WO2010125721A1 - Composition de résine photodurcissable et thermodurcissable - Google Patents

Composition de résine photodurcissable et thermodurcissable Download PDF

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Publication number
WO2010125721A1
WO2010125721A1 PCT/JP2010/001019 JP2010001019W WO2010125721A1 WO 2010125721 A1 WO2010125721 A1 WO 2010125721A1 JP 2010001019 W JP2010001019 W JP 2010001019W WO 2010125721 A1 WO2010125721 A1 WO 2010125721A1
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Prior art keywords
group
resin
resin composition
compound
curable
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PCT/JP2010/001019
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English (en)
Japanese (ja)
Inventor
伊藤信人
有馬聖夫
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太陽インキ製造株式会社
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Priority to KR1020117025281A priority Critical patent/KR101345066B1/ko
Priority to CN201080018824.1A priority patent/CN102414617B/zh
Publication of WO2010125721A1 publication Critical patent/WO2010125721A1/fr

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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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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 thermosetting resin composition that can be developed with a dilute alkaline aqueous solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a method using them
  • the present invention relates to a printed wiring board having a cured film.
  • solder resists are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density, and heat and / or light.
  • Liquid development type solder resist that undergoes final curing (main curing) upon irradiation is used, and in consideration of environmental problems, alkali development type photo solder resists that use dilute alkaline aqueous solution as the developer are the mainstream, and actual printing It is used in large quantities in the production of wiring boards.
  • solder resists are also required to have improved workability and high performance in response to the recent increase in the density of printed wiring boards as electronic devices become lighter, thinner and shorter.
  • the current alkali development type photo solder resist still has problems in terms of durability. That is, the alkali resistance, water resistance, heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type.
  • an alkali development type photo solder resist is mainly composed of a hydrophilic group, that is, a carboxyl group or a hydroxyl group in order to make alkali development possible. Decrease in adhesion and adhesion between the resist film and copper. As a result, acid resistance and alkali resistance as chemical resistance are weak.
  • semiconductor packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package)
  • PCT resistance pressure
  • Patent Document 1 discloses 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. A solder resist composition comprising a compound has been reported. Japanese Patent Laid-Open No.
  • Patent Document 2 adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed.
  • the epoxy resin used as a raw material already contains a large amount of chlorine ion impurities, and it is very difficult to remove this after the epoxy acrylate modification.
  • the present invention has been made in view of the problems of the prior art as described above, and its main purpose is to have excellent insulation reliability and chemical resistance, and also important PCT resistance as a solder resist for semiconductor packages,
  • the object is to provide a photocurable thermosetting resin composition capable of forming a cured film having HAST resistance and electroless gold plating resistance.
  • the object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and a solder resist using the dry film and the cured product.
  • An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.
  • a carboxyl group-containing resin (excluding a carboxyl group-containing resin starting from an epoxy resin), a photopolymerization initiator, and an amino resin are included.
  • a photocurable thermosetting resin composition that can be developed with a dilute alkaline aqueous solution is provided.
  • the carboxyl group-containing resin preferably does not contain a hydroxyl group, and preferably has a photosensitive group.
  • the amino resin is an amino resin having an alkoxymethyl group, and further a thermosetting component, preferably a cyclic ether structure and / or a cyclic thioether.
  • coating and drying the said photocurable thermosetting resin composition on a carrier film, and the said photocurable thermosetting resin composition Alternatively, a cured product obtained by photocuring a dry film, preferably by photocuring in a pattern with a light source having a wavelength of 350 to 410 nm is provided. Furthermore, according to the present invention, a print having a cured film obtained by photocuring the photocurable thermosetting resin composition or dry film into a pattern by direct drawing of ultraviolet rays and then thermosetting. A wiring board is also provided.
  • the photocurable thermosetting resin composition of the present invention uses a carboxyl group-containing resin that does not use an epoxy resin as a starting material as a component that can be developed with a dilute alkaline aqueous solution, the amount of halogen contained is significantly reduced. The electrical properties of the resulting cured coating are improved.
  • An amino resin contained in combination with this, particularly an amino resin having an alkoxymethyl group contributes to improving the hydrophobicity of the resulting cured coating film, and is particularly effective in resistance to gold plating. When used in combination with a carboxyl group-containing resin, it is very effective for further improving PCT resistance and HAST resistance.
  • the photo-curable thermosetting resin composition of the present invention has remarkably excellent insulation reliability and chemical resistance, and is also important as a solder resist for semiconductor packages.
  • PCT resistance, HAST resistance, electroless A cured film having gold plating resistance can be formed.
  • the cured product obtained by the present invention can achieve significantly lower halogen as compared with a cured coating film obtained by a conventional solder resist, that is, it has an excellent advantage for further halogen-free requirements in the future. It is thought to have.
  • the photocurable thermosetting resin composition of the present invention is characterized by a carboxyl group-containing resin, a photopolymerization initiator, and an amino resin, particularly an amino resin having an alkoxymethyl group, which do not use an epoxy resin as a starting material. It is characterized by containing.
  • the carboxyl group-containing resin various conventionally known carboxyl group-containing resins can be used as long as the carboxyl group-containing resin does not use an epoxy resin as a starting material. Among them, a carboxyl having an ethylenically unsaturated double bond in the molecule.
  • a group-containing photosensitive resin is preferable in terms of photocurability and development resistance.
  • the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
  • carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, one or more ethylenically unsaturated groups are contained in the molecule as described later. It is necessary to use a compound having a photosensitivity (photosensitive monomer) in combination.
  • carboxyl group-containing resin that can be used in the present invention, the following compounds (any of oligomers and polymers) are preferable.
  • Reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid
  • Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid and the like.
  • An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate.
  • a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type 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 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 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.
  • a functional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid, and the resulting primary hydroxyl group is reacted with phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.
  • a carboxyl group-containing polyester resin to which a dibasic acid anhydride such as an acid has been added is further added to one epoxy group and one or more (in one molecule such as glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate).
  • a carboxyl group-containing photosensitive resin obtained by adding a compound having a (meth) acryloyl group.
  • a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resins (1) to (7).
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the carboxyl group-containing resin used in the present invention does not use an epoxy resin as a starting material, it has a feature that the chloride ion impurity content is very low.
  • the chloride ion content of the carboxyl group-containing resin used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.
  • the carboxyl group-containing resin used in the present invention can easily obtain a resin containing no hydroxyl group.
  • the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance.
  • the outstanding point of the carboxyl group-containing resin of this invention compared with the epoxy acrylate modified resin currently used for the general solder resist is demonstrated.
  • a phenol novolak resin free from chlorine can be easily obtained.
  • Resin that has no hydroxyl group in the range of double bond equivalent 300-550, acid value 40-120 mgKOH / g by partial acrylation of phenol resin modified with alkyl oxide and introduction of acid anhydride It is possible to obtain
  • the double bond equivalent is 400 to 500 and the acid value is greatly increased to 100 mgKOH / g.
  • the acid concentration is high, the water resistance is poor, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.
  • urethane resin can also synthesize
  • a preferred resin is an isocyanate compound not using phosgene as a starting material and a carboxyl group-containing resin having a halogen content of 0 to 30 ppm synthesized from a raw material not using epihalohydrin, and more preferably synthesized so as not to theoretically contain a hydroxyl group. Resin. From such a viewpoint, the carboxyl group-containing resins (1) to (5) shown as specific examples above can be particularly preferably used.
  • a 3,4-epoxy is used with respect to the carboxyl group-containing resin (6) obtained by copolymerization with the unsaturated group-containing compound shown above.
  • a carboxyl group-containing photosensitive resin obtained by reacting cyclohexylmethyl (meth) acrylate also has a small amount of halogen since it uses an alicyclic epoxy, and can be suitably used.
  • the carboxyl group-containing resin (6) 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 There is a concern that the amount of chlorine will increase the amount of chlorine.
  • epoxy acrylate can also be used as a diol compound in the synthesis
  • a halogen component is contained, it can be used from the viewpoint that the amount of halogen can be controlled.
  • the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
  • the acid value of the carboxyl group-containing resin is in the range of 40 to 200 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g.
  • the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult.
  • the acid value exceeds 200 mgKOH / g dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary.
  • the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.
  • the weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally within the range of 2,000 to 150,000, more preferably 5,000 to 100,000.
  • the weight average molecular weight is less than 2,000, the tack-free performance of the dried 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.
  • the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
  • the blending amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the total composition.
  • the amount is less than the above range, the coating strength is lowered, which is not preferable.
  • the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.
  • the photopolymerization initiator is one or more selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
  • a photopolymerization initiator can be used.
  • oxime ester photopolymerization initiator examples include CGI-325, Irgacure OXE01, Irgacure OXE02, Adeka N-1919, and Adeka Arcles NCI-831 manufactured by Ciba Japan.
  • 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 an oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane 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 initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like.
  • Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.
  • acylphosphine oxide photopolymerization 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.
  • Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.
  • the blending amount of these ⁇ -aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane 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, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.
  • photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the photosensitive resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds.
  • a tertiary amine compound, a xanthone compound, etc. can be mentioned.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
  • anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
  • thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
  • ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
  • benzophenone compound examples include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
  • the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4- Dialkylamino group-containing coumarin compounds such as methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) , -Dimethylaminobenz
  • Kayacure DMBI 4-dimethylaminobenzoic acid
  • 2-ethylhexyl acid (Esolol 507 manufactured by Van Dyk), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.
  • thioxanthone compounds and tertiary amine compounds are preferred.
  • a thioxanthone compound is preferably included from the viewpoint of deep curability.
  • thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
  • the 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 urethane 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 provide 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 compounding 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 urethane 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 dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
  • 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 urethane resin having the biphenyl novolac structure. 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 amino resin having an alkoxymethyl group used in the photocurable thermosetting resin composition of the present invention not only functions as a crosslinking agent component in the composition of the present invention, but also for improving the hydrophobicity of the resulting solder resist. It is considered to work excellently. In particular, it was effective in gold plating resistance, and when used in combination with a carboxyl group-containing resin not using an epoxy resin as a starting material, it was further effective in PCT resistance and HAST resistance.
  • amino resins include melamine derivatives and benzoguanamine derivatives, and in particular, melamine derivatives having an alkoxymethyl group and benzoguanamine derivatives.
  • examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are the methylol groups 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.
  • Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (above, manufactured by Sanwa Chemical Co., Ltd.).
  • the amino resin as a thermosetting component as described above can be used alone or in combination of two or more.
  • the compounding amount of such an amino resin is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
  • amount of the amino resin is less than 5 parts by mass, the intended effect of the present invention is not confirmed.
  • the amount exceeds 50 parts by mass the tackiness of the dried coating film may be deteriorated or the development may be poor. Therefore, it is not preferable.
  • a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule.
  • thermosetting components having a cyclic (thio) ether group there are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on their structures.
  • a stronger three-dimensional cross-linking network is formed by performing a thermosetting reaction between a carboxyl group and a cyclic (thio) ether group, particularly an epoxy group, in the composition, resulting in chemical resistance, solder heat resistance and electroless gold.
  • a solder resist having plating resistance can be formed.
  • a thermosetting reaction between a carboxyl group and a cyclic (thio) ether group for example, an epoxy group
  • generates a hydroxyl group which generally improves adhesion to a substrate or a support. It is thought that there is an effect.
  • a stronger three-dimensional crosslinking is achieved by reacting an amino resin further having an alkoxymethyl group with a hydroxyl group generated by a thermosetting reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group).
  • a reaction system that forms a network and improves hydrophobicity.
  • the hydroxyl group produced by the thermosetting reaction of a carboxyl group and a cyclic (thio) ether group is reacted with an amino resin having an alkoxymethyl group to control the amount of the hydroxyl group, thereby achieving both water resistance and adhesion. Can be improved.
  • the carboxyl group of the carboxyl group-containing resin is first reacted with the cyclic (thio) ether group (for example, epoxy group) of the thermosetting component, and the resulting hydroxyl group is alkoxymethylated.
  • a two-stage curing method in which an amino resin having a group is reacted and cured is more effective in improving the characteristics.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule.
  • a compound having a plurality of epoxy groups in the molecule i.e., a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, i.e., a polyfunctional oxetane compound, a plurality of compounds in the molecule
  • examples thereof include compounds having a thioether group, that is, episulfide resins.
  • Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd.
  • A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd.
  • Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd.
  • Type A epoxy resin jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd.
  • Glycidylamine type epoxy resin Glycidylamine type epoxy resin
  • Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread
  • Celoxide 2021 manufactured by Daicel Chemical Industries and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin
  • Japan Epoxy Resin YL-6056, YX-4000, YL-6121 all trade names
  • Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as Epoxy Resin's jER157S (trade name); Tetraphenylolethane type such as Japan Epoxy Resin's jERYL-931, Ciba Japan's Araldide 163, etc.
  • Epoxy resin Aral made by Ciba Japan Heterocyclic epoxy resins such as id PT810, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resins such as Bremer DGT manufactured by NOF Corporation; tetraglycidyl xyleno such as ZX-1063 manufactured by Tohto Kasei Co., Ltd.
  • Irethane resin Naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by DIC; HP-7200 and HP-7200H manufactured by DIC Epoxy resin having a dicyclopentadiene skeleton such as CP-50S, CP-50M glycidyl methacrylate copolymer epoxy resin such as Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resin (For example, manufactured by Toto Kasei R-102, YR-450, etc.), epoxy-modified polybutadiene rubber derivatives (Daicel Chemical Industries, Ltd. PB-3600 etc.) and the like, but not limited thereto.
  • CTBN-modified epoxy resin Formula example, manufactured by Toto Kasei R-102, YR-450
  • 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-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 resin, Poly (p-hydroxystyrene
  • Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably 1 equivalent to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. Is in the range of 0.8 to 2.0 equivalents.
  • the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable.
  • the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
  • 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 bicyclic amidine compounds and salts thereof), and the like.
  • 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 a normal quantitative ratio, and is preferably, for example, with respect to 100 parts by mass of a carboxyl group-containing resin or a thermosetting component having 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.
  • the photocurable thermosetting resin composition of the present invention contains a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule in order to improve the curability of the composition and the toughness of the resulting cured film. Can be added.
  • a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
  • the compound which has, ie, a blocked isocyanate compound, etc. are mentioned.
  • polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
  • aromatic polyisocyanate 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 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.
  • aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example.
  • Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
  • 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 Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxi
  • the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
  • the compounds 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 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. The proportion of parts is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability falls and it is not preferable.
  • a urethanization catalyst can be added to the photo-curable thermosetting resin composition of the present invention in order to promote curing of hydroxyl groups, carboxyl groups and isocyanate groups.
  • the urethanization catalyst it is preferable to use 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. .
  • 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 made 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 conventionally 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-hydroxy Chill) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N, N, N′-trimethyl
  • Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5,4,0] undecene-7).
  • the compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio.
  • it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts per 100 parts by mass of the carboxyl group-containing resin. 0 parts by mass.
  • the photocurable thermosetting resin composition of the present invention can contain a colorant.
  • a colorant conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a 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.
  • -Indexes (CI; issued by The Society of Dyers and Colorists) are listed.
  • 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 colorant include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
  • the dye systems include 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 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used.
  • a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • Green colorant examples include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • Yellow colorant 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.
  • a colorant such as purple, orange, brown, or black may be added.
  • the blending ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. It is enough.
  • the compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention is photocured by irradiation with active energy rays, and the carboxyl group-containing resin is converted into an alkaline aqueous solution.
  • Insolubilize or help insolubilization examples include 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 Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.
  • 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 a plurality of ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. It is. When 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, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
  • the photo-curable thermosetting 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 and commonly used inorganic or organic fillers can be used.
  • barium sulfate, spherical silica and talc are preferably used.
  • metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers.
  • the amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.
  • a binder polymer can be used for the purpose of improving the touch drying property and the handling property.
  • 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 thermosetting resin composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving the brittleness of the cured product.
  • an elastomer for the purpose of imparting flexibility and improving the brittleness of the cured product.
  • a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used.
  • 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, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.
  • the photocurable thermosetting resin composition of the present invention uses an organic solvent for the synthesis of the 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. can do.
  • 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, 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 a
  • the photocurable thermosetting resin composition of the present invention includes In order to prevent oxidation, (1) radical scavengers that invalidate the generated radicals and / or (2) peroxidation that decomposes the generated peroxides into harmless substances and prevents the generation of new radicals. Antioxidants such as product decomposing agents can be added.
  • antioxidant that acts as a radical scavenger
  • hydroquinone 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p- Cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6, - tetramethyl-4-piperidyl) -
  • the radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100 Japan) Product name).
  • antioxidant that acts as a peroxide decomposer
  • phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′.
  • -Sulfur compounds such as thiodipropionate.
  • the peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
  • Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
  • the polymer material absorbs light, which causes decomposition / degradation. Therefore, the photo-curing thermosetting resin composition of the present invention has the above-mentioned antioxidant in order to take a countermeasure against stabilization against ultraviolet rays.
  • an ultraviolet absorber can be used.
  • 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 may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Japan, trade name) and the like.
  • Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, The molded product obtained from the photocurable thermosetting resin composition of this invention by using together with the said antioxidant. Can be stabilized.
  • thermosetting resin composition of the present invention known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as chain transfer agents in order to improve sensitivity. .
  • chain transfer agents include, for example, 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, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, 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, cyclo
  • the polyfunctional mercaptan-based compound is not particularly limited.
  • fat such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, etc.
  • Aromatic thiols such as aromatic thiols, xylylene dimercaptan, 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 tetrakis (mercaptoacetate), dipentaeri Poly (mercaptoacetate) s of polyhydric alcohols such as litholhexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3 -Mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate
  • heterocyclic compound having a mercapto group acting as a chain transfer agent examples include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto.
  • heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable thermosetting resin composition mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2, 1,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole are preferred.
  • chain transfer agents can be used alone or in combination of two or more.
  • an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.
  • Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents and the like.
  • the photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary.
  • a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc.
  • Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics.
  • Known and commonly used additives can be blended.
  • the thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization 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, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
  • the photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying) at a temperature of about 60 to 100 ° C.
  • the contact pattern (or non-contact pattern) is selectively exposed to active energy rays through a photomask having a pattern formed thereon, or directly exposed to a pattern using a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0). And a resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution.
  • a thermosetting component having a carboxyl group of the carboxyl group-containing resin and a plurality of cyclic ether groups and / or cyclic thioether groups in the molecule by heating to a temperature of about 140 to 180 ° C. and thermosetting.
  • the amino resin having an alkoxymethyl group reacts with the hydroxyl group generated by the reaction to form a stronger three-dimensional crosslinked network, and the hydrophobicity is improved, so that the heat resistance, chemical resistance, A cured coating film excellent in various properties such as moisture absorption resistance, adhesion, and electrical characteristics can be formed.
  • the base material examples include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.
  • Volatile drying performed after applying the photocurable thermosetting resin composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). And a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air in the dryer is blown onto the support from the nozzle.
  • the obtained coating film is exposed (irradiated with active energy rays).
  • the exposed portion (the portion irradiated by the active energy ray) is cured.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • an exposure apparatus equipped with a metal halide lamp and an (ultra) high pressure mercury lamp.
  • a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
  • the exposure amount varies depending on the film thickness and the like, but can generally be 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 maximum wavelength of 350 to 410 nm. .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the photo-curable thermosetting resin composition of the present invention is not a liquid and directly applied to a substrate, but also a dry resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance. It can also be used in the form of a film.
  • the case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.
  • the dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order.
  • the solder resist layer is a layer obtained by applying and drying an alkali-developable photocurable thermosetting resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.
  • the carrier film a thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
  • the alkali-developable photo-curable thermosetting resin composition is uniformly applied to a carrier film or cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
  • the 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.
  • a protective film permanent protective film
  • peel off the cover film layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc.
  • a solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed.
  • 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 “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
  • the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
  • a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
  • 293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air.
  • a reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring.
  • As the water produced by the reaction 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  • varnish A-1 332.5 g of the obtained novolak acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. 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. Hereinafter, this is referred to as varnish A-1.
  • Synthesis example 2 In a 5-liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,245 g of polycaprolactone diol (PLACEL208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, a dihydroxyl compound having a carboxyl group Dimethylolpropionic acid 201 g as polyisocyanate, 777 g of isophorone diisocyanate as polyisocyanate, 119 g of 2-hydroxyethyl acrylate as hydroxyl group-containing (meth) acrylate, p-methoxyphenol and di-t-butyl-hydroxytoluene each of 0 .5 g was added.
  • PACEL208 polycaprolactone diol
  • Synthesis example 3 In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Japan) 21.4 g of oil and fat Co., Ltd., trade name: Perbutyl O) was added and heated to 90 ° C.
  • varnish A-3 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) and dimethylbenzylamine 3 as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. .6 g, 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor was added, and the mixture was heated to 100 ° C. and stirred to carry out epoxy ring-opening addition reaction. After 16 hours, 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. Hereinafter, this is referred to as varnish A-3.
  • varnish R-1 a resin solution having a solid content of 65% was obtained.
  • varnish R-1 a resin solution having a solid content of 65% was obtained.
  • reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., and allowed to react for about 32 hours to obtain a reaction product having an acid value of 0.5 mg KOH / g.
  • 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha were added to this, heated to 95 ° C., reacted for about 6 hours, cooled, and solid acid value
  • a resin solution of a carboxyl group-containing photosensitive resin having 40 mg KOH / g and a nonvolatile content of 65% was obtained.
  • varnish R-2 this is referred to as varnish R-2.
  • the reaction was carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil / water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were charged, heated to 90 ° C., stirred and reacted. The mixture was dissolved.
  • reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g.
  • 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65% A resin solution was obtained.
  • varnish R-3 this is referred to as varnish R-3.
  • Examples 1 and 2 and Comparative Examples 1 to 3 Using the resin solutions obtained in each of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill. A photocurable thermosetting resin composition was prepared. The obtained photocurable thermosetting resin composition was quantified in terms of chloride ion impurity content (total of chloride and bromide) by using a flask combustion treatment ion chromatograph method based on the JPCA standard. The results are also shown in Table 1.
  • Examples 3 to 11 and Comparative Examples 4 to 6 Using the resin solution of the above synthesis example, blended in the proportions (parts by mass) shown in Table 2 together with various components shown in Table 2 below, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared. 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 Eriksen.
  • ⁇ 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 CZ-8100 manufactured by MEC Co., Ltd.), washed with water, dried, and then subjected to photocurable thermosetting resin compositions of the above examples and comparative examples.
  • the product was applied to the entire surface by a screen printing method, and dried for 60 minutes in an 80 ° C. hot air circulation drying oven. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains after developing (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) for 60 seconds.
  • the step tablet pattern is 7 steps, the optimum exposure was set.
  • ⁇ Developability> The photocurable thermosetting resin compositions of the examples and comparative examples were applied to a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 ⁇ m, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, development was performed with a 1 wt% sodium carbonate aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.
  • ⁇ Maximum development life> The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 20 minutes from 20 to 80 minutes, and allowed to cool to room temperature. .
  • the substrate was 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.
  • ⁇ Acid resistance> The evaluation substrate was immersed in a 10 wt% HCl aqueous solution at room temperature for 30 minutes, and the infiltration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed. ⁇ : No change is observed ⁇ : Only a slight change ⁇ : The coating film swells or swells and falls off
  • Electroless gold plating resistance Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5 ⁇ m and gold 0.05 ⁇ m, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. 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.
  • ⁇ PCT resistance> The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 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 Evaluated. Judgment criteria are as follows. ⁇ : No swelling, peeling, discoloration, or dissolution ⁇ : Some swelling, peeling, discoloration, or dissolution ⁇ : Many swelling, peeling, discoloration, or dissolution
  • Example 6 and Comparative Example 4 shown in Table 2 were allowed to stand at room temperature for 10 days, and the thickening rate and the maximum development life were confirmed.
  • the thickening rate was 106%
  • Comparative Example 4 the thickening rate was 228%.
  • the maximum development life after 10 days at room temperature was not changed in Example 6 in 60 minutes, whereas in Comparative Example 4, it was shortened to 20 minutes.
  • Example 6 using an amino resin is a composition that is stable even when stored at room temperature in one liquid, and is a one-pack type that can be stored at room temperature, which was very difficult with conventional epoxy resin systems. This result is considered to have the potential as a photosensitive resin composition.
  • Examples 12 to 17 and Comparative Examples 7 to 9 Each composition of Examples 4, 7, 8, 9, 10, and 11 and Comparative Examples 4, 5, and 6 prepared at the blending ratio shown in Table 2 was diluted with methyl ethyl ketone, applied onto a PET film, and 80 ° C. And dried for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 ⁇ m. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 12 to 17 and Comparative Examples 7 to 9, respectively.
  • ⁇ Dry film evaluation> The cover film is peeled off from the dry film obtained as described above, the film is thermally laminated on the patterned copper foil substrate, and then, under the same conditions as the substrate used for the coating film property evaluation of the above example. Exposed. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under 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 130 ° C. for 60 minutes and then at 150 ° C. for 30 minutes. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 4.
  • the photo-curable thermosetting resin composition of the present invention has electroless gold plating resistance, PCT resistance, HAST characteristics (required for a solder resist for semiconductor packages) ( It was confirmed that the composition was useful as a photo-curable thermosetting resin composition having electrical characteristics.

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Abstract

La présente invention concerne : une composition de résine photodurcissable et thermodurcissable permettant la formation d'un film de revêtement durci présentant une fiabilité élevée en termes d'isolation et une résistance chimique élevée ainsi que des résistances au PCT, au HAST et au dépôt autocatalytique d'or élevées qui sont importantes pour une épargne de soudage destinée à un boîtier semi-conducteur ; un film séché et un produit durci de cette composition ; et une carte de circuit imprimé sur laquelle est formé un film de revêtement durci (par exemple une épargne de soudage) produit à partir de cette composition ou de ce film séché. Plus précisément, l'invention concerne une composition de résine photodurcissable et thermodurcissable qui peut être développée avec une solution alcaline aqueuse diluée. Cette composition de résine comprend une résine contenant un groupe carboxyle (à l'exclusion d'une résine contenant un groupe carboxyle produite en utilisant une résine époxy comme matière brute de départ), un initiateur de photopolymérisation, et une aminorésine ayant un groupe alkoxyméthyle. La résine contenant un groupe carboxyle ne contient de préférence pas de groupe hydroxy, et de manière encore plus préférentielle contient un groupe photosensible. Un mode de réalisation préféré de la composition de résine photodurcissable et thermodurcissable contient en outre un élément thermodurcissable, et de préférence contient un agent colorant.
PCT/JP2010/001019 2009-04-27 2010-02-18 Composition de résine photodurcissable et thermodurcissable WO2010125721A1 (fr)

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JP5854600B2 (ja) * 2010-12-28 2016-02-09 太陽インキ製造株式会社 光硬化性樹脂組成物
KR101604557B1 (ko) 2011-06-17 2016-03-17 다이요 잉키 세이조 가부시키가이샤 광경화성 열경화성 수지 조성물
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