trade names; Hoffman Minerals) (Manufactured by Hoffmann-mineral)). These can be used alone or in combination of two or more.
- the photocurable resin composition of the present embodiment can use a silane coupling agent in order to improve the wettability of Neuburg silica particles and resins.
- a silane coupling agent is a compound composed of an organic substance (organic group) and silicon, and has two or more different reactive groups in the molecule. For this reason, it serves as an intermediary between an organic material and an inorganic material, which are usually very difficult to bond, and is used for improving the strength of composite materials, modifying resins, modifying surfaces, and the like.
- the Neuburg silica particle is composed of silica and kaolinite, so that the silane coupling agent works very effectively. Therefore, sufficient wettability with respect to the resins can be obtained by adding the silane coupling agent.
- the surface treatment is performed by using a silane coupling agent, and the wettability to the resin can be effectively improved. Further improvement in wettability can be obtained even in the surface-treated Neuburg silica particles.
- the surface treatment can be reliably performed by adding a silane coupling agent. .
- the compounding quantity of a silane coupling agent is 0.1 to 10 mass parts with respect to 100 mass parts of carboxyl group-containing resin. If the amount is less than 0.1 parts by mass, the effect is not confirmed. On the other hand, if the amount exceeds 10 parts by mass, the viscosity of the photocurable resin composition is increased or the cost is increased. More preferably, it is 5 parts by mass or less, or 5% by weight or less based on the amount of Neuburg silica particles to be used.
- organic groups contained in the silane coupling agent include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, polysulfide groups, and isocyanate groups. Can be mentioned.
- silane coupling agents examples include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, Examples thereof include KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names; manufactured by Shin-Etsu Silicone). These can be used alone or in combination of two or more.
- the surface treatment of Neuburg silica particles or the addition of a silane coupling agent provides sufficient wettability to the resins, eliminating the interface between the resins and Neuburg silica particles and further insulation.
- Various characteristics such as reliability, PCT resistance, and cured product properties can be improved.
- fillers in order to raise the physical strength of a coating film or hardened
- known inorganic or organic fillers can be used, but barium sulfate, spherical silica and talc are particularly preferable.
- metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as fillers.
- thermosetting component can be added to the photocurable resin composition of the present embodiment in order to impart heat resistance.
- Thermosetting components include isocyanates, blocked isocyanate compounds, amino resins, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, benzoguanamine derivatives, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, etc.
- a known thermosetting resin can be used.
- isocyanates blocked isocyanate compounds, and amino resins can easily react with hydroxyl groups or carboxyl groups. By reacting these, it is possible to obtain a cured product that is incorporated into a strong three-dimensional network and has a significantly increased flexibility.
- thermosetting components those having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule are preferable.
- cyclic (thio) ether groups there are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
- thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them.
- a compound having at least two epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional compound.
- examples include oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins.
- polyfunctional epoxy compound examples include bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, Alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixtures thereof, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic ring Epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, epoxy resin having dicyclopentadiene skeleton, Jill methacrylate copolymerization system epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, polybutadiene rubber derivative
- Polyfunctional oxetane compounds 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-oxetanyl)
- polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resins, poly (P-hydroxystyrene), card
- a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.
- These polyfunctional oxetane compounds can be used alone or in combination of two or more.
- episulfide resin examples include bisphenol A type episulfide resin.
- 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. These episulfide resins can be used alone or in combination of two or more.
- the compounding amount of the thermosetting component having two or more 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. It is preferable.
- the amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Decreases.
- the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8 to 2.0 equivalents.
- thermosetting components examples include 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.
- These melamine derivatives and benzoguanamine derivatives can be used alone or in combination of two or more.
- an isocyanate or a blocked isocyanate compound a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having two or more blocked isocyanate groups in one molecule, that is, a blocked isocyanate compound Etc.
- 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, o-xylylene diisocyanate, m- Examples include 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 listed above may be mentioned.
- the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by a reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
- the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
- the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
- the aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate mentioned above is used, 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, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl e
- polyisocyanate compounds and blocked isocyanate compounds can be used singly or in combination of two or more.
- the blending amount of such polyisocyanate compound and block isocyanate compound 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.
- a urethanization catalyst can be added in order to promote the curing reaction of hydroxyl groups, carboxyl groups and isocyanate groups.
- a urethanization catalyst one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts should be used. Is preferred.
- tin catalyst examples include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
- the metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.
- the metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Can be mentioned.
- the metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include copper sulfate.
- Examples of the amine compound include known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N “, N” -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N ′-(2 -Hydroxyethyl) -N, N, N'-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethyl-N'- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) N, N
- Examples of the amine salt include DBU (1,8-diaza-bicyclo [5,4,0] undecene-7) organic acid salt amine salt.
- the amount of these urethanization catalysts to be blended is a normal quantitative ratio, for example, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts per 100 parts by weight of the carboxyl group-containing resin. 0 parts by mass.
- thermosetting component having two or more 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; phosphorus compounds such as triphenylphosphine, and block isocyanates of dimethylamine Over preparative compounds, and bicyclic amidine compounds and their salts.
- 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. May be used.
- thermosetting catalysts is sufficient in the usual quantitative ratio, for example, carboxyl group-containing resin) or 100 parts by mass of thermosetting component having two or more cyclic (thio) ether groups in the molecule.
- the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.
- the photocurable resin composition of the present embodiment can contain a colorant.
- a colorant known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and pigments may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental burden and affecting the human body.
- red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
- blue colorants include phthalocyanine and anthraquinone.
- metal-substituted or unsubstituted phthalocyanine compounds can also be used.
- examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series.
- metal-substituted or unsubstituted phthalocyanine compounds can also be used.
- yellow colorants examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.
- a colorant such as purple, orange, brown, or black may be added.
- the mixing ratio of these colorants is not particularly limited, but 0 to 10 parts by mass is sufficient for 100 parts by mass of the carboxyl group-containing resin. More preferably, it is 0.1 to 5 parts by mass.
- a compound having two or more ethylenically unsaturated groups can be contained.
- known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like can be used.
- Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as relates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ⁇ -caprolactone Polyvalent acrylates such as adducts;
- 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.
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
- a hydroxy acrylate such as pentaerythritol triacrylate
- a diisocyanate such as isophorone diisocyanate
- the compounding amount of the compound having two or more 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.
- the photocurable resin composition of the present embodiment can contain a binder polymer for the purpose of improving dryness to touch and improving handling properties.
- a binder polymer for the purpose of improving dryness to touch and improving handling properties.
- polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used.
- These binder polymers can be used alone or as a mixture 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.
- a hydroxyl group-containing elastomer has a strong hydroxyl group by reacting with a hydroxyl group generated by a reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group) or by reacting the hydroxyl groups with each other. It can be incorporated into a dimensional network. Therefore, by using an amino resin, an isocyanate, or a blocked isocyanate that can easily react with a hydroxyl group or a carboxyl group, a cured product having remarkably softness can be obtained.
- polyester elastomers examples include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers.
- resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
- epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.
- the photocurable resin composition of the present embodiment may contain an organic solvent for the synthesis of a carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity 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. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methylcellosolve, butylcellosolve, carbitol, methylcarbitol, butylcarbitol, 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
- the photo-curable resin composition of the present embodiment can be added with an antioxidant to prevent oxidation.
- an antioxidant to prevent oxidation.
- oxidative degradation occurs in a chained manner, resulting in functional degradation of the polymeric material, but the functional degradation can be suppressed by the addition of an antioxidant. .
- Antioxidants are those that act as radical scavengers that invalidate the generated radicals, or peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. Is mentioned.
- the photocurable resin composition of the present embodiment can contain an ultraviolet absorber.
- an ultraviolet absorber In general, a polymer material absorbs light and decomposes and deteriorates. However, by adding an ultraviolet absorber, stabilization against ultraviolet rays can be achieved.
- ultraviolet absorber examples include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
- benzophenone derivative examples include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned.
- benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-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 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like.
- the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
- ultraviolet absorbers can be used singly or in combination of two or more.
- cured material obtained from the photocurable resin composition of this embodiment can be aimed at by using together with antioxidant.
- 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, cyclopentanethiol , Cyclohe
- polyfunctional mercaptan compounds can be used.
- the polyfunctional mercaptan-based compound is not particularly limited, and specifically, for example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, etc.
- Aromatic thiols such as aliphatic thiols, xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol Bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tet Poly (mercaptoacetate) s of polyhydric alcohols such as kiss (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris
- a heterocyclic compound having a mercapto group can be used as a chain transfer agent.
- 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-methyl-2-mercapto-4- Butyrolactam
- N-ethyl-2-mercapto-4-butyrolactam N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam
- 2- Mercapto-5-valerolactone 2-mercapto-4-butyrolactone
- mercaptobenzothiazole 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole which does not impair the developability of the photocurable resin composition -2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred.
- chain transfer agents can be used alone or in combination of two or more.
- the photocurable resin composition of the present embodiment can contain an adhesion promoter in order to improve the adhesion between layers or the adhesion between the resin layer and the substrate.
- an adhesion promoter in order to improve the adhesion between layers or the adhesion between the resin layer and the substrate.
- the photocurable resin composition of the present embodiment can 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., if necessary.
- Organic bentonite and hydrotalcite are highly stable over time as thixotropic agents, and hydrotalcite is particularly excellent in electrical characteristics.
- thermal polymerization inhibitors such as silicones, fluorines and polymers, silane coupling agents such as imidazoles, thiazoles and triazoles, rust inhibitors and bisphenols
- Known additives such as copper-based and triazinethiol-based copper damage inhibitors can be blended.
- the thermal polymerization inhibitor is used to prevent thermal polymerization or polymerization with time of the polymerizable compound.
- thermal polymerization inhibitors 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, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
- the photocurable resin composition of the present embodiment configured as described above is used as follows, for example. First, it is adjusted to a viscosity suitable for the coating method with an organic solvent, and coated on the substrate by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method. Then, a tack-free coating film is formed by volatile drying (temporary drying) of the organic solvent contained in the composition at a temperature of about 60 to 100 ° C.
- pattern exposure is selectively performed by irradiation with active energy rays and cured.
- the unexposed portion is developed with an alkaline aqueous solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a pattern.
- an alkaline aqueous solution for example, 0.3 to 3% aqueous sodium carbonate solution
- the formed pattern can be subjected to heat treatment (thermosetting) as necessary.
- thermosetting for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin, two or more cyclic ether groups and /
- a thermosetting component having a cyclic thioether group reacts to form a cured product excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
- thermosetting component Even if it does not contain a thermosetting component, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure is thermally radical polymerized by heat treatment, and the coating film characteristics are improved. Can be improved.
- the base material on which the coating film is formed in addition to a printed circuit board and a flexible printed circuit board on which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, Copper / non-woven cloth-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, all grades (FR-4, etc.) of copper using composite materials such as fluororesin, polyethylene, PPO, cyanate ester A tension laminate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.
- Volatile drying is performed by using a hot air circulating drying furnace, IR furnace, hot plate, convection oven, etc., equipped with a heat source of an air heating system using steam, and a method or nozzle for contacting hot air in the dryer in countercurrent contact. It can be performed by using a method of spraying on the support.
- an exposure machine that performs pattern exposure on the coating film using a photomask (contact or non-contact) and a direct drawing device that directly draws an image on the coating film using CAD data from a computer are used. be able to.
- a metal halide lamp, a (super) high pressure mercury lamp, a mercury short arc lamp, or the like can be used.
- a light source of the direct drawing apparatus a laser such as a gas laser or a solid laser, an ultraviolet lamp such as a (super) high pressure mercury lamp, or the like can be used.
- a direct drawing apparatus for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used.
- the active energy ray only needs to have a maximum wavelength in the range of 350 to 410 nm, and the exposure amount varies depending on the film thickness and the like, but is generally 5 to 500 mJ / cm 2 , preferably 5 to 200 mJ / cm 2 .
- a developing method As a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used.
- 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.
- the photocurable resin composition of this embodiment can be used in the form of a dry film other than the form in which a liquid composition is directly applied to a substrate.
- the dry film has a structure in which a carrier film, a dry coating film obtained by applying and drying a photocurable resin composition, and a peelable cover film used as necessary are sequentially laminated. is there.
- Such a dry film can be obtained by forming a dry coating film on a carrier film and then laminating a cover film thereon or forming a dry coating film on a cover film and laminating this laminate on a carrier film. It is done.
- the dry coating film is formed by, for example, uniformly applying a liquid photocurable resin composition with a thickness of 10 to 150 ⁇ m using a blade coater, a lip coater, a comma coater, a film coater, and the like, followed by drying. Is done.
- the carrier film a polyester film having a thickness of 2 to 150 ⁇ m, a thermoplastic film such as polyethylene terephthalate is used.
- a cover film although a polyethylene film, a polypropylene film, etc. can be used, the adhesive force with a soldering resist layer is smaller than a carrier film.
- the cover film is peeled off as necessary, and a dry coating film and circuit formation of the photocurable resin composition are performed.
- the formed base materials are stacked and bonded together using a laminator or the like, and a photocurable resin composition layer is formed on the circuit-formed base material.
- a cured product cured coating film
- the carrier film may be peeled off either before exposure or after exposure.
- Synthesis example 1 A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name; Shonor (registered trademark) CRG951, OH equivalent: 119.4) is added to an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device ) 119.4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the system was purged with nitrogen while stirring, and the temperature was raised.
- varnish A-1 a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained.
- varnish A-1 a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained.
- varnish A-1 a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71%.
- Synthesis example 2 In a 5-liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name: Plaxel (registered trademark) 208, molecular weight 830) as a polymer polyol, 245 g, 201 g of dimethylolpropionic acid as a dihydroxyl compound having a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, p-methoxyphenol and di- 0.5 g each of t-butyl-hydroxytoluene was added.
- polycaprolactone diol manufactured by Daicel Chemical Industries, Ltd., trade name: Plaxel (registered trademark) 208, molecular weight 830
- the mixture was stopped by heating to 60 ° C. while stirring, and 0.8 g of dibutyltin dilaurate was added.
- the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C. to confirm that the isocyanate group absorption spectrum (2280 cm ⁇ 1 ) has disappeared in the infrared absorption spectrum.
- a viscous liquid urethane acrylate compound was obtained.
- varnish A-2 a resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained.
- varnish A-2 a resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained.
- varnish A-2 a resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained.
- varnish A-2 a resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50%
- Synthesis example 3 In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (day) as a polymerization initiator 21.4 g of Oil Co., Ltd., trade name: Perbutyl (registered trademark) O) was added and heated to 90 ° C.
- varnish A-3 a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained.
- varnish A-3 a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained.
- varnish A-3 a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained.
- varnish A-3 a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained.
- varnish A-3 a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained.
- triphenylphosphine was charged, heated to 110 ° C., reacted for 2 hours, heated to 120 ° C., and further reacted for 12 hours.
- 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were charged, reacted at 110 ° C. for 4 hours, and cooled.
- varnish R-1 a resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained.
- varnish R-1 a resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained.
- varnish R-1 a resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained.
- varnish R-1 a resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65%.
- reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g.
- 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha were charged into this, heated to 95 ° C., reacted for about 6 hours, and cooled.
- varnish R-2 a resin solution of a carboxyl group-containing photosensitive resin having a solid content acid value of 40 mgKOH / g and a non-volatile content of 65% was obtained.
- varnish R-2 a resin solution of a carboxyl group-containing photosensitive resin having a solid content acid value of 40 mgKOH / g and a non-volatile content of 65% was obtained.
- varnish R-2 this is referred to as varnish R-2.
- varnish R-3 a resin solution having a solid content acid value of 100 mgKOH / g and a solid content of 65% was obtained.
- varnish R-3 a resin solution having a solid content acid value of 100 mgKOH / g and a solid content of 65% was obtained.
- varnish R-3 a resin solution having a solid content acid value of 100 mgKOH / g and a solid content of 65% was obtained.
- actidyl AM (manufactured by HOFFMANN MINEAL) 500g, Calbitoacetate 500g as a solvent, N-phenyl-3-aminopropyltrimethoxysilane 15g as a silane coupling agent are mixed and stirred, and 0.5 ⁇ m zirconia beads are mixed with a bead mill. Was used for distributed processing. This was repeated twice, and an actidyl AM slurry was prepared by passing through a 3 ⁇ m filter.
- actidyl MM slurry 500 g of Actidyl MM (manufactured by HOFFMANN MINEAL), 500 g of carbitoacetate as a solvent, and 15 g of N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent are mixed and stirred, and 0.5 ⁇ m zirconia beads are mixed with a bead mill. Was used for distributed processing. This was repeated twice, and an actidyl MM slurry was prepared by passing through a 3 ⁇ m filter.
- ⁇ Optimum exposure amount> A circuit pattern substrate having a copper thickness of 18 ⁇ m was subjected to a copper surface roughening treatment (MEC Etch Bond (registered trademark) CZ-8100 manufactured by MEC Co., Ltd.), washed with water and dried. Then, the photocurable resin compositions of Example 1-11 and Comparative Example 1-3 were applied to the entire surface of the substrate using a roll coater so that the dry film thickness was about 20 ⁇ m, and a hot air circulation type at 80 ° C. It was dried for 60 minutes in a drying furnace.
- MEC Etch Bond registered trademark
- CZ-8100 manufactured by MEC Co., Ltd.
- step tablet Karl Fischer No. 2
- Development (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) was performed for 60 seconds, and the exposure amount when the remaining step tablet pattern was 7 steps was defined as the optimal exposure amount.
- Example 1-11 and Comparative Example 1-3 were applied on the entire surface of the patterned copper foil substrate using a roll coater so that the dry film thickness was about 20 ⁇ m. Drying was performed at ° C. Then, the substrate was taken out every 10 minutes from 20 minutes to 80 minutes and allowed to cool to room temperature.
- the substrates having different drying times were each developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
- Cured product evaluation The photocurable resin compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate using a roll coater so that the dry film thickness was about 20 ⁇ m, and dried at 80 ° C. for 30 minutes. And allowed to cool to room temperature. After exposing the pattern with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp on this substrate, development was performed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds. Got.
- 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 to obtain an evaluation substrate on which a cured product pattern was formed.
- ⁇ Acid resistance> The evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to tape peeling was confirmed. The judgment criteria are as follows. ⁇ : No change is observed ⁇ : Only a slight change ⁇ : The coating film swells or swells and falls off
- ⁇ Alkali resistance> The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to tape peeling was confirmed. The judgment criteria are as follows. ⁇ : No change is observed ⁇ : Only a slight change ⁇ : The coating film swells or swells and falls off
- ⁇ Solder heat resistance> After applying the rosin flux to the evaluation substrate, it was immersed in a solder bath set at 260 ° C. in advance. Then, after washing the flux with denatured alcohol, the resist layer was visually evaluated for swelling and peeling. The judgment criteria are as follows. ⁇ : No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more. ⁇ : A little peeling occurs when the immersion for 10 seconds is repeated 3 times or more. X: The resist layer swells and peels within 3 times for 10 seconds.
- the presence or absence of peeling of the resist layer or the presence or absence of plating penetration was evaluated by tape peeling, and then the presence or absence of peeling of the resist layer was evaluated by tape peeling.
- the judgment criteria are as follows. ⁇ : No penetration after plating, no peeling after tape peeling ⁇ : Whitening is confirmed after plating, but no peeling after tape peeling ⁇ : slight penetration after plating, peeling after tape peeling Can also be seen
- ⁇ PCT resistance> The evaluation substrate subjected to electroless gold plating in the same manner as the evaluation of electroless gold plating resistance was subjected to conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec Corp.). The PCT resistance was evaluated according to the state of the coating film. The judgment criteria are as follows. ⁇ : No swelling, peeling, discoloration, or dissolution ⁇ : Some swelling, peeling, discoloration, or dissolution ⁇ : Many swelling, peeling, discoloration, or dissolution
- ⁇ Cold shock resistance> Similarly, with respect to a thermal shock resistance evaluation board obtained by forming a cured product pattern with ⁇ on the substrate and without ⁇ , the thermal thermal shock tester (manufactured by ETAC Co., Ltd.) can be used at ⁇ 55 ° C./30 minutes to A durability test of 1000 cycles was performed with 150 ° C./30 minutes as one cycle.
- substrate was put into the high temperature / humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the in-chamber HAST test was done for 168 hours.
- the insulation resistance value in the tank at the time of 168 hours elapsed was measured, and HAST resistance was evaluated.
- the judgment criteria are as follows. ⁇ : 10 8 ⁇ or more ⁇ : 10 6 to 10 8 ⁇ ⁇ : 10 6 ⁇ or less
- ⁇ CTE measurement> A cured product of a photocurable resin composition having a thickness of about 40 ⁇ m was formed, and the coefficient of linear expansion (CTE) was measured by TMA (TMA / SS 6100 manufactured by SII Nanotechnology Co., Ltd.). In order to eliminate the influence of curing shrinkage and the like, the annealing treatment was performed with 1stRun, and the CTE was calculated by measuring 2ndRun. The measured CTE value was determined as an average value of 30 ° C. to 80 ° C.
- ⁇ Resolution evaluation> A cured product pattern of a photocurable resin composition having an opening of 100 ⁇ m was formed on the substrate, and observed with an SEM (scanning electron microscope). By measuring the obtained aperture diameter, it was evaluated by the rate of change in resolution with respect to the negative dimensions. Evaluation criteria were judged as follows. ⁇ : Opening diameter reduction rate of less than 15% ⁇ : Opening diameter reduction rate of 15% or more
- Examples 12 to 22 and Comparative Examples 4 to 6 The photocurable resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 prepared at the blending ratios shown in Table 1 were diluted with methyl ethyl ketone and applied onto a PET film. This was dried at 80 ° C. for 30 minutes to form a dry coating film having a thickness of 20 ⁇ m, and a cover film was further bonded thereon to produce dry films of Examples 12 to 22 and Comparative Examples 4 to 6. The obtained dry film was evaluated as follows.
- ⁇ Dry film evaluation> The cover film was peeled off from the obtained dry film, and the dry film was heat-laminated on the patterned copper foil substrate. Subsequently, pattern exposure was performed with an optimum exposure amount using an exposure apparatus having a high-pressure mercury lamp mounted on the substrate.
- the carrier film was peeled off, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds to obtain a 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 to obtain an evaluation substrate on which a cured product pattern was formed.
- the photocurable resin composition of the present embodiment and its dry film have excellent coating properties, and the cured product is required for, for example, a solder resist for semiconductor packages.
- PCT resistance, thermal shock resistance, and HAST resistance as well as excellent cured product properties and resolution.
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Abstract
Description
本発明の一実施形態の光硬化性樹脂組成物は、カルボキシル基含有樹脂と、光重合開始剤と、ノイブルグ珪土粒子とを含有することを特徴とするものである。
(2)後述するような2官能(固形)エポキシ樹脂の水酸基を、さらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に、(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。
(3)1分子中に2個以上のエポキシ基を有するエポキシ化合物に、1分子中に少なくとも1個のアルコール性水酸基と1個のフェノール性水酸基を有する化合物と、(メタ)アクリル酸などの不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、アジピン酸などの多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(4)ビスフェノールA、ビスフェノールF、ビスフェノールS、ノボラック型フェノール樹脂、ポリ-p-ヒドロキシスチレン、ナフトールとアルデヒド類の縮合物、ジヒドロキシナフタレンとアルデヒド類との縮合物などの1分子中に2個以上のフェノール性水酸基を有する化合物と、エチレンオキシド、プロピレンオキシドなどのアルキレンオキシドとを反応させて得られる反応生成物に、(メタ)アクリル酸などの不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(5)1分子中に2個以上のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネートなどの環状カーボネート化合物とを反応させて得られる反応生成物に、不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(6)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネートなどのジイソシアネート化合物と、ポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基及びアルコール性ヒドロキシル基を有する化合物などのジオール化合物の重付加反応によるウレタン樹脂の末端に、酸無水物を反応させてなる末端カルボキシル基含有ウレタン樹脂。
(7)ジイソシアネートと、ジメチロールプロピオン酸、ジメチロール酪酸などのカルボキシル基含有ジアルコール化合物と、ジオール化合物との重付加反応によるカルボキシル基含有ウレタン樹脂の合成中に、ヒドロキシアルキル(メタ)アクリレートなどの分子中に1つの水酸基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。
(8)ジイソシアネートと、カルボキシル基含有ジアルコール化合物と、ジオール化合物との重付加反応によるカルボキシル基含有ウレタン樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子中に1つのイソシアネート基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。
(9)(メタ)アクリル酸などの不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレンなどの不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。
(10)後述するような多官能オキセタン樹脂に、アジピン酸、フタル酸、ヘキサヒドロフタル酸などのジカルボン酸を反応させ、生じた1級の水酸基に、2塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂に、さらにグリシジル(メタ)アクリレート、α-メチルグリシジル(メタ)アクリレートなどの1分子中に1つのエポキシ基と1つ以上の(メタ)アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。
(11)上述した(1)~(10)のカルボキシル基含有樹脂に、1分子中に環状エーテル基と(メタ)アクリロイル基を有する化合物を付加させたカルボキシル基含有感光性樹脂。
このようなカルボキシル基含有樹脂の中でも、上述したように、エポキシ樹脂を出発原料として用いていないカルボキシル基含有樹脂を好適に用いることができる。従って、上述したカルボキシル基含有樹脂の具体例のうち、(4)~(8)を特に好適に用いることができる。
このようなカルボキシル基含有樹脂は、バックボーン・ポリマーの側鎖に多数のカルボキシル基を有するため、アルカリ水溶液による現像が可能である。
これらの着色剤の配合割合は、特に制限はないが、カルボキシル基含有樹脂100質量部に対して、0~10質量部で充分である。より好ましくは0.1~5質量部である。
これらの酸化防止剤は、1種を単独で又は2種以上を組み合わせて用いることができる。
トリアジン誘導体の具体的な例としては、ヒドロキシフェニルトリアジン、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジンなどが挙げられる。
これらの連鎖移動剤は、単独又は2種以上を併用することができる。
先ず、有機溶剤で塗布方法に適した粘度に調整し、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法などの方法により塗布する。そして、約60~100℃の温度で、組成物中に含まれる有機溶剤を揮発乾燥(仮乾燥)させることにより、タックフリーの塗膜を形成する。
ドライフィルムは、キャリアフィルムと、光硬化性樹脂組成物を塗布・乾燥して得られる乾燥塗膜と、必要に応じて用いられる剥離可能なカバーフィルムとが、順次積層された構造を有するものである。
(カルボキシル基含有樹脂の合成)
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(昭和高分子(株)製、商品名;ショーノール(登録商標)CRG951、OH当量:119.4)119.4g、水酸化カリウム1.19g及びトルエン119.4gを仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。
このようにして、固形物の酸価88mgKOH/g、不揮発分71%のカルボキシル基含有感光性樹脂の樹脂溶液を得た。以下、これをワニスA-1と称す。
温度計、撹拌機及び環流冷却器を備えた5リットルのセパラブルフラスコに、ポリマーポリオールとしてポリカプロラクトンジオール(ダイセル化学工業(株)製、商品名;プラクセル(登録商標)208、分子量830)1,245g、カルボキシル基を有するジヒドロキシル化合物としてジメチロールプロピオン酸201g、ポリイソシアナートとしてイソホロンジイソシアナート777g及びヒドロキシル基を有する(メタ)アクリレートとして2-ヒドロキシエチルアクリレート119g、さらにp-メトキシフェノール及びジ-t-ブチル-ヒドロキシトルエンを各々0.5gずつ投入した。
攪拌機、温度計、還流冷却器、滴下ロート及び窒素導入管を備えた2リットルのセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル900g、及び重合開始剤としてt-ブチルパーオキシ2-エチルヘキサノエート(日油(株)製、商品名;パーブチル(登録商標)O)21.4gを加えて90℃に加熱した。
ジエチレングリコールモノエチルエーテルアセテート600gにオルソクレゾールノボラック型エポキシ樹脂(大日本インキ化学工業(株)製、商品名;EPICLON(登録商標)N-695、軟化点95℃、エポキシ当量214、平均官能基数7.6)1070g(グリシジル基数(芳香環総数):5.0モル)、アクリル酸360g(5.0モル)、及びハイドロキノン1.5gを仕込み、100℃に加熱攪拌し、均一溶解した。
クレゾールノボラック型エポキシ樹脂(日本化薬(株)製、商品名;EOCN(登録商標)-104S、軟化点92℃、エポキシ当量220)2200部、ジメチロールプロピオン酸134部、アクリル酸648.5部、メチルハイドロキノン4.6部、カルビトールアセテート1131部及びソルベントナフサ484.9部を仕込み、9 0℃に加熱し撹拌し、反応混合物を溶解した。
エポキシ当量800、軟化点79℃のビスフェノールF型固型エポキシ樹脂400部をエピクロルヒドリン925部とジメチルスルホキシド462.5部を溶解させた後、攪拌下70℃で、98.5%NaOH 81.2部を、100分かけて添加した。添加後、さらに70℃で3時間反応を行なった。
シリチンN85ピュリススラリーの調製;
シリチンN85ピュリス(HOFFMANN MINERAL社製)500gと、溶剤としてカルビトーアセテート500g、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン15gを混合攪拌し、ビーズミルにて0.5μmのジルコニアビーズを用い分散処理を行った。これを2回繰り返して、3μmのフィルターを通すことで、シリチンN85ピュリススラリーを調製した。
アクティジルAM(HOFFMANN MINERAL社製)500gと、溶剤としてカルビトーアセテート500g、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン15gを混合攪拌し、ビーズミルにて0.5μmのジルコニアビーズを用い分散処理を行った。これを2回繰り返して、3μmのフィルターを通すことで、アクティジルAMスラリーを調製した。
アクティジルMM(HOFFMANN MINERAL社製)500gと、溶剤としてカルビトーアセテート500g、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン15gを混合攪拌し、ビーズミルにて0.5μmのジルコニアビーズを用い分散処理を行った。これを2回繰り返して、3μmのフィルターを通すことで、アクティジルMMスラリーを調製した。
これら合成例の樹脂溶液を用い、表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、光硬化性樹脂組成物を調製した。ここで、得られた光硬化性樹脂組成物の分散度を、エリクセン社製グラインドメータによる粒度測定にて評価したところ、15μm以下であった。
<最適露光量>
銅厚18μmの回路パターン基板を、銅表面粗化処理(メック(株)製メックエッチボンド(登録商標)CZ-8100)後、水洗し、乾燥した。そして、基板全面に、実施例1-11及び比較例1-3の光硬化性樹脂組成物を、乾燥膜厚が約20μmになるようにロールコーターを用いて塗布し、80℃の熱風循環式乾燥炉で60分間乾燥させた。
実施例1-11及び比較例1-3の光硬化性樹脂組成物を、パターン形成された銅箔基板上に、乾燥膜厚が約20μmになるようにロールコーターを用いて全面塗布し、80℃で乾燥を行った。そして、20分から80分まで10分おきに基板を取り出し、それぞれ室温まで放冷した。
実施例及び比較例の光硬化性樹脂組成物を、パターン形成された銅箔基板上に、乾燥膜厚が約20μmになるようにロールコーターを用いて全面塗布し、80℃で30分間乾燥し、室温まで放冷した。この基板に高圧水銀灯を搭載した露光装置を用いて、最適露光量でパターンを露光した後、30℃の1wt%炭酸ナトリウム水溶液により、スプレー圧0.2MPaの条件で、90秒間現像を行い、パターンを得た。
評価基板を、10vol%H2SO4水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープピーリングによる剥がれを確認した。判定基準は以下のとおりである。
○:変化が認められないもの
△:ほんの僅か変化しているもの
×:塗膜に膨れあるいは膨潤脱落があるもの
評価基板を、10vol%NaOH水溶液に室温で30分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープピーリングによる剥がれを確認した。判定基準は以下のとおりである。
○:変化が認められないもの
△:ほんの僅か変化しているもの
×:塗膜に膨れあるいは膨潤脱落があるもの
評価基板にロジン系フラックスを塗布した後、予め260℃に設定したはんだ槽に浸漬した。そして、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
○:10秒間浸漬を3回以上繰り返しても剥がれが認められない
△:10秒間浸漬を3回以上繰り返すと少し剥がれる
×:10秒間浸漬を3回以内にレジスト層に膨れ、剥がれがある
評価基板について、市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル5μm、金0.05μmの条件でめっきを行った。メッキされた評価基板において、テープピーリングにより、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
○:めっき後にしみ込みが見られず、テープピーリング後に剥がれはない
△:めっき後に白化が確認されるが、テープピーリング後の剥がれはない
×:めっき後に僅かなしみ込みが確認され、テープピーリング後に剥がれも見られる
耐無電解金めっき性の評価と同様に無電解金めっきを施した評価基板を、PCT装置(エスペック(株)製HAST SYSTEM TPC-412MD)を用いて、121℃、飽和、0.2MPaの条件で168時間処理し、塗膜の状態によりPCT耐性を評価した。判定基準は以下のとおりである。
○:膨れ、剥がれ、変色、溶出のないもの
△:若干の膨れ、剥がれ、変色、溶出があるもの
×:膨れ、剥がれ、変色、溶出が多く見られるもの
同様にして、基板上に□抜き、○抜きの硬化物パターンを形成して得られた冷熱衝撃耐性評価基板について、冷熱衝撃試験器(エタック(株)製)により、-55℃/30分~150℃/30分を1サイクルとして、1000サイクルの耐性試験を行った。
○:クラック発生率30%未満
△:クラック発生率30~50%
×:クラック発生率50%以上
クシ型電極(ライン/スペース=30ミクロン/30ミクロン)が形成されたBT基板上に、同様にして光硬化性樹脂組成物の硬化物パターンを形成し、HAST耐性評価基板を作成した。この評価基板を、130℃、湿度85%の雰囲気下の高温高湿槽に入れ、電圧12Vを荷電し、168時間、槽内HAST試験を行った。
○:108Ω以上
△:106~108Ω
×:106Ω以下
約40μm厚の光硬化性樹脂組成物の硬化物を形成し、TMA(エスアイアイ・ナノテクノロジー(株)社製 TMA/SS 6100)により、線膨張係数(CTE)を測定した。測定は硬化収縮などの影響を排除するため、1stRunでアニール処理を行い、2ndRunの測定にてCTEを算出した。また測定したCTEの値は、30℃~80℃の平均値として決定した。
基板上に、100μmの開口を有する光硬化性樹脂組成物の硬化物パターンを形成し、SEM(走査型電子顕微鏡)により観察した。得られた開口径を測長することで、ネガ寸法に対しての解像性の変化率により評価した。評価基準は下記のように判断した。
○:開口径縮小率15%未満
×:開口径縮小率15%以上
表1に示す配合割合で調製した実施例1~11及び比較例1~3の各光硬化性樹脂組成物を、メチルエチルケトンにて希釈し、PETフィルム上に塗布した。これを80℃で30分乾燥し、厚さ20μmの乾燥塗膜を形成し、さらにその上にカバーフィルムを貼り合わせて、実施例12~22、比較例4~6のドライフィルムを作製した。
得られたドライフィルムについて、以下のように評価を行った。
得られたドライフィルムからカバーフィルムを剥がし、パターン形成された銅箔基板に、ドライフィルムを熱ラミネートした。次いで、この基板に高圧水銀灯を搭載した露光装置を用いて、最適露光量でパターン露光を行った。
Claims (6)
- カルボキシル基含有樹脂と、光重合開始剤と、ノイブルグ珪土粒子とを含有することを特徴とする光硬化性樹脂組成物。
- 前記ノイブルグ珪土粒子は、表面処理が施されていることを特徴とする請求項1に記載の光硬化性樹脂組成物。
- さらに、シランカップリング剤を含有することを特徴とする請求項1又は請求項2に記載の光硬化性樹脂組成物。
- 請求項1から請求項3のいずれかに記載の光硬化性樹脂組成物を、フィルム上に塗布乾燥して得られる乾燥塗膜を備えることを特徴とするドライフィルム。
- 請求項1から請求項3のいずれかに記載の光硬化性樹脂組成物を基材上に塗布乾燥し、又は請求項4に記載のドライフィルムを基材上に張り付けることにより、基材上に形成された乾燥塗膜を、活性エネルギー線照射により硬化させて得られることを特徴とする硬化物。
- 請求項5に記載の硬化物を備えることを特徴とするプリント配線板。
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2011
- 2011-02-02 US US13/577,590 patent/US20120308838A1/en not_active Abandoned
- 2011-02-02 KR KR1020127020706A patent/KR101523134B1/ko active IP Right Grant
- 2011-02-02 CN CN2011800085767A patent/CN102754030A/zh active Pending
- 2011-02-02 WO PCT/JP2011/000568 patent/WO2011096206A1/ja active Application Filing
- 2011-02-08 TW TW100104108A patent/TWI528107B/zh active
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US20130081858A1 (en) * | 2011-09-30 | 2013-04-04 | Taiyo Ink Mfg. Co. Ltd. | Photosensitive resin composition, cured film thereof and printed circuit board |
JP2013083961A (ja) * | 2011-09-30 | 2013-05-09 | Taiyo Ink Mfg Ltd | 感光性樹脂組成物、その硬化皮膜およびプリント配線板 |
CN104020640A (zh) * | 2011-09-30 | 2014-09-03 | 太阳油墨制造株式会社 | 感光性树脂组合物、其固化皮膜和印刷电路板 |
WO2015111577A1 (ja) * | 2014-01-23 | 2015-07-30 | 株式会社カネカ | 硬化性組成物 |
JPWO2015111577A1 (ja) * | 2014-01-23 | 2017-03-23 | 株式会社カネカ | 硬化性組成物 |
US10150895B2 (en) | 2014-01-23 | 2018-12-11 | Kaneka Corporation | Curable composition |
Also Published As
Publication number | Publication date |
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JP5661293B2 (ja) | 2015-01-28 |
JP2011164270A (ja) | 2011-08-25 |
CN102754030A (zh) | 2012-10-24 |
TWI528107B (zh) | 2016-04-01 |
KR101523134B1 (ko) | 2015-05-26 |
US20120308838A1 (en) | 2012-12-06 |
TW201142497A (en) | 2011-12-01 |
KR20120109610A (ko) | 2012-10-08 |
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