WO2011122027A1 - Composition de résine thermodurcissable photodurcissable - Google Patents

Composition de résine thermodurcissable photodurcissable Download PDF

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Publication number
WO2011122027A1
WO2011122027A1 PCT/JP2011/001924 JP2011001924W WO2011122027A1 WO 2011122027 A1 WO2011122027 A1 WO 2011122027A1 JP 2011001924 W JP2011001924 W JP 2011001924W WO 2011122027 A1 WO2011122027 A1 WO 2011122027A1
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WIPO (PCT)
Prior art keywords
group
resin
carboxyl group
formula
resistance
Prior art date
Application number
PCT/JP2011/001924
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English (en)
Japanese (ja)
Inventor
信人 伊藤
有馬　聖夫
真司 恩田
嘉久 曽根
Original Assignee
太陽ホールディングス株式会社
エア・ウォーター株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2010083421A external-priority patent/JP5439255B2/ja
Priority claimed from JP2010083422A external-priority patent/JP5439256B2/ja
Application filed by 太陽ホールディングス株式会社, エア・ウォーター株式会社 filed Critical 太陽ホールディングス株式会社
Priority to CN201180017054.3A priority Critical patent/CN102822747B/zh
Priority to KR1020127024534A priority patent/KR101730682B1/ko
Publication of WO2011122027A1 publication Critical patent/WO2011122027A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • 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
    • G03F7/038—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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photocurable thermosetting resin composition used as a solder resist for a printed wiring board, and more particularly to a dilute alkali development type photocurable thermosetting resin composition suitable for a resist for an IC package. .
  • 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.
  • a liquid development type photo solder resist that undergoes final curing (main curing) upon irradiation is used.
  • an alkali developing type using a dilute alkaline aqueous solution as a developing solution has become the mainstream in consideration of environmental problems, and is used in large quantities in the actual production of printed 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.
  • an alkali development type photo solder resist mainly contains a hydrophilic group in order to enable alkali development, and chemicals, water, water vapor, etc. can easily permeate, resulting in reduced chemical resistance and resist film. It is considered that the adhesion between copper and copper is lowered. As a result, alkali resistance as chemical resistance is weakened, and PCT resistance (pressure cooker test resistance), which can be called moisture and heat resistance, is particularly good in semiconductor packages such as BGA (ball grid array) and CSP (chip scale package).
  • BGA ball grid array
  • CSP chip scale package
  • an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used as a carboxyl group-containing resin in a conventional solder resist.
  • 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 has been reported (for example, (See Patent Document 1).
  • (meth) acrylic acid is added to the epoxy resin obtained by reacting the reaction product of salicylaldehyde and monohydric phenol with epichlorohydrin, and polybasic carboxylic acid or its anhydride is further reacted.
  • a solder resist composition composed of a photosensitive resin, a photopolymerization initiator, an organic solvent, and the like is disclosed (see, for example, Patent Document 2).
  • the carboxyl group-containing resins used in these conventional solder resist compositions have poor electrical characteristics.
  • the present invention is a dilute alkali development type light suitable for obtaining a cured film excellent in adhesion of a substrate, chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless gold plating resistance, electrical insulation, etc.
  • An object is to provide a curable thermosetting resin composition.
  • thermosetting resin composition comprising a carboxyl group-containing resin, a photosensitive resin having a structure represented by the following general formulas (1) to (3), and a photopolymerization initiator A thermosetting resin composition is provided.
  • R 1 represents a group of the following formula (2)
  • R 2 represents a methyl group or an OR 1 group
  • n + m 1.5 to 6.0
  • n 0 to 6.0
  • m 0 to 6.0
  • l 0 to 3
  • n: m 100: 0 to 0: 100
  • R 3 represents hydrogen or a methyl group
  • R 4 represents a group or hydrogen of the following (3)
  • k 0.3 to 10.0.
  • R 5 represents hydrogen or a methyl group.
  • a photocurable thermosetting resin composition containing a carboxyl group-containing photosensitive resin having a structure represented by the following general formulas (4) to (7) and a photopolymerization initiator. Is provided.
  • R 1 represents a group of the following formula (5)
  • R 2 represents a methyl group or an OR 1 group
  • n + m 1.5 to 4.0
  • n 0 to 4.0
  • m 0 to 4.0
  • l 0 to 3
  • n: m 100: 0 to 0: 100
  • R 3 represents hydrogen or a methyl group
  • R 4 represents a group or hydrogen of the following (6) or (7)
  • k 0.3 to 10.0
  • R 5 represents hydrogen or a methyl group.
  • substrate, chemical resistance, solder heat resistance, PCT resistance, a thermal shock resistance, electroless gold plating resistance, electrical insulation, etc. can be obtained.
  • coating and drying said photocurable thermosetting resin composition on a film is provided. By using such a dry film, a resist layer can be easily formed without applying a photocurable resin composition on a substrate.
  • a cured product obtained by curing the above-mentioned photocurable thermosetting resin composition or film by irradiation with active energy rays and / or heating.
  • a cured product having excellent chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless gold plating resistance, electrical insulation, and the like can be obtained.
  • cured material obtained by hardening said photocurable thermosetting resin composition or film by active energy ray irradiation and / or a heating is provided. Is done. Thereby, the highly reliable printed wiring board which has the said characteristic can be provided.
  • the workability is excellent, and in the cured product, adhesion to the substrate, chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless It is excellent in gold plating resistance, electrical insulation, etc., and can be advantageously applied to the formation of resists for IC packages, such as solder resists for printed wiring boards.
  • R 1 represents a group of the following formula (2)
  • R 2 represents a methyl group or an OR 1 group
  • n + m 1.5 to 6.0
  • n 0 to 6.0
  • m 0 to 6.0
  • l 0 to 3
  • n: m 100: 0 to 0: 100
  • R 3 represents hydrogen or a methyl group
  • R 4 represents a group or hydrogen of the following (3)
  • k 0.3 to 10.0.
  • R 5 represents hydrogen or a methyl group.
  • the inventors of the present invention also provide a photocurable thermosetting resin composition containing a carboxyl group-containing photosensitive resin having a structure represented by the following general formulas (4) to (7) and a photopolymerization initiator. It has been found that the above-mentioned problem can also be achieved by using a product.
  • R 1 represents a group of the following formula (5)
  • R 2 represents a methyl group or an OR 1 group
  • n + m 1.5 to 4.0
  • n 0 to 4.0
  • m 0 to 4.0
  • l 0 to 3
  • n: m 100: 0 to 0: 100
  • R 3 represents hydrogen or a methyl group
  • R 4 represents a group or hydrogen of the following (6) or (7)
  • k 0.3 to 10.0
  • R 5 represents hydrogen or a methyl group.
  • the photocurable thermosetting resin composition according to the first embodiment contains a carboxyl group-containing resin, a photosensitive resin having a structure represented by the following general formulas (1) to (3), and a photopolymerization initiator. It is characterized by.
  • R 1 represents a group of the following formula (2)
  • R 2 represents a methyl group or an OR 1 group
  • n + m 1.5 to 6.0
  • n 0 to 6.0
  • m 0 to 6.0
  • l 0 to 3
  • n: m 100: 0 to 0: 100
  • R 3 represents hydrogen or a methyl group
  • R 4 represents a group or hydrogen of the following (3)
  • k 0.3 to 10.0.
  • R 5 represents hydrogen or a methyl group.
  • the photosensitive resin used in the photocurable thermosetting resin composition of the first embodiment can be formed by chain extension by reaction addition of the corresponding phenol resin of the general formula (1) and alkylene oxide or cyclocarbonate.
  • An oligomer having a reactive group can be obtained by reacting an unsaturated group-containing monocarboxylic acid with a hydroxyl group generated at the end of the extended chain.
  • the corresponding phenol skeleton of the general formula (1) has excellent hydrophobicity and heat resistance, it is possible to develop various characteristics by reacting this oligomer and incorporating it into a cured product. Become.
  • the photosensitive resin does not substantially contain a hydrophilic alcoholic hydroxyl group and has the above-described excellent hydrophobic skeleton, the moisture resistance is remarkably improved, and PCT resistance and HAST resistance can be improved. It becomes.
  • the phenol of the precursor of the said photosensitive resin is mentioned as a characteristic that a hydroxyl equivalent is large compared with normal phenol or a cresol type novolak resin. That is, it is possible to impart good flexibility to the obtained cured product. Accordingly, it is possible to improve thermal shock resistance, PCT resistance, and HAST resistance. For example, it is possible to impart excellent characteristics necessary for resists for IC packages.
  • the photosensitive resin having the structure represented by the general formulas (1) to (3) is an oligomer, and thus exhibits excellent development resistance with respect to development using an aqueous alkali solution after reaction by light irradiation. In addition, it exhibits excellent hydrophobicity and heat resistance derived from its mother skeleton, and further exhibits various properties that are derived from the mother skeleton and also have excellent flexibility and elongation due to chain extension effect by modification with alkylene oxide or cyclocarbonate. Can be imparted to the cured product.
  • the photosensitive resin having the structure represented by the general formulas (1) to (3) of the present embodiment can be easily obtained by, for example, the following method. Specific examples are shown below. [1] A photosensitive resin obtained by reacting a reaction product obtained by reacting a phenol resin with an alkylene oxide with an unsaturated group-containing monocarboxylic acid. [2] A photosensitive resin obtained by reacting a reaction product obtained by reacting a phenol resin with a cyclocarbonate compound with an unsaturated group-containing monocarboxylic acid.
  • an oligomer as a photocuring aid improves the development resistance and improves the physical properties of the obtained cured product.
  • an epoxy (meth) acrylate oligomer obtained by reacting an unsaturated group-containing monocarboxylic acid with an epoxy resin, but the effect is less than expected.
  • the epoxy (meth) acrylate oligomer contains a large amount of hydroxyl groups, it has been confirmed that it has the effect of hindering the improvement in the target development resistance. In general, the presence of a hydroxyl group has an effect of improving the adhesiveness, but on the other hand, it has been confirmed that the developability and the hydrophilicity are improved, so that the PCT resistance and the insulation reliability are deteriorated. Furthermore, since it is synthesized from an epoxy resin, a large amount of chlorine ion impurities are mixed therein, and there is a concern that it may adversely affect the insulation reliability, and it has not been widely used.
  • the photosensitive resin of the present embodiment can be obtained using a phenol resin as a starting material, can provide a photosensitive resin having almost no chloride ion impurities, and can greatly reduce the chloride ion impurity concentration.
  • the chlorine ion impurity content of such a photosensitive resin is preferably 100 ppm or less, and more preferably 50 ppm or less.
  • a photosensitive resin substantially free of hydroxyl groups can be obtained. Note that “substantially free of hydroxyl groups” means that a trace amount of hydroxyl groups is allowed.
  • the mother skeleton has excellent hydrophobicity and heat resistance, it has been clarified that excellent development resistance, PCT resistance, and insulation reliability, which have not been conventionally confirmed, are given.
  • the photosensitive resin according to the present embodiment suppresses chloride ion impurities, does not substantially contain a hydroxyl group, and can exhibit excellent insulation reliability and PCT resistance derived from a mother skeleton having good physical properties. Become.
  • the phenol resin used in the photosensitive resin of the present embodiment has a biphenyl skeleton, a phenylene skeleton, or a skeleton of both, and phenol, ⁇ ⁇ ⁇ o-cresol, p-cresol, m-cresol, a phenolic hydroxyl group-containing compound, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethyl
  • hydroquinone trimethylhydroquinone, pyrogallol, phloroglucinol, etc.
  • alkylene oxide used in the photosensitive resin of the present embodiment examples include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.
  • ethylene oxide and propylene oxide are preferable from the viewpoints of price and supply system. .
  • These alkylene oxides can be used alone or in admixture of two or more.
  • cyclocarbonate compound known carbonate compounds can be used, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, etc., preferably 5-membered ethylene carbonate, propylene carbonate Is good in terms of reactivity and supply system. These carbonate compounds can be used alone or in admixture of two or more.
  • alkylene oxides or cyclocarbonate compounds can be converted from phenolic hydroxyl groups to alcoholic groups by addition reaction to the phenolic hydroxyl groups of the corresponding phenol resins of the resin having the structure represented by the general formula (1) using a basic catalyst. It can be modified into a resin having a hydroxyl group.
  • unsaturated group-containing monocarboxylic acids examples include (meth) acrylic acid, or, further, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, penta
  • unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adduct. More preferred is (meth) acrylic acid.
  • These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.
  • n + m represented by the general formula (1) is preferably in the range of 1.5 to 6.0.
  • n + m is 1.5 or less, the molecular weight is small, so that there are cases where improvement of the intended properties cannot be expected. On the other hand, if it is 6.0 or more, developability may be adversely affected.
  • the optimum n of the photosensitive resin having the structure represented by the general formulas (1) to (3) is about 2.0 to 5.0.
  • the weight average molecular weight of the photosensitive resin of the present embodiment varies depending on the resin skeleton, but is generally preferably 1,000 to 30,000. If the weight average molecular weight is less than 1,000, this performance may not be sufficiently exhibited. On the other hand, when the weight average molecular weight exceeds 30,000, the developability may be remarkably deteriorated, and the developability as a resist composition may be significantly reduced. More preferably, it is in the range of 1,000 to 20,000.
  • the blending amount of such a photosensitive resin is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 5.0 parts by mass, the effect on various properties is poor, and when it exceeds 60 parts by mass, there is a concern that the developability with respect to an alkaline developer may be reduced. More preferably, it is 10 to 50 parts by mass.
  • the carboxyl group-containing resin used in the photocurable thermosetting resin composition according to the first embodiment a known carboxyl group-containing resin can be used.
  • a carboxyl group-containing resin that does not use an epoxy resin as a starting material as the carboxyl group-containing resin that is considered not to deteriorate the insulation reliability (has a very low halide ion content).
  • a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance.
  • the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
  • carboxyl group-containing resin examples include the compounds listed below (any of oligomers and polymers).
  • Polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., with respect to the alcoholic hydroxyl group of the resulting reaction product by reacting with the contained monocarboxylic acid
  • a carboxyl group-containing photosensitive resin obtained by reacting a product.
  • 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 polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and 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 copolymerizing 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 carboxyl group-containing polyester obtained by reacting a difunctional acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a polyfunctional oxetane resin described later, and adding a dibasic acid anhydride to the resulting primary hydroxyl group
  • Carboxyl group-containing photosensitivity obtained 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 resin. Resin.
  • 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 (10).
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • a carboxyl group-containing resin not using an epoxy resin as a starting material can be suitably used. Since such a carboxyl group-containing resin does not use an epoxy resin as a starting material, it has a feature that there are very few chlorine ion impurities.
  • the chlorine ion impurity content of the carboxyl group-containing resin suitably used in this embodiment is 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less. Accordingly, the carboxyl group-containing resins (4) to (8) listed above can be used particularly preferably.
  • a carboxyl group-containing resin that does not use an epoxy resin as a starting material can easily obtain a resin that does not contain a 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 superior point of the carboxyl group-containing resin which does not use the epoxy resin as a starting material compared with the epoxy acrylate modified resin used for the general solder resist is demonstrated.
  • Phenol novolac resin without chlorine can be easily obtained.
  • a resin having no theoretical hydroxyl group in the range of double bond equivalent of 300 to 550 and acid value of 40 to 120 mgKOH / g is obtained. It is possible to obtain.
  • urethane resins can be easily synthesized by combining the equivalents of hydroxyl groups and isocyanate groups.
  • the preferred resin is an isocyanate compound not using phosgene as a starting material, and a carboxyl group-containing resin having a chlorine ion impurity amount of 30 ppm or less synthesized from a raw material not using epihalohydrin, and more preferably synthesized so as not to theoretically contain a hydroxyl group. Resin.
  • the carboxyl group-containing resins (1) to (3) described above as specific examples can also be used. However, they have better PCT resistance, HAST resistance, and thermal shock resistance as a solder resist for semiconductor packages.
  • the carboxyl group-containing resins (4) to (8) can be more preferably used.
  • a 3,4-epoxy as a compound with respect to the carboxyl group-containing resin (9) obtained by copolymerization with the unsaturated group-containing compound shown above a carboxyl group-containing photosensitive resin obtained by reacting cyclohexylmethyl (meth) acrylate can be suitably used because it uses alicyclic epoxy and has few chloride ion impurities.
  • the carboxyl group-containing resin (9) is reacted with glycidyl (meth) acrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or glycidyl (meth) as an unsaturated group-containing compound.
  • glycidyl (meth) acrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule
  • glycidyl (meth) as an unsaturated group-containing compound.
  • the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH / g.
  • the acid value is less than 40 mgKOH / g, alkali development becomes difficult.
  • the acid value exceeds 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. It is difficult to draw a normal resist pattern due to dissolution and peeling with a developer without distinction between the unexposed area and the unexposed area. More preferably, it is 40 to 130 mgKOH / g.
  • the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 100,000. 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 100,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is in the range of 2,000 to 80,000.
  • 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. When it is less than the above range, the coating film strength is lowered. On the other hand, when the amount is larger than the above range, the viscosity is increased or the coating property is decreased.
  • the carboxyl group-containing resin used in the photocurable thermosetting resin composition according to the first embodiment has a structure represented by general formulas (4) to (7) according to a second embodiment described later.
  • a carboxyl group-containing photosensitive resin can also be used.
  • Examples of the photopolymerization initiator used in the photocurable thermosetting resin composition of the present embodiment include an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide system.
  • One or more photopolymerization initiators selected from the group consisting of photopolymerization initiators can be used.
  • oxime ester photopolymerization initiator examples include CGI-325, Irgacure® OXE01, Irgacure® OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles® NCI-831.
  • a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used.
  • Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (8). .
  • 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.
  • the blending amount of such an oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated.
  • it exceeds 5 parts by mass 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 resin. If the blending amount is less than 0.01 parts by mass, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.
  • a photopolymerization initiator a photoinitiator assistant, and a sensitizer that can be suitably used for the photocurable thermosetting resin composition of the present embodiment
  • a benzoin compound an acetophenone compound, an anthraquinone compound, a thioxanthone compound
  • examples include ketal compounds, 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.
  • the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc.
  • 4,4′-dimethylaminobenzophenone Non-dimethylaminobenzophenone
  • Dialkylaminobenzophenones such as 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (die
  • Dialkylamino group-containing coumarin compounds ethyl 4-dimethylaminobenzoate (Kayacure EPA, Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, International Bio-Synthetics), 4-dimethyl Minobenzoic acid (n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd.
  • thioxanthone compounds and tertiary amine compounds are preferred.
  • the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability.
  • thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
  • the blending amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. If the blending amount exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.
  • a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
  • 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 blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
  • the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
  • the total amount of such photopolymerization initiator, photoinitiator 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.
  • thermosetting component can be added to the photocurable thermosetting resin composition of the present embodiment in order to impart heat resistance.
  • thermosetting components include block isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Resin can be used.
  • 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.
  • 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 a plurality of cyclic (thio) ether groups in the molecule contains either one of the three-, four- or five-membered cyclic ether groups or cyclic thioether groups or two types of groups in the molecule.
  • a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a plurality of thioether groups in the molecule.
  • Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by DIC, Epototo YD-011, YD manufactured by Toto Kasei Co., Ltd. -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.
  • 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. (all trade names); 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; 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; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, 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 resins having a dicyclopentadiene skeleton such as CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resins manufactured by Nippon Oil &Fats
  • Copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate Epoxy-modified polybutadiene Rubber derivatives (eg Iseru Chemical Co.
  • CTBN modified epoxy resin e.g., Tohto Kasei Co. YR-102, YR-450, etc.
  • CTBN modified epoxy resin e.g., Tohto Kasei Co. YR-102, YR-450, etc.
  • These epoxy resins can be used alone or in combination of two or more.
  • 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) In addition to 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 novolac resin, poly (P-hydroxystyrene), card
  • episulfide resin examples 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 relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin.
  • the amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are lowered.
  • the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dried 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.
  • thermosetting components can be used alone or in combination of two or more.
  • the photocurable thermosetting resin composition of the present embodiment has 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.
  • the compound having can be added.
  • Such 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, ⁇ -valerolactam, ⁇ -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, acetaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and
  • 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 compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the blending amount is less than 1 part by mass, sufficient coating film toughness cannot be obtained.
  • it exceeds 100 mass parts storage stability falls. More preferably, it is 2 to 70 parts by mass.
  • a urethanization catalyst can be added to the photocurable thermosetting resin composition of the present embodiment in order to accelerate the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group.
  • the urethanization catalyst it is possible 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. preferable.
  • the tin-based 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-hydroxyethyl) ) -
  • amine salt examples 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 a usual quantitative ratio, and for example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 with respect to 100 parts by mass of the carboxyl group-containing resin. Part by mass.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
  • Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
  • Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are 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 embodiment can be blended with 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 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 .; The Society of Dyers and Colorists (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.
  • Benzimidazolone series Pigment Red 171, 175, 176, 185, 208.
  • Perylene series Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224.
  • Diketopyrrolopyrrole type Pigment Red 254, 255, 264, 270, 272.
  • Condensed azo series Pigment Red 220, 144, 166, 214, 220, 221, 242.
  • Anthraquinone series Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207.
  • Quinacridone series Pigment Red 122, 202, 206, 207, 209.
  • Blue colorant include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigment, specifically, Pigment Blue 15, 15: 1 , 15: 2, 15: 3, 15: 4, 15: 6, 16, 60.
  • Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 etc. can be used as the dye system.
  • a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • the green colorant includes phthalocyanine, anthraquinone, and perylene, and specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28, and the like can be used.
  • 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, 108, 193, 147, 199, 202.
  • Isoindolinone series Pigment Yellow 110, 109, 139, 179, 185.
  • Condensed azo type Pigment Yellow 93, 94, 95, 128, 155, 166, 180.
  • Benzimidazolone series Pigment Yellow 120, 151, 154, 156, 175, 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 for the purpose of adjusting the color tone.
  • Specific examples include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Brown 23, 25, Pigment Black 1, 7, etc.
  • the blending ratio of these colorants is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
  • the compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present embodiment is photocured by irradiation with active energy rays to convert the carboxyl group-containing resin into an alkali. It helps insolubilize or insolubilize in an aqueous solution.
  • 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 Aminoalkyl acrylates such as acrylate; 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; polyvalent
  • 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 preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, and the compounding amount is 5 parts by mass. If it is less than the range, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when 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 thermosetting resin composition of the present embodiment can contain a filler as necessary in order to increase the physical strength of the coating film.
  • a filler known inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc, and Neuburg Silyce earth are particularly preferable.
  • metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can also be used as a filler.
  • the photocurable thermosetting resin composition of the present embodiment can use 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 thermosetting resin composition of the present embodiment can further use other elastomers 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-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 thermosetting resin composition of the present embodiment contains 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 be used.
  • 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 embodiment is used.
  • radical scavengers that invalidate the generated radicals and / or peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals, etc.
  • An antioxidant 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.), Sumilyzer TPS (Sumitomo Chemical). Company name, product name).
  • ADK STAB TPP trade name, manufactured by Asahi Denka Co., Ltd.
  • Mark AO-412S trade name, manufactured by Adeka Argus Chemical Co., Ltd.
  • Sumilyzer TPS Sumilyzer 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 photocurable thermosetting resin composition of the present embodiment has the above-described oxidation 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.
  • triazine derivative examples 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 (manufactured by Ciba Japan, trade name) and the like.
  • ultraviolet absorbers can be used singly or in combination of two or more, and can stabilize the molded product obtained by using in combination with the above-mentioned antioxidant.
  • thermosetting resin composition of the present embodiment known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, etc. can be used as chain transfer agents in order to improve sensitivity. .
  • chain transfer agent examples include 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, Chain transfer agents having a hydroxyl group such as 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, cyclopentanethiol
  • Polyfunctional mercaptan compounds can be used and are not particularly limited.
  • Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythri Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipent
  • Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz -NR1 (above, Showa Denko).
  • 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 Examples include group-containing benzotriazoles and silane coupling agents.
  • the photocurable thermosetting 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.
  • Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics.
  • Known additives such as copper damage preventing agents such as triazine and triazine thiol can be blended.
  • the thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound contained in the photocurable thermosetting resin composition of the present embodiment.
  • 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
  • the photocurable thermosetting resin composition of the present embodiment described above is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a substrate, a dip coating method, a flow coating method, a roll coating method, Tack-free coating film is applied by bar coater method, screen printing method, curtain coating method, etc., and the organic solvent contained in the composition is evaporated and dried (temporary drying) at a temperature of about 60-100 ° C. Can be formed. Thereafter, the contact pattern (or non-contact pattern) is selectively exposed with an active energy ray through a photomask on which a pattern is formed, or directly exposed with a pattern using a laser direct exposure machine. A resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution.
  • thermosetting component for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and a plurality of cyclic ( A thermosetting component having a thio) ether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
  • thermosetting component by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.
  • Base materials include printed circuit boards and flexible printed circuit boards with pre-formed circuits, paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin, Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET film A glass substrate, a ceramic substrate, a wafer plate or the like can be used.
  • Volatile drying performed after applying the photocurable thermosetting resin composition of the present embodiment is a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like (having a heat source of an air heating method using steam). And a method in which the hot air in the dryer is brought into countercurrent contact and a method in which the hot air 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 device for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer
  • an exposure device equipped with a metal halide lamp and an (ultra) high-pressure mercury lamp
  • an exposure machine mounted an exposure machine mounted with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.
  • an ultraviolet lamp such as a (super) high pressure mercury lamp.
  • the active energy ray either 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 dose varies depending on the film thickness and the like, but is generally 5 to 500 mJ / cm 2 , preferably 5 to 300 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. .
  • dipping method As the developing method, dipping method, shower method, spray method, brush method, etc. can be used, and as the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia
  • An alkaline aqueous solution such as amines can be used.
  • the photocurable thermosetting resin composition of the present embodiment is a liquid having a solder resist layer formed by previously applying a solder resist to a film of polyethylene terephthalate or the like in addition to a method of directly applying it to a substrate in a liquid state. It can also be used in the form of a film. The case where the photocurable thermosetting resin composition of this embodiment 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.
  • thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
  • the photocurable thermosetting resin composition of the present embodiment is uniformly applied to a carrier film or a cover film with a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
  • cover film a polyethylene film, a polypropylene film or the like can be used, but it is preferable that the adhesive force with the solder resist layer is smaller than that of the carrier film.
  • a protective film permanent protective film
  • 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.
  • thermosetting composition according to the first embodiment will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. It is. In the following description, “parts” and “%” are based on mass unless otherwise specified.
  • resin solution A-1 1450.0 g of the purified methacrylate resin solution was distilled off while replacing with 206.3 g of diethylene glycol monoethyl ether acetate, and 0.21 g of 4-methoxyphenol was added.
  • a 2 L glass flask was charged with 925.0 g of the resulting propylene oxide adduct solution, 0.95 g of 4-methoxyphenol, 826.6 g of toluene, 156.2 g of methacrylic acid, and 38.2 g of methanesulfonic acid, and a temperature of 100 to 110 ° C.
  • the esterification reaction was carried out for 8 hours. 32.7 g of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting methacrylate resin solution was neutralized with 163.6 g of 15% potassium hydroxide solution, and washed once with 5% saline and three times with pure water. The resin content in the solution was 33.5%.
  • the resulting propylene oxide adduct solution 800.0 g, 0.52 g of 4-methoxyphenol, 773.9 g of toluene, 152.1 g of methacrylic acid, and 22.4 g of methanesulfonic acid were charged into a 2 L glass flask, and the temperature was 100 to 110 ° C.
  • the water produced by the reaction was an azeotrope with toluene, and 31.8 g of water was distilled off. Thereafter, the mixture was cooled to room temperature, and the resulting methacrylate resin solution was neutralized with 87.2 g of 15% potassium hydroxide solution, and washed once with 5% saline and three times with pure water.
  • the resin content of the obtained purified methacrylate resin solution was 35.5%.
  • Resin Solution A-3 While distilling off 1500.0 g of purified methacrylate resin solution of toluene, 133.1 g of diethylene glycol monoethyl ether acetate was substituted, and 0.20 g of 4-methoxyphenol was added.
  • a 2 L glass flask was charged with 780.0 g of the resulting propylene oxide adduct solution, 0.51 g of 4-methoxyphenol, 772.6 g of toluene, 154.4 g of methacrylic acid, and 22.2 g of methanesulfonic acid, and a temperature of 100 to 110 ° C.
  • the esterification reaction was carried out for 6 hours.
  • generated by reaction was distilling 32.3g of water as an azeotrope with toluene. Then, it cooled to room temperature and neutralized the obtained methacrylate resin solution with 86.4g of 15% potassium hydroxide solution. Further, the methacrylate resin solution was purified by washing once with 5% saline and three times with pure water. The resin content in the solution was 36.0%.
  • the obtained propylene oxide adduct solution 718.0 g, 4-methoxyphenol 0.36 g, toluene 459.6 g, acrylic acid 28.8 g, and methanesulfonic acid 12.1 g were charged into a 2 L glass flask, and the temperature was 100 to 110 ° C.
  • generated by reaction was distilling 7.2g of water as an azeotrope with toluene. Then, it cooled to room temperature and neutralized with 51.8 g of 15% potassium hydroxide aqueous solution. Further, the acrylate resin solution was purified by washing once with 5% saline and three times with pure water. The resin content in the solution was 36.1%.
  • 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.
  • Examples 1 to 6, Comparative Examples 1 and 2 About the composition of the Example shown in Table 1, and a comparative example, performance evaluation and characteristic evaluation were performed with the evaluation method shown below. The evaluation results are shown in Table 2. Performance evaluation: ⁇ 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), washed with water and dried, and then the compositions of Examples and Comparative Examples shown in Table 1 were screen printed. It was coated on the entire surface and dried for 60 minutes in a hot air circulation drying oven at 80 ° C. to obtain a dried coating film of about 20 ⁇ m. Then, it is exposed through a step tablet (Kodak No.
  • ⁇ Maximum development life> The compositions of Examples and Comparative Examples shown in Table 1 were applied on the entire surface of a patterned copper foil substrate so as to have a dry film thickness of about 20 ⁇ m by screen printing, dried at 80 ° C. and dried for 20 to 80 minutes. The substrate was taken out every minute and allowed to cool to room temperature. This substrate was developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 90 seconds under a spray pressure of 0.2 MPa, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.
  • This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes.
  • the characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.
  • the evaluation substrate was plated on a ball pad having an opening of 80 ⁇ m under the conditions of nickel 5 ⁇ m and gold 0.05 ⁇ m using commercially available electroless nickel plating bath and electroless gold plating bath.
  • 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 and no peeling after tape peeling ⁇ : Whitening is confirmed after plating, but no peeling after tape peeling ⁇ : Peeling is confirmed after plating
  • PCT resistance Similar to the evaluation of electroless gold plating resistance, various evaluation substrates subjected to electroless gold plating can be used under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec). PCT resistance was evaluated according to the state of the coating film. The judgment criteria are as follows. ⁇ : After 300 hours test, no swelling, peeling, discoloration, or dissolution ⁇ : When 168 hours testing elapsed, no swelling, peeling, discoloration, no dissolution ⁇ : After 168 hours testing, swelling, peeling, discoloration, Elution is seen
  • Examples 7 to 12 Each composition of Examples 1 to 6 prepared at the blending ratio shown in Table 1 was diluted with methyl ethyl ketone, coated on a PET film, dried at 80 ° C. for 30 minutes, and a photosensitive resin composition layer having a thickness of 20 ⁇ m. Formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 7 to 12, respectively.
  • the cover film is peeled off from the dry film obtained as described above, the film is heat laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the above-mentioned coating film property evaluation. .
  • the carrier film was peeled off, and a 1% 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 150 ° C. for 60 minutes.
  • substrate which has the obtained cured film, performance evaluation and characteristic evaluation were performed with said evaluation method. The evaluation results are shown in Table 3.
  • the photo-curable thermosetting resin composition of the present invention has the PCT resistance, the thermal shock resistance, and the HAST characteristics required for the solder resist for semiconductor packages. It became clear that a highly reliable solder resist cured coating film was obtained, and was found to be useful as a photocurable thermosetting resin composition.
  • the photocurable thermosetting resin composition according to the second embodiment is characterized by containing a carboxyl group-containing photosensitive resin having a structure represented by general formulas (4) to (7) and a photopolymerization initiator. Yes.
  • R 1 represents a group of the following formula (5)
  • R 2 represents a methyl group or an OR 1 group
  • n + m 1.5 to 4.0
  • n 0 to 4.0
  • m 0 to 4.0
  • l 0 to 3
  • n: m 100: 0 to 0: 100
  • R 3 represents hydrogen or a methyl group
  • R 4 represents a group or hydrogen of the following (6) or (7)
  • k 0.3 to 10.0
  • R 5 represents hydrogen or a methyl group.
  • the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) is the same as the photosensitive resin having the structure represented by the general formulas (1) to (3) according to the first embodiment. Furthermore, it is excellent in flexibility and elongation by chain extension by reaction addition of a phenol resin and alkylene oxide or cyclocarbonate.
  • unsaturated group-containing monocarboxylic acid and polybasic acid anhydride are added to the terminal hydroxyl group generated by the addition reaction of alkylene oxide or cyclocarbonate, and the unsaturated group or carboxyl group is on the same side chain. Since it does not exist and is located at the end of each side chain, it has excellent reactivity. Furthermore, it has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain.
  • the carboxyl group-containing photosensitive resin is excellent in moisture absorption resistance because it does not substantially contain a hydrophilic alcoholic hydroxyl group.
  • the presence of a hydroxyl group has excellent characteristics such as improved adhesion due to hydrogen bonding, but it is known to significantly reduce moisture resistance. Therefore, moisture resistance can be improved by not containing a hydroxyl group substantially. And improvement of PCT tolerance is attained by improvement in moisture resistance.
  • the hydroxyl group equivalent is larger than that of ordinary phenol or cresol type novolac resin. That is, the cured product derived from the precursor of the carboxyl group-containing photosensitive resin according to the second embodiment has better flexibility than general novolak resins. Accordingly, the composition derived from the precursor of the carboxyl group-containing photosensitive resin of the present embodiment improves the thermal shock resistance and PCT resistance of the resulting cured product as compared with general novolak resins. It is possible.
  • the photocurable thermosetting resin composition according to the second embodiment is excellent in workability as well as the selection of the coating film, like the photocurable thermosetting resin composition according to the first embodiment.
  • a cured film having excellent adhesion, chemical resistance, electroless gold plating resistance, thermal shock resistance, PCT resistance, electrical insulation, and the like can be obtained by subject exposure, development and finish curing.
  • the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) is obtained by reacting a polybasic acid anhydride with the photosensitive resin obtained by the same method as [1] and [2] above. Can be obtained. Therefore, the phenol resin, alkylene oxide, cyclocarbonate compound, and unsaturated group-containing monocarboxylic acid used in the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) are included in the first embodiment. This is the same as the photosensitive resin having the structure represented by the general formulas (1) to (3).
  • polybasic acid anhydride examples include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylene Alicyclic dibasic acid anhydrides such as tetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride Aliphatic or aromatic dibasic acid anhydrides such as biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride,
  • the amount of alkylene oxide or cyclocarbonate compound used in the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) is in the range of 0.3 to 10 mol per equivalent of the phenolic hydroxyl group. It is preferable that When the addition amount is less than the above range, a reaction with an unsaturated group-containing monocarboxylic acid or polybasic acid anhydride described later hardly occurs, and the photosensitivity and solubility in a dilute alkaline aqueous solution are lowered. On the other hand, when the addition amount exceeds the above range, the water resistance is lowered due to the generated ether bond, and the electrical insulation property, HAST resistance and the like are lowered. More preferably, it is in the range of 0.8 to 5 mol, and still more preferably in the range of 1.0 to 3 mol.
  • the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) can be obtained using a phenol resin as a starting material in the same manner as the above-described photosensitive resin. Since the phenol resin which hardly contains chloride ion impurities can be easily obtained, the chloride ion impurity concentration in the obtained carboxyl group-containing photosensitive resin can be suppressed.
  • Such a carboxyl group-containing photosensitive resin preferably has a chlorine ion impurity content of 100 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less.
  • a carboxyl group-containing photosensitive resin substantially free of hydroxyl groups can be obtained.
  • the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) has a certain high molecular weight in order to exhibit excellent film forming performance and film physical properties.
  • n + m represented by the general formula (4) is preferably in the range of 1.5 to 4.0.
  • n + m is 1.5 or less, a carboxyl group-containing photosensitive resin having a precisely controlled structure cannot be obtained.
  • the optimum n of the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) is about 2.5 to 4.0.
  • the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) of the present embodiment has many free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution is possible. become.
  • the acid value is preferably in the range of 50 to 200 mgKOH / g. When the acid value is less than 50 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, the exposed portion is dissolved by the developing solution, so that the line becomes thinner than necessary. Dissolving and peeling with a developer without distinction between unexposed areas makes it difficult to draw a normal resist pattern. More preferably, it is 50 to 150 mgKOH / g.
  • the weight average molecular weight of the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7) varies depending on the resin skeleton, but is generally in the range of 1,000 to 20,000. preferable. If the weight average molecular weight is less than 1,000, 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 20,000, developability may be remarkably deteriorated and storage stability may be inferior. More preferably, it is 1,000 to 10,000.
  • the blending amount of such a carboxyl group-containing photosensitive resin is preferably 20 to 60% by mass in the entire composition. When it is less than the above range, the coating film strength is lowered. On the other hand, when the amount is larger than the above range, the viscosity is increased or the coating property is decreased. More preferably, it is 30 to 50% by mass.
  • the photocurable thermosetting resin composition according to the second embodiment has a structure represented by general formulas (4) to (7) in order to adjust the balance of various properties such as developability and tackiness.
  • a known carboxyl-containing resin as described above may be used in combination.
  • thermosetting composition according to the second embodiment will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. It is. In the following description, “parts” and “%” are based on mass unless otherwise specified.
  • the carboxyl group-containing photosensitive resin B-1 and the carboxyl group-containing resins R-1 and R-2 used in this example are the same as those in the example according to the first embodiment.
  • a 2 L glass flask was charged with 800.0 g of the resulting propylene oxide adduct solution, 0.42 g of 4-methoxyphenol, 563.9 g of toluene, 46.4 g of acrylic acid, and 14.1 g of methanesulfonic acid, and a temperature of 100 to 110 ° C.
  • the esterification reaction was carried out for 6 hours.
  • the water produced by the reaction was an azeotrope with toluene, and 11.6 g of water was distilled off. Then, it cooled to room temperature and neutralized with 60.4 g of 15% potassium hydroxide aqueous solution.
  • the acrylate resin solution was purified by washing once with 5% saline and three times with pure water. The resin content in the solution was 37.1%.
  • the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 59.6 g of 15% potassium hydroxide solution, washed once with 5% saline and three times with pure water to purify the acrylate resin solution. .
  • the resin content in the solution was 36.2%.
  • a 2 L glass flask was charged with 920.0 g of the resulting propylene oxide adduct solution, 0.52 g of 4-methoxyphenol, 737.2 g of toluene, 78.5 g of acrylic acid, and 15.6 g of methanesulfonic acid, and a temperature of 100 to 110 ° C.
  • the esterification reaction was carried out for 6 hours. 19.6 g of water was distilled from the water produced by the reaction as an azeotrope with toluene.
  • the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 60.7 g of 15% potassium hydroxide solution, washed once with 5% saline and three times with pure water to purify the acrylate resin solution. .
  • the resin content in the solution was 37.0%.
  • the obtained propylene oxide adduct solution 900.0 g, 4-methoxyphenol 0.50 g, toluene 694.2 g, acrylic acid 69.2 g, and methanesulfonic acid 15.0 g were charged into a 2 L glass flask, and a temperature of 100 to 110 ° C.
  • the esterification reaction was carried out for 6 hours. 17.3 g of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting acrylate resin solution was neutralized with 58.4 g of 15% potassium hydroxide solution, washed once with 5% saline and three times with pure water to purify the acrylate resin solution. .
  • the resin content in the solution was 36.5%.
  • Examples 13 to 20, Comparative Examples 3 to 6 Using the resin solution of the above synthesis example, blended in various components and proportions (parts by mass) shown in Table 4, premixed with a stirrer, kneaded with a three-roll mill, and photosensitive resin composition for solder resist was prepared. When the dispersion degree of the photosensitive resin composition obtained here was evaluated by particle size measurement using a grindometer manufactured by Eriksen Co., it was 15 ⁇ m or less.
  • the compositions of Comparative Examples 4 and 6 are the same compositions as Comparative Examples 1 and 2 in Table 1, respectively.
  • Examples 21 to 28 ⁇ Dry film evaluation> Each composition of Examples 13 to 20 prepared at the blending ratio shown in Table 4 was diluted with methyl ethyl ketone, applied onto a PET film, dried at 80 ° C. for 30 minutes, and a photosensitive resin composition layer having a thickness of 20 ⁇ m. Formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 21 to 28, respectively.
  • the cover film is peeled off from the dry film obtained as described above, the film is heat laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the above-mentioned coating film property evaluation. .
  • the carrier film was peeled off, and a 1% 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 150 ° C. for 60 minutes.
  • substrate which has the obtained cured film, performance evaluation and characteristic evaluation were performed with said evaluation method. The evaluation results are shown in Table 6.
  • the photocurable thermosetting resin composition according to the second embodiment is the same as the photocurable thermosetting resin composition according to the first embodiment.
  • a highly reliable solder resist cured coating film having both PCT resistance, thermal shock resistance and HAST characteristics required for solder resists for semiconductor packages can be obtained. It has been found useful as a composition.

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Abstract

L'invention concerne une composition de résine thermodurcissable photodurcissable du type à développement d'alcali dilué, qui peut être utilisée pour obtenir un film de revêtement durci présentant d'excellentes propriétés d'adhérence à un substrat, de résistance chimique, de résistance thermique à la soudure, de résistance PCT, de résistance au choc thermique, de résistance à la dorure anélectrolytique, d'isolation électrique, etc. La composition de résine thermodurcissable photodurcissable décrite est caractérisée en ce qu'elle comprend: une résine contenant un groupe carboxyle, une résine photosensible comportant une structure représentée par les formules générales (1-3), et un initiateur de photopolymérisation. (Dans la formule (1) R1 représente le groupe représenté par la formule (2), R2 représente un groupe méthyle ou un groupe OR1, n+m=1,5-6,0, n=0-6,0, m=0-6,0, 1=0-3, et n:m=100:0-0:100.) (Dans la formule (2) R3 représente un hydrogène ou un groupe méthyle, R4 représente un hydrogène ou le groupe représenté par la formule (3), et k=0,3-10,0). (Dans la formule (3), R5 représente un hydrogène ou un groupe méthyle).
PCT/JP2011/001924 2010-03-31 2011-03-30 Composition de résine thermodurcissable photodurcissable WO2011122027A1 (fr)

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CN104115066A (zh) * 2012-04-27 2014-10-22 太阳油墨制造株式会社 光固化热固化性树脂组合物、固化物、以及印刷电路板
CN104470962A (zh) * 2012-07-13 2015-03-25 日本化药株式会社 碱显影型树脂、使用该树脂的感光性树脂组合物
EP2781530A4 (fr) * 2011-11-15 2015-06-24 Goo Chemical Co Ltd Résine contenant un carboxyle, composition de résine pour l'utilisation dans une épargne de soudure, et procédé de fabrication pour la résine contenant un carboxyle
TWI795523B (zh) * 2018-02-05 2023-03-11 日商Ｊｓｒ股份有限公司 配線構件

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CN105377911B (zh) * 2013-07-25 2017-05-24 昭和电工株式会社 组合物、固化性组合物、其制造方法及固化物
CN104950573A (zh) * 2014-03-31 2015-09-30 太阳油墨（苏州）有限公司 光固化性热固化性树脂组合物、干膜、固化物、及印刷电路板
JP6802207B2 (ja) * 2018-03-23 2020-12-16 株式会社タムラ製作所 感光性樹脂組成物
JP7310802B2 (ja) * 2018-04-10 2023-07-19 Dic株式会社 感光性樹脂組成物、硬化物、絶縁材料、ソルダーレジスト用樹脂材料及びレジスト部材

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EP2781530A4 (fr) * 2011-11-15 2015-06-24 Goo Chemical Co Ltd Résine contenant un carboxyle, composition de résine pour l'utilisation dans une épargne de soudure, et procédé de fabrication pour la résine contenant un carboxyle
US9458284B2 (en) 2011-11-15 2016-10-04 Goo Chemical Co., Ltd. Carboxyl-containing resin, resin composition for solder mask, and method of preparing carboxyl-containing resin
CN104115066A (zh) * 2012-04-27 2014-10-22 太阳油墨制造株式会社 光固化热固化性树脂组合物、固化物、以及印刷电路板
CN104115066B (zh) * 2012-04-27 2019-04-26 太阳油墨制造株式会社 光固化热固化性树脂组合物、固化物、以及印刷电路板
CN104470962A (zh) * 2012-07-13 2015-03-25 日本化药株式会社 碱显影型树脂、使用该树脂的感光性树脂组合物
KR20150036042A (ko) * 2012-07-13 2015-04-07 닛뽄 가야쿠 가부시키가이샤 알칼리 현상형 수지, 그것을 사용한 감광성 수지 조성물
KR102031014B1 (ko) 2012-07-13 2019-10-11 닛뽄 가야쿠 가부시키가이샤 알칼리 현상형 수지, 그것을 사용한 감광성 수지 조성물
TWI795523B (zh) * 2018-02-05 2023-03-11 日商Ｊｓｒ股份有限公司 配線構件

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CN102822747A (zh) 2012-12-12
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