WO2011122027A1 - Photo-curable thermosetting resin composition - Google Patents

Photo-curable thermosetting resin composition 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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WO
WIPO (PCT)
Prior art keywords
group
resin
carboxyl group
formula
resistance
Prior art date
Application number
PCT/JP2011/001924
Other languages
French (fr)
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.)
Filing date
Publication date
Priority claimed from JP2010083421A external-priority patent/JP5439255B2/en
Priority claimed from JP2010083422A external-priority patent/JP5439256B2/en
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 KR1020127024534A priority Critical patent/KR101730682B1/en
Priority to CN201180017054.3A priority patent/CN102822747B/en
Publication of WO2011122027A1 publication Critical patent/WO2011122027A1/en

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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

Disclosed is a dilute alkali development-type photo-curable thermosetting resin composition which is suitable for use in obtaining a cured coating film which exhibits excellent adhesion with a substrate, chemical resistance, solder heat resistance, PCT resistance, thermal shock resistance, electroless gold plating resistance, electrical insulation properties, etcetera. The disclosed photo-curable thermosetting resin composition is characterised by comprising: a carboxyl group-containing resin, a photosensitive resin having a structure represented by general formulas (1)-(3), and a photopolymerization initiator. (In formula (1) R1 represents the group represented by formula (2), R2 represents a methyl group or an OR1 group, n+m=1.5-6.0, n=0-6.0, m=0-6.0, 1=0-3, and n:m=100:0-0:100.) (In formula (2) R3 represents hydrogen or a methyl group, R4 represents hydrogen or the group represented by formula (3), and k=0.3-10.0) (In formula (3) R5 represents hydrogen or a methyl group.)

Description

光硬化性熱硬化性樹脂組成物Photo-curable thermosetting resin composition
　本発明は、プリント配線基板のソルダーレジスト等として用いられる光硬化性熱硬化性樹脂組成物に関し、特に、ＩＣパッケージ用のレジストに適した希アルカリ現像型の光硬化性熱硬化性樹脂組成物に関する。 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. .
　現在、一部の民生用プリント配線板並びにほとんどの産業用プリント配線板のソルダーレジストには、高精度、高密度の観点から、紫外線照射後、現像することにより画像形成し、熱及び／又は光照射で仕上げ硬化（本硬化） する液状現像型フォトソルダーレジストが使用されている。このようなソルダーレジストには、環境問題への配慮から、現像液として希アルカリ水溶液を用いるアルカリ現像型が主流になっており、実際のプリント配線板の製造において大量に使用されている。また、近年のエレクトロニクス機器の軽薄短小化に伴うプリント配線板の高密度化に対応して、ソルダーレジストにも作業性や高性能化が要求されている。 At present, some consumer printed wiring boards and most industrial printed wiring board 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. For such a solder resist, 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. In addition, 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.
　しかしながら、現行のアルカリ現像型のフォトソルダーレジストは、耐久性の点ではまだまだ問題がある。すなわち従来の熱硬化型、溶剤現像型のものに比べて耐アルカリ性、耐水性、耐熱性等が劣る。一般に、アルカリ現像型のフォトソルダーレジストはアルカリ現像可能にするために親水性基を有するものが主成分となっており、薬液、水、水蒸気等が浸透しやすく、耐薬品性の低下やレジスト皮膜と銅との密着性を低下させると考えられる。結果として耐薬品性としてのアルカリ耐性が弱くなり、ＢＧＡ（ボール・グリッド・アレイ）やＣＳＰ（チップ・スケール・パッケージ）等の半導体パッケージにおいては、特に耐湿熱性ともいうべきＰＣＴ耐性（プレッシャークッカーテスト耐性）が必要であるが、このような厳しい条件下においては数時間～十数時間程度しかもたないのが現状である。また、加湿条件下電圧を印加した状態でのＨＡＳＴ試験（高度加速寿命試験）ではほとんどの場合、数時間でマイグレーションの発生による不良が確認されている。 However, the current alkali development type photo solder resist still has problems in terms of durability. That is, the alkali resistance, water resistance, heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type. In general, 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). ) Is necessary, but under such severe conditions, it is only several hours to several tens of hours. Also, in most cases in the HAST test (highly accelerated life test) in a state where a voltage is applied under humidification conditions, defects due to the occurrence of migration have been confirmed within a few hours.
　近年では、表面実装への移行、また環境問題への配慮に伴う鉛フリー半田の使用などパッケージにかかる温度が非常に高くなる傾向がある。これに伴いパッケージ内外部の到達温度は著しく高くなり、従来の液状感光性レジストでは、熱衝撃により塗膜にクラックが発生したり、基板や封止材から剥離してしまうという問題からその改良が求められている。 In recent years, there is a tendency for the temperature applied to the package to become very high, such as the use of lead-free solder due to the shift to surface mounting and consideration of environmental issues. Along with this, the temperature reached inside and outside of the package is remarkably increased, and the conventional liquid photosensitive resist is improved due to the problem that the coating film cracks due to thermal shock or peels off from the substrate or sealing material. It has been demanded.
　一方、従来のソルダーレジストには、カルボキシル基含有樹脂として、エポキシ樹脂の変性により誘導されたエポキシアクリレート変性樹脂が一般的に用いられている。例えば、ノボラック型エポキシ化合物と不飽和一塩基酸の反応生成物に酸無水物を付加した感光性樹脂、光重合開始剤、希釈剤及びエポキシ化合物からなるソルダーレジスト組成物が報告されている（例えば特許文献１など参照）。 On the other hand, 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. For example, 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).
　また、サリチルアルデヒドと一価フェノールとの反応生成物にエピクロロヒドリンを反応させて得られたエポキシ樹脂に（メタ）アクリル酸を付加し、さらに多塩基性カルボン酸又はその無水物を反応させて得られる感光性樹脂、光重合開始剤、有機溶剤等からなるソルダーレジスト組成物が開示されている（例えば特許文献２など参照）。しかしながら、これら従来のソルダーレジスト組成物に用いられていたカルボキシル基含有樹脂は電気特性が悪かった。 In addition, (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). However, the carboxyl group-containing resins used in these conventional solder resist compositions have poor electrical characteristics.
特開昭６１－２４３８６９号公報（特許請求の範囲）JP 61-243869 (Claims) 特開平３－２５００１２号公報（特許請求の範囲）Japanese Patent Laid-Open No. 3-250012 (Claims)
　本発明は、基板の密着性、耐薬品性、はんだ耐熱性、ＰＣＴ耐性、冷熱衝撃耐性、無電解金めっき耐性、電気絶縁性等に優れる硬化皮膜を得るのに適した希アルカリ現像型の光硬化性熱硬化性樹脂組成物を提供することを目的とする。 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.
　上記目的を達成するために、本発明の一態様によれば、カルボキシル基含有樹脂、下記一般式（１）～（３）に示す構造を有する感光性樹脂および光重合開始剤を含有する光硬化性熱硬化性樹脂組成物が提供される。 In order to achieve the above object, according to one embodiment of the present invention, photocuring 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.
Figure JPOXMLDOC01-appb-C000001
 （式（１）中、Ｒ１は下記式（２）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～６．０、ｎ＝０～６．０、ｍ＝０～６．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
Figure JPOXMLDOC01-appb-C000001
 (In the formula (1), 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)
Figure JPOXMLDOC01-appb-C000002
 （式（２）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（３）の基または水素を示し、ｋ＝０．３～１０．０である。）
Figure JPOXMLDOC01-appb-C000002
 (In formula (2), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (3), and k = 0.3 to 10.0.)
Figure JPOXMLDOC01-appb-C000003
 （式（３）中、Ｒ５は水素またはメチル基を示す。）
Figure JPOXMLDOC01-appb-C000003
 (In formula (3), R 5 represents hydrogen or a methyl group.)
　また、本発明の一態様によれば、下記一般式（４）～（７）で示される構造を有するカルボキシル基含有感光性樹脂および光重合開始剤を含有する光硬化性熱硬化性樹脂組成物が提供される。 Further, according to one aspect of the present invention, 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.
Figure JPOXMLDOC01-appb-C000004
 （式（４）中、Ｒ１は下記式（５）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～４．０、ｎ＝０～４．０、ｍ＝０～４．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
Figure JPOXMLDOC01-appb-C000004
 (In the formula (4), 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)
Figure JPOXMLDOC01-appb-C000005
 （式（５）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（６）あるいは（７）の基または水素を示し、ｋ＝０．３～１０．０である。）
Figure JPOXMLDOC01-appb-C000005
 (In Formula (5), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (6) or (7), and k = 0.3 to 10.0)
Figure JPOXMLDOC01-appb-C000006
 （式（６）中、Ｒ５は水素またはメチル基を示す。）
Figure JPOXMLDOC01-appb-C000006
 (In formula (6), R 5 represents hydrogen or a methyl group.)
Figure JPOXMLDOC01-appb-C000007
 （式(７)中のＸは酸無水物残基を表す。）
Figure JPOXMLDOC01-appb-C000007
 (X in the formula (7) represents an acid anhydride residue.)
　上記した構成とすることにより、基板の密着性、耐薬品性、はんだ耐熱性、ＰＣＴ耐性、冷熱衝撃耐性、無電解金めっき耐性、電気絶縁性等に優れる硬化皮膜を得ることができる。
　また、本発明の一態様によれば、上記の光硬化性熱硬化性樹脂組成物をフィルム上に塗布乾燥して得られる光硬化性熱硬化性のフィルムが提供される。このようなドライフィルムを用いることにより、基材上に光硬化性樹脂組成物を塗布することなく、容易にレジスト層を形成することができる。 By setting it as the above-mentioned structure, the cured film excellent in the adhesiveness of a board | substrate, chemical resistance, solder heat resistance, PCT resistance, a thermal shock resistance, electroless gold plating resistance, electrical insulation, etc. can be obtained.
Moreover, according to 1 aspect of this invention, the photocurable thermosetting film obtained by apply | 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.
　また、本発明の一態様によれば、上記の光硬化性熱硬化性樹脂組成物又はフィルムを、活性エネルギー線照射及び／又は加熱により硬化させて得られる硬化物が提供される。このような硬化物において、耐薬品性、はんだ耐熱性、ＰＣＴ耐性、冷熱衝撃耐性、無電解金めっき耐性、電気絶縁性等に優れた硬化物を得ることができる。 Moreover, according to one aspect of the present invention, there is provided a cured product obtained by curing the above-mentioned photocurable thermosetting resin composition or film by irradiation with active energy rays and / or heating. In such a cured product, 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.
　また、本発明の一態様によれば、上記の光硬化性熱硬化性樹脂組成物又はフィルムを、活性エネルギー線照射及び／又は加熱により硬化させて得られる硬化物を具備するプリント配線板が提供される。これにより、上記特性を有する信頼性の高いプリント配線板を提供することができる。 Moreover, according to 1 aspect of this invention, the printed wiring board provided with the hardened | 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.
　本発明の光硬化性熱硬化性樹脂組成物によれば、作業性に優れると共に、その硬化物において、基板との密着性、耐薬品性、はんだ耐熱性、ＰＣＴ耐性、冷熱衝撃耐性、無電解金めっき耐性、電気絶縁性等に優れ、例えばプリント配線基板のソルダーレジスト等の、特にＩＣパッケージ用のレジストの形成に有利に適用できる。 According to the photocurable thermosetting resin composition of the present invention, 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.
　本発明の発明者らは、上記課題に鑑み鋭意検討した結果、カルボキシル基含有樹脂、下記一般式（１）～（３）に示す構造を有する感光性樹脂および光重合開始剤を含有する光硬化性熱硬化性樹脂組成物を用いることによって、上記課題を達成し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above problems, the inventors of the present invention have found that photocuring containing 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 has been found that the above-mentioned problems can be achieved by using a heat-curable thermosetting resin composition, and the present invention has been completed.
Figure JPOXMLDOC01-appb-C000008
 （式（１）中、Ｒ１は下記式（２）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～６．０、ｎ＝０～６．０、ｍ＝０～６．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
Figure JPOXMLDOC01-appb-C000008
 (In the formula (1), 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)
Figure JPOXMLDOC01-appb-C000009
 （式（２）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（３）の基または水素を示し、ｋ＝０．３～１０．０である。）
Figure JPOXMLDOC01-appb-C000009
 (In formula (2), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (3), and k = 0.3 to 10.0.)
Figure JPOXMLDOC01-appb-C000010
 （式（３）中、Ｒ５は水素またはメチル基を示す。）
Figure JPOXMLDOC01-appb-C000010
 (In formula (3), R 5 represents hydrogen or a methyl group.)
　また、本発明の発明者らは、下記一般式（４）～（７）で示される構造が導入されたカルボキシル基含有感光性樹脂および光重合開始剤を含有する光硬化性熱硬化性樹脂組成物を用いることによっても、上記課題を達成し得ることを見出した。 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.
Figure JPOXMLDOC01-appb-C000011
 （式（４）中、Ｒ１は下記式（５）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～４．０、ｎ＝０～４．０、ｍ＝０～４．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
Figure JPOXMLDOC01-appb-C000011
 (In the formula (4), 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)
Figure JPOXMLDOC01-appb-C000012
 （式（５）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（６）あるいは（７）の基または水素を示し、ｋ＝０．３～１０．０である。）
Figure JPOXMLDOC01-appb-C000012
 (In Formula (5), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (6) or (7), and k = 0.3 to 10.0)
Figure JPOXMLDOC01-appb-C000013
 （式（６）中、Ｒ５は水素またはメチル基を示す。）
Figure JPOXMLDOC01-appb-C000013
 (In formula (6), R 5 represents hydrogen or a methyl group.)
Figure JPOXMLDOC01-appb-C000014
 （式(７)中のＸは酸無水物残基を表す。）
Figure JPOXMLDOC01-appb-C000014
 (X in the formula (7) represents an acid anhydride residue.)
　以下、本実施形態の光硬化性熱硬化性樹脂組成物について詳細に説明する。
　先ず、第一の実施形態にかかる光硬化性熱硬化性樹脂組成物について詳細に説明する。第一の実施形態にかかる光硬化性熱硬化性樹脂組成物は、カルボキシル基含有樹脂、下記一般式（１）～（３）に示す構造を有する感光性樹脂及び光重合開始剤を含有することを特徴とする。 Hereinafter, the photocurable thermosetting resin composition of the present embodiment will be described in detail.
First, the photocurable thermosetting resin composition according to the first embodiment will be described in detail. 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.
Figure JPOXMLDOC01-appb-C000015
 （式（１）中、Ｒ１は下記式（２）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～６．０、ｎ＝０～６．０、ｍ＝０～６．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
Figure JPOXMLDOC01-appb-C000015
 (In the formula (1), 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)
Figure JPOXMLDOC01-appb-C000016
 （式（２）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（３）の基または水素を示し、ｋ＝０．３～１０．０である。）
Figure JPOXMLDOC01-appb-C000016
 (In formula (2), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (3), and k = 0.3 to 10.0.)
Figure JPOXMLDOC01-appb-C000017
 　（式（３）中、Ｒ５は水素またはメチル基を示す。）
Figure JPOXMLDOC01-appb-C000017
 (In formula (3), R 5 represents hydrogen or a methyl group.)
　第一の実施形態の光硬化性熱硬化性樹脂組成物に用いられる感光性樹脂は、一般式（１）の対応するフェノール樹脂とアルキレンオキサイド又はシクロカーボネートとを反応付加することで鎖延長による可撓性、伸びに優れ、また、その延長鎖の末端に生じた水酸基に、不飽和基含有モノカルボン酸を反応させることで、反応性基を有するオリゴマーが得られる。
　また、これら一般式（１）の対応するフェノール骨格が優れた疎水性、耐熱性を有することから、このオリゴマーを反応させ、硬化物中に組み込むことで優れた諸特性を発現させることが可能となる。 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.
In addition, since 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.
　さらに、上記感光性樹脂は、実質的に親水性のアルコール性水酸基を含まず、上記した優れた疎水性の高い骨格を有するため、著しく耐湿性が向上し、ＰＣＴ耐性、ＨＡＳＴ耐性の向上が可能となる。また、上記感光性樹脂の前駆体のフェノールは、通常のフェノール、あるいはクレゾール型ノボラック樹脂と比較して水酸基当量が大きいことが特徴として挙げられる。即ち、得られる硬化物に対して良好な可とう性を付与することが可能となる。これに伴い、冷熱衝撃耐性とＰＣＴ耐性、ＨＡＳＴ耐性を向上させることが可能であり、例えばＩＣパッケージ用のレジストに必要な優れた諸特性の付与が可能となる。 Furthermore, since 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. Moreover, 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.
　このように一般式（１）～（３）に示す構造を有する感光性樹脂は、オリゴマーであるため、光照射により反応した後、アルカリ水溶液を用いた現像に対して優れた耐現像性を発現することができ、また、その母骨格由来の優れた疎水性、耐熱性を示し、更には母骨格由来、またアルキレンオキサイド或いはシクロカーボネート変性による鎖延長効果により可撓性、伸びに優れた諸物性を硬化物に与えることが可能となる。 As described above, 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.
　本実施形態の一般式（１）～（３）に示す構造を有する感光性樹脂は、例えば下記に示す方法により容易に得ることができる。以下に具体例を示す。
　［１］フェノール樹脂とアルキレンオキサイドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させて得られる感光性樹脂。
　［２］フェノール樹脂とシクロカーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させて得られる感光性樹脂。 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.
　一般的に光硬化助剤としてオリゴマーを添加することは、優れた耐現像性の発現、得られた硬化物の物性を向上させると考えられる。従来はエポキシ樹脂に不飽和基含有モノカルボン酸を反応させたエポキシ（メタ）アクリレートオリゴマーなどを用いる例があったが、その効果は期待より薄いものであった。 In general, it is considered that the addition of an oligomer as a photocuring aid improves the development resistance and improves the physical properties of the obtained cured product. Conventionally, there has been an example of using 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.
　エポキシ（メタ）アクリレートオリゴマーは水酸基を多く含有するため、目的とする耐現像性の向上を阻害する効果が確認されていた。一般的に水酸基の存在は密着性を向上させるなどの効果はあるが、その反面、現像性や親水性が向上するためにＰＣＴ耐性、絶縁信頼性を悪化させることが確認されている。更にはエポキシ樹脂より合成されていることから塩素イオン不純物が非常に多く混入するため、絶縁信頼性に悪影響を与えることが懸念され、幅広く用いられてはいなかった。 Since 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.
　一方、本実施形態の感光性樹脂はフェノール樹脂を出発原料として得ることができ、塩素イオン不純物がほとんどない感光性樹脂を与えることができ、塩素イオン不純物濃度を大幅に抑えることができる。このような感光性樹脂の塩素イオン不純物含有量は１００ｐｐｍ以下であることが好ましく、更に好ましくは５０ｐｐｍ以下である。 On the other hand, 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.
　また、このような方法により、実質的に水酸基を含まない感光性樹脂を得ることができる。なお、実質的に水酸基を含まないとは、微量の水酸基を含むことが許容されることを意味する。 Further, by such a method, 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.
　更に母骨格が優れた疎水性、耐熱性を有することから従来では確認されなかった優れた耐現像性、ＰＣＴ耐性、絶縁信頼性を与えることが明らかとなった。
　このように、本実施形態の感光性樹脂は塩素イオン不純物を抑え、実質的に水酸基を含まず、良好な物性を有する母骨格由来の優れた絶縁信頼性、ＰＣＴ耐性を発現させることが可能となる。 Furthermore, since 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.
As described above, 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.
　本実施形態の感光性樹脂に用いられるフェノール樹脂は、ビフェニル骨格、或いはフェニレン骨格、又はその両方の骨格を有し、フェノール性水酸基含有化合物としてフェノール、 ｏ－クレゾール、ｐ－クレゾール、ｍ－クレゾール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、２，６－キシレノール、３，４－キシレノール、３，５－キシレノール、カテコール、レゾルシノール、ハイドロキノン、メチルハイドロキノン、２，６－ジメチルハイドロキノン、トリメチルハイドロキノン、ピロガロール、フロログルシノール等を用いることで様々な骨格を有するフェノール樹脂を誘導することが可能となる。即ち、目的とする諸特性を考慮した上で様々な分子設計を行うことができる。 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, ゾ ー ル 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 By using hydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc., it becomes possible to derive phenol resins having various skeletons. In other words, various molecular designs can be performed in consideration of the target properties.
　本実施形態の感光性樹脂に用いられるアルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、トリメチレンオキサイド、テトラヒドロフラン、テトラヒドロピラン等が挙げられ、好ましくはエチレンオキサイド、プロピレンオキサイドが価格、供給体制の面から良い。これらアルキレンオキサイドは単独で又は２種類以上を混合して用いることができる。 Examples of the alkylene oxide used in the photosensitive resin of the present embodiment include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. Preferably, 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.
　また、シクロカーボネート化合物としては、公知のカーボネート化合物が使用でき、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、２，３－カーボネートプロピルメタクリレートなどが挙げられ、好ましくは５員環のエチレンカーボネート、プロピレンカーボネートが反応性、供給体制の面から良い。これらのカーボネート化合物は、単独で又は２種類以上を混合して用いることができる。 Further, as the 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.
　これらアルキレンオキサイド又はシクロカーボネート化合物は、一般式（１）に示す構造を有する樹脂の対応するフェノール樹脂のフェノール性水酸基に、塩基性触媒を用いて、付加反応させることにより、フェノール性水酸基からアルコール性水酸基を持つ樹脂に変性できる。 These 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.
　不飽和基含有モノカルボン酸としては、（メタ）アクリル酸、あるいはさらに、ヒドロキシエチル（メタ） アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、フェニルグリシジル（メタ）アクリレート、（メタ）アクリル酸カプロラクトン付加物などの水酸基含有アクリレートの不飽和二塩基酸無水物付加物などが挙げられ、より好ましくは（メタ）アクリル酸である。これら不飽和基含有モノカルボン酸は単独で又は２種以上を組み合わせて用いることができる。 Examples of unsaturated group-containing monocarboxylic acids include (meth) acrylic acid, or, further, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, penta Examples include 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.
　一般式（１）～（３）に示す構造を有する感光性樹脂は一般式（１）に示したｎ＋ｍが１．５～６．０の範囲であることが好ましい。ｎ＋ｍが１．５以下であると分子量が小さいことから、目的とする諸特性の向上が期待できない場合がある。一方、６．０以上であると現像性に悪影響を与える可能性がある。一般式（１）～（３）に示す構造を有する感光性樹脂の最適なｎは２．０～５．０程度である。 In the photosensitive resin having the structure represented by the general formulas (1) to (3), n + m represented by the general formula (1) is preferably in the range of 1.5 to 6.0. When 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.
　本実施形態の感光性樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に１，０００～３０，０００であることが好ましい。重量平均分子量が１，０００未満であると、本性能を十分に発揮できないことがある。一方、重量平均分子量が３０，０００を超えると、現像性が著しく悪くなることがあり、レジスト組成物としての現像性を大幅に低下させることがある。より好ましくは１，０００～２０，０００の範囲である。 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.
　このような感光性樹脂の配合量は、カルボキシル基含有樹脂１００質量部に対して、５～６０質量部であることが好ましい。配合量が５．０質量部未満であると、諸特性に与える効果は乏しく、６０質量部を超えると、アルカリ現像液に対する現像性を低下させることが懸念される。より好ましくは、１０～５０質量部である。 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. When 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.
　第一の実施形態にかかる光硬化性熱硬化性樹脂組成物に用いられるカルボキシル基含有樹脂としては、公知のカルボキシル基含有樹脂を用いることができる。好ましくは、絶縁信頼性を悪くしない（ハロゲン化物イオン含有量が非常に少ない）と考えられるカルボキシル基含有樹脂として、エポキシ樹脂を出発原料として使用していないカルボキシル基含有樹脂を用いることが望ましい。それらの中でも、分子中にエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂が、光硬化性や耐現像性の面から好ましい。そして、その不飽和二重結合は、アクリル酸もしくはメタクリル酸又はそれらの誘導体由来のものが好ましい。尚、エチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のみを用いる場合、組成物を光硬化性とするためには、後述するような分子中に１個以上のエチレン性不飽和基を有する化合物（感光性モノマー）を併用する必要がある。 As 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. Preferably, it is desirable to use 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). Among them, 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. When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, one or more ethylenically unsaturated groups are contained in the molecule as described later. It is necessary to use a compound (photosensitive monomer) having
　このようなカルボキシル基含有樹脂の具体例としては、例えば以下に列挙するような化合物（オリゴマー及びポリマーのいずれでもよい）が挙げられる。
（１）後述する２官能又はそれ以上の多官能（固形）エポキシ樹脂に（メタ）アクリル酸を反応させ、側鎖に存在する水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 Specific examples of such a carboxyl group-containing resin include the compounds listed below (any of oligomers and polymers).
(1) (Meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, which will be described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride is added.
（２）後述する２官能（固形）エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に（メタ）アクリル酸を反応させ、生じた水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂。 (2) A polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin.
（３）１分子中に複数のエポキシ基を有するエポキシ化合物に、１分子中に少なくとも１個のアルコール性水酸基と１個のフェノール性水酸基を有する化合物と、（メタ）アクリル酸等の不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、アジピン酸等の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (3) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group such as (meth) acrylic acid 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.
（４）ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ノボラック型フェノール樹脂、ポリ－ｐ－ヒドロキシスチレン、ナフトールとアルデヒド類の縮合物、ジヒドロキシナフタレンとアルデヒド類との縮合物などの１分子中に複数のフェノール性水酸基を有する化合物と、エチレンオキサイド、プロピレンオキサイドなどのアルキレンオキサイドとを反応させて得られる反応生成物に、（メタ）アクリル酸等の不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (4) Bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. Reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid with a reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
（５）１分子中に複数のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネートなどの環状カーボネート化合物とを反応させて得られる反応生成物に、（メタ）アクリル酸等の不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。 (5) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is added to an unsaturated group-containing compound such as (meth) acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a carboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.
（６）脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネート化合物と、ポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールＡ系アルキレンオキサイド付加体ジオール、フェノール性ヒドロキシル基及びアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるウレタン樹脂の末端に酸無水物を反応させてなる末端カルボキシル基含有ウレタン樹脂。 (6) 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.
（７）ジイソシアネートと、ジメチロールプロピオン酸、ジメチロール酪酸等のカルボキシル基含有ジアルコール化合物と、ジオール化合物との重付加反応によるカルボキシル基含有ウレタン樹脂の合成中に、ヒドロキシアルキル（メタ）アクリレート等の分子中に１つの水酸基と１つ以上の（メタ）アクリロイル基を有する化合物を加え、末端（メタ）アクリル化したカルボキシル基含有ウレタン樹脂。 (7) During synthesis of 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.
（８）ジイソシアネートと、カルボキシル基含有ジアルコール化合物と、ジオール化合物との重付加反応によるカルボキシル基含有ウレタン樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物など、分子中に１つのイソシアネート基と１つ以上の（メタ）アクリロイル基を有する化合物を加え、末端（メタ）アクリル化したカルボキシル基含有ウレタン樹脂。 (8) During synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. 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.
（９）（メタ）アクリル酸等の不飽和カルボン酸と、スチレン、α－メチルスチレン、低級アルキル（メタ）アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。 (9) 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, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
（１０）後述する多官能オキセタン樹脂に、アジピン酸、フタル酸、ヘキサヒドロフタル酸等のジカルボン酸を反応させ、生じた１級の水酸基に、２塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂に、さらにグリシジル（メタ）アクリレート、α－メチルグリシジル（メタ）アクリレート等の１分子中に１つのエポキシ基と１つ以上の（メタ）アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。 (10) 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 α-methylglycidyl (meth) acrylate to the resin. Resin.
（１１）前記（１）～（１０）のカルボキシル基含有樹脂に、１分子中に環状エーテル基と（メタ）アクリロイル基を有する化合物を付加させたカルボキシル基含有感光性樹脂。なお、本明細書において、（メタ）アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語で、他の類似の表現についても同様である。 (11) 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). In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
　これらカルボキシル基含有樹脂の中でも、上述したように、エポキシ樹脂を出発原料として用いていないカルボキシル基含有樹脂を好適に用いることができる。このようなカルボキシル基含有樹脂は、エポキシ樹脂を出発原料として用いていないため、塩素イオン不純物が非常に少ないといった特徴がある。本実施形態に好適に用いられるカルボキシル基含有樹脂の塩素イオン不純物含有量は１００ｐｐｍ以下、より好ましくは５０ｐｐｍ以下、さらに好ましくは３０ｐｐｍ以下である。従って、上記に列挙したカルボキシル基含有樹脂（４）～（８）が特に好適に用いることができる。 Among these carboxyl group-containing resins, as described above, 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.
　また、エポキシ樹脂を出発原料として用いていないカルボキシル基含有樹脂は、水酸基を含まない樹脂を容易に得ることができる。一般的に水酸基の存在は水素結合による密着性の向上など優れた特徴も有しているが、著しく耐湿性を低下させることが知られている。以下に、一般的なソルダーレジストに使用されているエポキシアクリレート変性樹脂と比較した、エポキシ樹脂を出発原料として用いていないカルボキシル基含有樹脂の優れた点を説明する。 Also, 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. In general, 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. Below, 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.
　塩素分のないフェノールノボラック樹脂は、容易に入手することができる。これをアルキルオキサイド変性したフェノール樹脂の部分的なアクリル化、及び酸無水物の導入により、二重結合当量３００～５５０、酸価４０～１２０ｍｇＫＯＨ／ｇの範囲で理論上水酸基を有さない樹脂を得ることが可能である。 フ ェ ノ ー ル Phenol novolac resin without chlorine can be easily obtained. By partially acrylating a phenol resin modified with an alkyl oxide and introducing an acid anhydride, 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.
　一方、類似のフェノールノボラック樹脂から合成されたエポキシ樹脂のエポキシ基を全てアクリル化し、全ての水酸基に酸無水物を導入すると、二重結合当量４００～５００で酸価が非常に大きくなってしまい、露光後でも耐現像性を有する塗膜が得られなくなる。さらには、酸価が高いことから、耐水性に劣り、絶縁信頼性、ＰＣＴ耐性を著しく低下させる。即ち、類似のフェノールノボラック型エポキシ樹脂から誘導されたエポキシアクリレート系樹脂から完全に水酸基を無くすことは非常に困難である。 On the other hand, when all the epoxy groups of an epoxy resin synthesized from a similar phenol novolac resin are acrylated and acid anhydrides are introduced into all the hydroxyl groups, the acid value becomes very large with a double bond equivalent of 400 to 500, Even after exposure, a film having development resistance cannot be obtained. Furthermore, since the acid value is high, the water resistance is inferior, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.
　また、ウレタン樹脂も、水酸基とイソシアネート基の当量を合わせることにより、水酸基を含まない樹脂を容易に合成することができる。好ましい樹脂は、ホスゲンを出発原料として用いていないイソシアネート化合物、エピハロヒドリンを使用しない原料から合成される塩素イオン不純物量３０ｐｐｍ以下のカルボキシル基含有樹脂であり、さらに好ましくは水酸基を理論上含まないように合成した樹脂である。 Also, 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.
　このような観点から、先に具体例として示したカルボキシル基含有樹脂（１）～（３）も用いることができるが、半導体パッケージ用ソルダーレジストとしてより優れたＰＣＴ耐性、ＨＡＳＴ耐性、冷熱衝撃耐性を有するソルダーレジスト組成物を得るためには、前記カルボキシル基含有樹脂（４）～（８）がより好適に用いることができる。 From this point of view, 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. In order to obtain a solder resist composition having the above, the carboxyl group-containing resins (4) to (8) can be more preferably used.
　また、先に示した不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂（９）に対し、一分子中に環状エーテル基と（メタ）アクリロイル基を有する化合物として３，４－エポキシシクロヘキシルメチル（メタ）アクリレートを反応させたカルボキシル基含有感光性樹脂も、脂環式エポキシを使用していることから塩素イオン不純物が少なく、好適に用いることができる。 In addition, as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, 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.
　一方、カルボキシル基含有樹脂（９）に、１分子中に環状エーテル基と（メタ）アクリロイル基を有する化合物としてグリシジル（メタ）アクリレートを反応させたものや、不飽和基含有化合物としてグリシジル（メタ）アクリレートを共重合させたものは、塩素イオン不純物量が多くなる懸念がある。また、ウレタン樹脂の合成の際にジオール化合物としてエポキシアクリレート変性原料を使用することもできる。塩素イオン不純物は入ってしまうが、塩素イオン不純物量をコントロールできるといった点から使用することは可能である。 On the other hand, 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. Those obtained by copolymerizing acrylates have a concern that the amount of chlorine ion impurities increases. Moreover, an epoxy acrylate modified raw material can also be used as a diol compound in the synthesis of a urethane resin. Although chlorine ion impurities enter, it can be used from the viewpoint that the amount of chlorine ion impurities can be controlled.
　上記のようなカルボキシル基含有樹脂は、バックボーン・ポリマーの側鎖に多数のカルボキシル基を有するため、アルカリ水溶液による現像が可能になる。
　また、上記カルボキシル基含有樹脂の酸価は、４０～１５０ｍｇＫＯＨ／ｇの範囲が好ましい。酸価が４０ｍｇＫＯＨ／ｇ未満であるとアルカリ現像が困難となり、一方、１５０ｍｇＫＯＨ／ｇを超えると現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となる。より好ましくは４０～１３０ｍｇＫＯＨ／ｇである。 Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with an alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH / g. When the acid value is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when 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.
　また、上記カルボキシル基含有樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に２，０００～１００，０００であることが好ましい。重量平均分子量が２，０００未満であると、タックフリー性能が劣ることがあり、露光後の塗膜の耐湿性が悪く、現像時に膜減りが生じ、解像度が大きく劣ることがある。一方、重量平均分子量が１００，０００を超えると、現像性が著しく悪くなることがあり、貯蔵安定性が劣ることがある。より好ましくは２，０００～８０，０００の範囲である。 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.
　このようなカルボキシル基含有樹脂の配合量は、全組成物中に、２０～６０質量％、好ましくは３０～５０質量％である。上記範囲より少ない場合、塗膜強度が低下したりする。一方、上記範囲より多い場合、粘性が高くなったり、塗布性等が低下する。 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.
　なお、第一の実施形態に係る光硬化性熱硬化性樹脂組成物に用いられるカルボキシル基含有樹脂として、後述する第二の実施形態に係る一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂を用いることもできる。 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.
　本実施形態の光硬化性熱硬化性樹脂組成物に用いられる光重合開始剤としては、オキシムエステル基を有するオキシムエステル系光重合開始剤、α－アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤からなる群から選択される１種以上の光重合開始剤を使用することができる。 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 α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide system. One or more photopolymerization initiators selected from the group consisting of photopolymerization initiators can be used.
　オキシムエステル系光重合開始剤としては、市販品として、チバ・ジャパン社製のＣＧＩ－３２５、イルガキュアー ＯＸＥ０１、イルガキュアー ＯＸＥ０２、アデカ社製のＮ－１９１９、アデカアークルズ ＮＣＩ－８３１などが挙げられる。また、分子内に２個のオキシムエステル基を有する光重合開始剤も好適に用いることができ、具体的には、下記一般式（８）で表されるカルバゾール構造を有するオキシムエステル化合物が挙げられる。 Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure® OXE01, Irgacure® OXE02 manufactured by Ciba Japan, N-1919 manufactured by Adeka, and Adeka Arcles® NCI-831. . In addition, 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). .
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｘは、水素原子、炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、フェニル基、フェニル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１～１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、アントリレン、チエニレン、フリレン、２，５－ピロール－ジイル、４，４’－スチルベン－ジイル、４，２’－スチレン－ジイルを表し、ｎは０又は１の整数である。）
　特に式中、Ｘ、Ｙが、それぞれ、メチル基又はエチル基であり、Ｚはメチル又はフェニルであり、ｎは０であり、Ａｒは、フェニレン、ナフチレン、又はチエニレンであることが好ましい。
Figure JPOXMLDOC01-appb-C000018
 (In the formula, 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). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And 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. Alkyl groups having 8 to 8 alkoxy groups, halogen groups, phenyl groups, phenyl groups (alkyl groups having 1 to 17 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, amino groups, alkyl groups having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthrylene, thienylene, Furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)
In particular, in the formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is preferably phenylene, naphthylene, or thienylene.
　このようなオキシムエステル系光重合開始剤の配合量は、前記カルボキシル基含有樹脂１００質量部に対して、０．０１～５質量部とすることが好ましい。配合量が０．０１質量部未満であると、銅上での光硬化性が不足し、塗膜が剥離するとともに、耐薬品性などの塗膜特性が低下する。一方、５質量部を超えると、ソルダーレジスト塗膜表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。より好ましくは、０．５～３質量部である。 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. When 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. On the other hand, when 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.
　α－アミノアセトフェノン系光重合開始剤としては、具体的には２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、Ｎ，Ｎ－ジメチルアミノアセトフェノンなどが挙げられる。市販品としては、チバ・ジャパン社製のイルガキュアー９０７、イルガキュアー３６９、イルガキュアー３７９などが挙げられる。 Specific examples of α-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.
　アシルホスフィンオキサイド系光重合開始剤としては、具体的には２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス(２，４，６－トリメチルベンゾイル)－フェニルホスフィンオキサイド、ビス(２，６－ジメトキシベンゾイル)－２，４，４－トリメチル－ペンチルホスフィンオキサイドなどが挙げられる。市販品としては、ＢＡＳＦ社製のルシリンＴＰＯ、チバ・ジャパン社製のイルガキュアー８１９などが挙げられる。 Specific examples of 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.
　これらα－アミノアセトフェノン系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤の配合量は、前記カルボキシル基含有樹脂１００質量部に対して、０．０１～１５質量部であることが好ましい。配合量が０．０１質量部未満であると、同様に銅上での光硬化性が不足し、塗膜が剥離するとともに、耐薬品性などの塗膜特性が低下する。一方、１５質量部を超えると、アウトガスの低減効果が得られず、さらにソルダーレジスト塗膜表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。より好ましくは０．５～１０質量部である。 The blending amount of these α-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.
　その他、本実施形態の光硬化性熱硬化性樹脂組成物に好適に用いることができる光重合開始剤、光開始助剤及び増感剤としては、ベンゾイン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、３級アミン化合物、及びキサントン化合物などを挙げることができる。 In addition, as 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.
　ベンゾイン化合物としては、具体的には、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどが挙げられる。 Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
　アセトフェノン化合物としては、具体的には、例えばアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノンなどが挙げられる。 Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
　アントラキノン化合物としては、具体的には、例えば２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノンなどが挙げられる。 Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
　チオキサントン化合物としては、具体的には、例えば２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントンなどが挙げられる。 Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
　ケタール化合物としては、具体的には、例えばアセトフェノンジメチルケタール、ベンジルジメチルケタールなどが挙げられる。 Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
　ベンゾフェノン化合物としては、具体的には、例えばベンゾフェノン、４－ベンゾイルジフェニルスルフィド、４－ベンゾイル－４’－メチルジフェニルスルフィド、４－ベンゾイル－４’－エチルジフェニルスルフィド、４－ベンゾイル－４’－プロピルジフェニルスルフィドなどが挙げられる。 Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
　３級アミン化合物としては、具体的には、例えばエタノールアミン化合物、ジアルキルアミノベンゼン構造を有する化合物、例えば、市販品では、４，４’－ジメチルアミノベンゾフェノン（日本曹達社製ニッソキュアーＭＡＢＰ）、４，４’－ジエチルアミノベンゾフェノン（保土ヶ谷化学社製ＥＡＢ）などのジアルキルアミノベンゾフェノン、７－（ジエチルアミノ）－４－メチル－２Ｈ－１－ベンゾピラン－２－オン（７－（ジエチルアミノ）－４－メチルクマリン）などのジアルキルアミノ基含有クマリン化合物、４－ジメチルアミノ安息香酸エチル（日本化薬社製カヤキュアーＥＰＡ）、２－ジメチルアミノ安息香酸エチル（インターナショナルバイオ－シンセエティックス社製Ｑｕａｎｔａｃｕｒｅ　ＤＭＢ）、４－ジメチルアミノ安息香酸（ｎ－ブトキシ）エチル（インターナショナルバイオ－シンセエティックス社製Ｑｕａｎｔａｃｕｒｅ　ＢＥＡ）、ｐ－ジメチルアミノ安息香酸イソアミルエチルエステル（日本化薬社製カヤキュアーＤＭＢＩ）、４－ジメチルアミノ安息香酸２－エチルヘキシル（Ｖａｎ　Ｄｙｋ社製Ｅｓｏｌｏｌ　５０７）、４，４’－ジエチルアミノベンゾフェノン（保土ヶ谷化学社製ＥＡＢ）などが挙げられる。 Specific examples of 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. 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. Kayacure DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like.
　これらのうち、チオキサントン化合物及び３級アミン化合物が好ましい。特に、チオキサントン化合物が含まれることが、深部硬化性の面から好ましい。中でも、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントンなどのチオキサントン化合物を含むことが好ましい。 Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Of these, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
　このようなチオキサントン化合物の配合量は、前記カルボキシル基含有樹脂１００質量部に対して、２０質量部以下であることが好ましい。配合量が２０質量部を超えると、厚膜硬化性が低下するとともに、製品のコストアップに繋がる。より好ましくは１０質量部以下である。 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.
　また、３級アミン化合物としては、ジアルキルアミノベンゼン構造を有する化合物が好ましく、中でも、ジアルキルアミノベンゾフェノン化合物、最大吸収波長が３５０～４５０ｎｍにあるジアルキルアミノ基含有クマリン化合物及びケトクマリン類が特に好ましい。 As the tertiary amine compound, 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.
　ジアルキルアミノベンゾフェノン化合物としては、４，４’－ジエチルアミノベンゾフェノンが、毒性も低く好ましい。ジアルキルアミノ基含有クマリン化合物は、最大吸収波長が３５０～４１０ｎｍと紫外線領域にあるため、着色が少なく、無色透明な感光性組成物はもとより、着色顔料を用い、着色顔料自体の色を反映した着色ソルダーレジスト膜を提供することが可能となる。特に、７－（ジエチルアミノ）－４－メチル－２Ｈ－１－ベンゾピラン－２－オンが、波長４００～４１０ｎｍのレーザー光に対して優れた増感効果を示すことから好ましい。 As the 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. In particular, 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.
　このような３級アミン化合物の配合量は、前記カルボキシル基含有樹脂１００質量部に対して、０．１～２０質量部であることが好ましい。配合量が０．１質量部未満であると、十分な増感効果を得ることができない傾向にある。一方、２０質量部を超えると、３級アミン化合物による乾燥ソルダーレジスト塗膜の表面での光吸収が激しくなり、深部硬化性が低下する傾向がある。より好ましくは０．１～１０質量部である。これらの光重合開始剤、光開始助剤及び増感剤は、単独で又は２種類以上の混合物として使用することができる。 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. When the blending amount is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when 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. These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
　このような光重合開始剤、光開始助剤、及び増感剤の総量は、前記カルボキシル基含有樹脂１００質量部に対して３５質量部以下であることが好ましい。３５質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。 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.
　なお、これら光重合開始剤、光開始助剤、及び増感剤は、特定の波長を吸収するため、場合によっては感度が低くなり、紫外線吸収剤として働くことがある。しかしながら、これらは組成物の感度を向上させることだけの目的に用いられるものではない。必要に応じて特定の波長の光を吸収させて、表面の光反応性を高め、レジストのライン形状及び開口を垂直、テーパー状、逆テーパー状に変化させるとともに、ライン幅や開口径の加工精度を向上させることができる。 In addition, since 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.
　さらに本実施形態の光硬化性熱硬化性樹脂組成物には、耐熱性を付与するために、熱硬化性成分を加えることができる。熱硬化性成分としては、具体的にはブロックイソシアネート化合物、アミノ樹脂、マレイミド化合物、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、多官能エポキシ化合物、多官能オキセタン化合物、エピスルフィド樹脂などの公知の熱硬化性樹脂が使用できる。これらの中でも好ましい熱硬化性成分は、１分子中に複数の環状エーテル基及び／又は環状チオエーテル基（以下、環状（チオ）エーテル基と略称する）を有する熱硬化性成分である。これら環状（チオ）エーテル基を有する熱硬化性成分は、市販されている種類が多く、その構造によって多様な特性を付与することができる。 Furthermore, a thermosetting component can be added to the photocurable thermosetting resin composition of the present embodiment in order to impart heat resistance. Specific examples of 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. Among these, 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. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
　このような分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分は、分子中に３、４又は５員環の環状エーテル基又は環状チオエーテル基のいずれか一方又は２種類の基を複数有する化合物であり、例えば、分子中に複数のエポキシ基を有する化合物、すなわち多官能エポキシ化合物、分子中に複数のオキセタニル基を有する化合物、すなわち多官能オキセタン化合物、分子中に複数のチオエーテル基を有する化合物、すなわちエピスルフィド樹脂などが挙げられる。 Such a 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. A compound having the same, that is, an episulfide resin.
　多官能エポキシ化合物としては、例えば、ジャパンエポキシレジン社製のｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００４、ＤＩＣ社製のエピクロン８４０、エピクロン８５０、エピクロン１０５０、エピクロン２０５５、東都化成社製のエポトートＹＤ－０１１、ＹＤ－０１３、ＹＤ－１２７、ＹＤ－１２８、ダウケミカル社製のＤ．Ｅ．Ｒ．３１７、Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．６６１、Ｄ．Ｅ．Ｒ．６６４、チバ・ジャパン社のアラルダイド６０７１、アラルダイド６０８４、アラルダイドＧＹ２５０、アラルダイドＧＹ２６０、住友化学工業社製のスミ－エポキシＥＳＡ－０１１、ＥＳＡ－０１４、ＥＬＡ－１１５、ＥＬＡ－１２８、旭化成工業社製のＡ．Ｅ．Ｒ．３３０、Ａ．Ｅ．Ｒ．３３１、Ａ．Ｅ．Ｒ．６６１、Ａ．Ｅ．Ｒ．６６４等（何れも商品名）のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲＹＬ９０３、ＤＩＣ社製のエピクロン１５２、エピクロン１６５、東都化成社製のエポトートＹＤＢ－４００、ＹＤＢ－５００、ダウケミカル社製のＤ．Ｅ．Ｒ．５４２、チバ・ジャパン社製のアラルダイド８０１１、住友化学工業社製のスミ－エポキシＥＳＢ－４００、ＥＳＢ－７００、旭化成工業社製のＡ．Ｅ．Ｒ．７１１、Ａ．Ｅ．Ｒ．７１４等（何れも商品名）のブロム化エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲ１５２、ｊＥＲ１５４、ダウケミカル社製のＤ．Ｅ．Ｎ．４３１、Ｄ．Ｅ．Ｎ．４３８、ＤＩＣ社製のエピクロンＮ－７３０、エピクロンＮ－７７０、エピクロンＮ－８６５、東都化成社製のエポトートＹＤＣＮ－７０１、ＹＤＣＮ－７０４、チバ・ジャパン社製のアラルダイドＥＣＮ１２３５、アラルダイドＥＣＮ１２７３、アラルダイドＥＣＮ１２９９、アラルダイドＸＰＹ３０７、日本化薬社製のＥＰＰＮ－２０１、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０４Ｓ、ＲＥ－３０６、住友化学工業社製のスミ－エポキシＥＳＣＮ－１９５Ｘ、ＥＳＣＮ－２２０、旭化成工業社製のＡ．Ｅ．Ｒ．ＥＣＮ－２３５、ＥＣＮ－２９９等（何れも商品名）のノボラック型エポキシ樹脂；ＤＩＣ社製のエピクロン８３０、ジャパンエポキシレジン社製ｊＥＲ８０７、東都化成社製のエポトートＹＤＦ－１７０、ＹＤＦ－１７５、ＹＤＦ－２００４、チバ・ジャパン社製のアラルダイドＸＰＹ３０６等（何れも商品名）のビスフェノールＦ型エポキシ樹脂；東都化成社製のエポトートＳＴ－２００４、ＳＴ－２００７、ＳＴ－３０００（商品名）等の水添ビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲ６０４、東都化成社製のエポトートＹＨ－４３４、チバ・ジャパン社製のアラルダイドＭＹ７２０、住友化学工業社製のスミ－エポキシＥＬＭ－１２０等（何れも商品名）のグリシジルアミン型エポキシ樹脂；チバ・ジャパン社製のアラルダイドＣＹ－３５０（商品名）等のヒダントイン型エポキシ樹脂；ダイセル化学工業社製のセロキサイド２０２１、チバ・ジャパン社製のアラルダイドＣＹ１７５、ＣＹ１７９等（何れも商品名）の脂環式エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ－９３３、ダウケミカル社製のＴ．Ｅ．Ｎ．、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２等（何れも商品名）のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン社製のＹＬ－６０５６、ＹＸ－４０００、ＹＬ－６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬社製ＥＢＰＳ－２００、旭電化工業社製ＥＰＸ－３０、ＤＩＣ社製のＥＸＡ－１５１４（商品名）等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲ１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン社製のｊＥＲＹＬ－９３１、チバ・ジャパン社製のアラルダイド１６３等（何れも商品名）のテトラフェニロールエタン型エポキシ樹脂；チバ・ジャパン社製のアラルダイドＰＴ８１０、日産化学工業社製のＴＥＰＩＣ等（何れも商品名）の複素環式エポキシ樹脂；日本油脂社製ブレンマーＤＧＴ等のジグリシジルフタレート樹脂；東都化成社製ＺＸ－１０６３等のテトラグリシジルキシレノイルエタン樹脂；新日鐵化学社製ＥＳＮ－１９０、ＥＳＮ－３６０、ＤＩＣ社製ＨＰ－４０３２、ＥＸＡ－４７５０、ＥＸＡ－４７００等のナフタレン基含有エポキシ樹脂；ＤＩＣ社製ＨＰ－７２００、ＨＰ－７２００Ｈ等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂社製ＣＰ－５０Ｓ、ＣＰ－５０Ｍ等のグリシジルメタアクリレート共重合系エポキシ樹脂；さらにシクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂；エポキシ変性のポリブタジエンゴム誘導体（例えばダイセル化学工業製ＰＢ－３６００等）、ＣＴＢＮ変性エポキシ樹脂（例えば東都化成社製のＹＲ－１０２、ＹＲ－４５０等）等が挙げられるが、これらに限られるものではない。これらのエポキシ樹脂は、単独で又は２種以上を組み合わせて用いることができる。 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. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldide ECN1235, Araldide ECN1273, Araldide ECN1299, manufactured by Ciba Japan Araldide XPY307, Nippon Kayaku EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (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. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as Epoxy Resin's jER157S (trade name); Tetraphenylolethane type such as Japan Epoxy Resin's jERYL-931, Ciba Japan's Araldide 163, etc. (all trade names) 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. PB-3600, etc.), CTBN modified epoxy resin (e.g., Tohto Kasei Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more.
　多官能オキセタン化合物としては、ビス［（３－メチル－３－オキセタニルメトキシ）メチル］エーテル、ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エーテル、１，４－ビス［（３－メチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、（３－メチル－３－オキセタニル）メチルアクリレート、（３－エチル－３－オキセタニル）メチルアクリレート、（３－メチル－３－オキセタニル）メチルメタクリレート、（３－エチル－３－オキセタニル）メチルメタクリレートやそれらのオリゴマー又は共重合体等の多官能オキセタン類の他、オキセタンアルコールとノボラック樹脂、ポリ（ｐ－ヒドロキシスチレン）、カルド型ビスフェノール類、カリックスアレーン類、カリックスレゾルシンアレーン類、又はシルセスキオキサンなどの水酸基を有する樹脂とのエーテル化物などが挙げられる。その他、オキセタン環を有する不飽和モノマーとアルキル（メタ）アクリレートとの共重合体なども挙げられる。 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), cardo bisphenol S, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.
　エピスルフィド樹脂としては、例えば、ジャパンエポキシレジン社製のＹＬ７０００（ビスフェノールＡ型エピスルフィド樹脂）などが挙げられる。また、同様の合成方法を用いて、ノボラック型エポキシ樹脂のエポキシ基の酸素原子を硫黄原子に置き換えたエピスルフィド樹脂なども用いることができる。 Examples of the episulfide resin 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.
　このような分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分の配合量は、前記カルボキシル基含有樹脂のカルボキシル基１当量に対して、０．６～２．５当量が好ましい。配合量が０．６未満である場合、ソルダーレジスト膜にカルボキシル基が残り、耐熱性、耐アルカリ性、電気絶縁性などが低下する。一方、２．５当量を超える場合、低分子量の環状（チオ）エーテル基が乾燥塗膜に残存することにより、塗膜の強度などが低下する。より好ましくは、０．８～２．０当量である。 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. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when 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.
　さらに、好適に用いることができる熱硬化性成分として、メラミン誘導体、ベンゾグアナミン誘導体などが挙げられる。例えばメチロールメラミン化合物、メチロールベンゾグアナミン化合物、メチロールグリコールウリル化合物及びメチロール尿素化合物などがある。さらに、アルコキシメチル化メラミン化合物、アルコキシメチル化ベンゾグアナミン化合物、アルコキシメチル化グリコールウリル化合物及びアルコキシメチル化尿素化合物は、それぞれのメチロールメラミン化合物、メチロールベンゾグアナミン化合物、メチロールグリコールウリル化合物及びメチロール尿素化合物のメチロール基をアルコキシメチル基に変換することにより得られる。このアルコキシメチル基の種類については特に限定されるものではなく、例えばメトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基等とすることができる。特に人体や環境に優しいホルマリン濃度が０．２％以下のメラミン誘導体が好ましい。 Furthermore, examples of thermosetting components that can be suitably used include melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, 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. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
　これらの市販品としては、例えばサイメル３００、同３０１、同３０３、同３７０、同３２５、同３２７、同７０１、同２６６、同２６７、同２３８、同１１４１、同２７２、同２０２、同１１５６、同１１５８、同１１２３、同１１７０、同１１７４、同ＵＦＲ６５、同３００（以上、三井サイアナミッド社製）、ニカラックＭｘ－７５０、同Ｍｘ－０３２、同Ｍｘ－２７０、同Ｍｘ－２８０、同Ｍｘ－２９０、同Ｍｘ－７０６、同Ｍｘ－７０８、同Ｍｘ－４０、同Ｍｘ－３１、同Ｍｓ－１１、同Ｍｗ－３０、同Ｍｗ－３０ＨＭ、同Ｍｗ－３９０、同Ｍｗ－１００ＬＭ、同Ｍｗ－７５０ＬＭ、（以上、三和ケミカル社製）等を挙げることができる。これら熱硬化性成分は単独又は２種以上を併用することができる。 Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx-290 Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw-750LM (Above, manufactured by Sanwa Chemical Co., Ltd.). These thermosetting components can be used alone or in combination of two or more.
　また、本実施形態の光硬化性熱硬化性樹脂組成物には、組成物の硬化性及び得られる硬化膜の強靭性を向上させるために１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物を加えることができる。このような１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物は、１分子中に複数のイソシアネート基を有する化合物、すなわちポリイソシアネート化合物、又は１分子中に複数のブロック化イソシアネート基を有する化合物、すなわちブロックイソシアネート化合物などが挙げられる。 In addition, 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.
　ポリイソシアネート化合物としては、例えば芳香族ポリイソシアネート、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートが用いられる。芳香族ポリイソシアネートの具体例としては、４，４’－ジフェニルメタンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ナフタレン－１，５－ジイソシアネート、ｏ－キシリレンジイソシアネート、ｍ－キシリレンジイソシアネート及び２，４－トリレンダイマーが挙げられる。脂肪族ポリイソシアネートの具体例としては、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、メチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、４，４－メチレンビス（シクロヘキシルイソシアネート）及びイソホロンジイソシアネートが挙げられる。脂環式ポリイソシアネートの具体例としてはビシクロヘプタントリイソシアネートが挙げられる。並びに先に挙げられたイソシアネート化合物のアダクト体、ビューレット体及びイソシアヌレート体が挙げられる。 As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the 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. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
　ブロックイソシアネート化合物に含まれるブロック化イソシアネート基は、イソシアネート基がブロック剤との反応により保護されて一時的に不活性化された基である。所定温度に加熱されたときにそのブロック剤が解離してイソシアネート基が生成する。 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.
　ブロックイソシアネート化合物としては、イソシアネート化合物とイソシアネートブロック剤との付加反応生成物が用いられる。ブロック剤と反応し得るイソシアネート化合物としては、イソシアヌレート型、ビウレット型、アダクト型等が挙げられる。このイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートが用いられる。芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネートの具体例としては、先に例示したような化合物が挙げられる。 As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, 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.
　イソシアネートブロック剤としては、例えば、フェノール、クレゾール、キシレノール、クロロフェノール及びエチルフェノール等のフェノール系ブロック剤；ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム及びβ－プロピオラクタム等のラクタム系ブロック剤；アセト酢酸エチル及びアセチルアセトンなどの活性メチレン系ブロック剤；メタノール、エタノール、プロパノール、ブタノール、アミルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ベンジルエーテル、グリコール酸メチル、グリコール酸ブチル、ジアセトンアルコール、乳酸メチル及び乳酸エチル等のアルコール系ブロック剤；ホルムアルデヒドキシム、アセトアルドキシム、アセトキシム、メチルエチルケトキシム、ジアセチルモノオキシム、シクロヘキサンオキシム等のオキシム系ブロック剤；ブチルメルカプタン、ヘキシルメルカプタン、ｔ－ブチルメルカプタン、チオフェノール、メチルチオフェノール、エチルチオフェノール等のメルカプタン系ブロック剤；酢酸アミド、ベンズアミド等の酸アミド系ブロック剤；コハク酸イミド及びマレイン酸イミド等のイミド系ブロック剤；キシリジン、アニリン、ブチルアミン、ジブチルアミン等のアミン系ブロック剤；イミダゾール、２－エチルイミダゾール等のイミダゾール系ブロック剤；メチレンイミン及びプロピレンイミン等のイミン系ブロック剤等が挙げられる。 Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-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 ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is done.
　ブロックイソシアネート化合物は市販のものであってもよく、例えば、スミジュールＢＬ－３１７５、ＢＬ－４１６５、ＢＬ－１１００、ＢＬ－１２６５、デスモジュールＴＰＬＳ－２９５７、ＴＰＬＳ－２０６２、ＴＰＬＳ－２０７８、ＴＰＬＳ－２１１７、デスモサーム２１７０、デスモサーム２２６５（以上、住友バイエルウレタン社製、商品名）、コロネート２５１２、コロネート２５１３、コロネート２５２０（以上、日本ポリウレタン工業社製、商品名）、Ｂ－８３０、Ｂ－８１５、Ｂ－８４６、Ｂ－８７０、Ｂ－８７４、Ｂ－８８２（三井武田ケミカル社製、商品名）、ＴＰＡ－Ｂ８０Ｅ、１７Ｂ－６０ＰＸ、Ｅ４０２－Ｂ８０Ｔ（旭化成ケミカルズ社製、商品名）等が挙げられる。なお、スミジュールＢＬ－３１７５、ＢＬ－４２６５はブロック剤としてメチルエチルオキシムを用いて得られるものである。上記の１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物は、１種を単独で又は２種以上を組み合わせて用いることができる。 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. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Company), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.). Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
　このような１分子中に複数のイソシアネート基又はブロック化イソシアネート基を有する化合物の配合量は、前記カルボキシル基含有樹脂１００質量部に対して、１～１００質量部であることが好ましい。配合量が、１質量部未満の場合、十分な塗膜の強靭性が得られない。一方、１００質量部を超えた場合、保存安定性が低下する。より好ましくは、２～７０質量部である。 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. When the blending amount is less than 1 part by mass, sufficient coating film toughness cannot be obtained. On the other hand, when it exceeds 100 mass parts, storage stability falls. More preferably, it is 2 to 70 parts by mass.
　本実施形態の光硬化性熱硬化性樹脂組成物には、水酸基やカルボキシル基とイソシアネート基との硬化反応を促進させるためにウレタン化触媒を加えることができる。ウレタン化触媒としては錫系触媒、金属塩化物、金属アセチルアセトネート塩、金属硫酸塩、アミン化合物、又は／及びアミン塩よりなる群から選択される１種以上のウレタン化触媒を使用することが好ましい。 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. As 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.
　錫系触媒としては、例えばスタナスオクトエート、ジブチル錫ジラウレートなどの有機錫化合物、無機錫化合物などが挙げられる。
　金属塩化物としては、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ又はＡｌからなる金属の塩化物で、例えば、塩化第二コバルト、塩化第一ニッケル、塩化第二鉄などが挙げられる。
　金属アセチルアセトネート塩としては、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ又はＡｌからなる金属のアセチルアセトネート塩であり、例えば、コバルトアセチルアセトネート、ニッケルアセチルアセトネート、鉄アセチルアセトネートなどが挙げられる。
　金属硫酸塩としては、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｃｕ又はＡｌからなる金属の硫酸塩で、例えば、硫酸銅などが挙げられる。 Examples of the tin-based catalyst 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.
　アミン化合物としては、例えば、従来公知のトリエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル－１，６－ヘキサンジアミン、ビス（２－ジメチルアミノエチル）エーテル、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジエチレントリアミン、Ｎ－メチルモルフォリン、Ｎ－エチルモルフォリン、Ｎ，Ｎ－ジメチルエタノールアミン、ジモルホリノジエチルエーテル、Ｎ－メチルイミダゾール、ジメチルアミノピリジン、トリアジン、Ｎ’－（２－ヒドロキシエチル）－Ｎ，Ｎ，Ｎ’－トリメチルービス（２－アミノエチル）エーテル、Ｎ，Ｎ－ジメチルヘキサノールアミン、Ｎ，Ｎ－ジメチルアミノエトキシエタノール、Ｎ，Ｎ，Ｎ’－トリメチル－Ｎ’－（２－ヒドロキシエチル）エチレンジアミン、Ｎ－（２－ヒドロキシエチル）－Ｎ，Ｎ’，Ｎ”，Ｎ”－テトラメチルジエチレントリアミン、Ｎ－（２－ヒドロキシプロピル）－Ｎ，Ｎ’，Ｎ”，Ｎ”－テトラメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’－トリメチル－Ｎ’－（２－ヒドロキシエチル）プロパンジアミン、Ｎ－メチル－Ｎ’－（２－ヒドロキシエチル）ピペラジン、ビス（Ｎ，Ｎ－ジメチルアミノプロピル）アミン、ビス（Ｎ，Ｎ－ジメチルアミノプロピル）イソプロパノールアミン、２－アミノキヌクリジン、３－アミノキヌクリジン、４－アミノキヌクリジン、２－キヌクリジオール、３－キヌクリジノール、４－キヌクリジノール、１－（２’－ヒドロキシプロピル）イミダゾール、１－（２’－ヒドロキシプロピル）－２－メチルイミダゾール、１－（２’－ヒドロキシエチル）イミダゾール、１－（２’－ヒドロキシエチル）－２－メチルイミダゾール、１－（２’－ヒドロキシプロピル）－２－メチルイミダゾール、１－（３’－アミノプロピル）イミダゾール、１－（３’－アミノプロピル）－２－メチルイミダゾール、１－（３’－ヒドロキシプロピル）イミダゾール、１－（３’－ヒドロキシプロピル）－２－メチルイミダゾール、Ｎ，Ｎ－ジメチルアミノプロピル－Ｎ’－（２－ヒドロキシエチル）アミン、Ｎ，Ｎ－ジメチルアミノプロピル－Ｎ’，Ｎ’－ビス（２－ヒドロキシエチル）アミン、Ｎ，Ｎ－ジメチルアミノプロピル－Ｎ’，Ｎ’－ビス（２－ヒドロキシプロピル）アミン、Ｎ，Ｎ－ジメチルアミノエチル－Ｎ’，Ｎ’－ビス（２－ヒドロキシエチル）アミン、Ｎ，Ｎ－ジメチルアミノエチル－Ｎ’，Ｎ’－ビス（２－ヒドロキシプロピル）アミン、メラミン又は／及びベンゾグアナミンなどが挙げられる。 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) ) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl- N ′-(2-hydroxyethyl) propanediamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropanol Amine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (2′-hydroxyethyl) imidazo 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-amino) Propyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) ) Amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N , N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N Examples include '-bis (2-hydroxypropyl) amine, melamine and / or benzoguanamine.
　アミン塩としては、例えば、ＤＢＵ（１，８－ジアザ－ビシクロ［５，４，０］ウンデセン－７）の有機酸塩系のアミン塩などが挙げられる。
　ウレタン化触媒の配合量は、通常の量的割合で充分であり、例えばカルボキシル基含有樹脂１００質量部に対して、好ましくは０．１～２０質量部、より好ましくは０．５～１０．０質量部である。 Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5,4,0] undecene-7).
The compounding amount of the urethanization catalyst is sufficient in 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.
　分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分を使用する場合、熱硬化触媒を含有することが好ましい。そのような熱硬化触媒としては、例えば、イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、４－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール等のイミダゾール誘導体；ジシアンジアミド、ベンジルジメチルアミン、４－（ジメチルアミノ）－Ｎ，Ｎ－ジメチルベンジルアミン、４－メトキシ－Ｎ，Ｎ－ジメチルベンジルアミン、４－メチル－Ｎ，Ｎ－ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物；トリフェニルホスフィン等のリン化合物などが挙げられる。 When using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Examples of such 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.
　また、市販されているものとしては、例えば四国化成工業社製の２ＭＺ－Ａ、２ＭＺ－ＯＫ、２ＰＨＺ、２Ｐ４ＢＨＺ、２Ｐ４ＭＨＺ（いずれもイミダゾール系化合物の商品名）、サンアプロ社製のＵ－ＣＡＴ（登録商標）３５０３Ｎ、Ｕ－ＣＡＴ３５０２Ｔ（いずれもジメチルアミンのブロックイソシアネート化合物の商品名）、ＤＢＵ、ＤＢＮ、Ｕ－ＣＡＴＳＡ１０２、Ｕ－ＣＡＴ５００２（いずれも二環式アミジン化合物及びその塩）などが挙げられる。特に、これらに限られるものではなく、エポキシ樹脂やオキセタン化合物の熱硬化触媒、もしくはエポキシ基及び／又はオキセタニル基とカルボキシル基の反応を促進するものであればよく、単独で又は２種以上を混合して使用してもかまわない。また、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、２，４－ジアミノ－６－メタクリロイルオキシエチル－Ｓ－トリアジン、２－ビニル－２，４－ジアミノ－Ｓ－トリアジン、２－ビニル－４，６－ジアミノ－Ｓ－トリアジン・イソシアヌル酸付加物、２，４－ジアミノ－６－メタクリロイルオキシエチル－Ｓ－トリアジン・イソシアヌル酸付加物等のＳ－トリアジン誘導体を用いることもでき、好ましくはこれら密着性付与剤としても機能する化合物を上記の熱硬化触媒と併用する。 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. In particular, it is not limited to these, as long as it is a 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. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. Is also used in combination with the above thermosetting catalyst.
　これら熱硬化触媒の配合量は、通常の量的割合で充分であり、例えばカルボキシル基含有樹脂又は分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分１００質量部に対して、好ましくは０．１～２０質量部、より好ましくは０．５～１５．０質量部である。 The compounding amount of these 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.
　本発実施形態の光硬化性熱硬化性樹脂組成物は、着色剤を配合することができる。着色剤としては、赤、青、緑、黄などの公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。但し、環境負荷低減並びに人体への影響の観点からハロゲンを含有しないことが好ましい。 The photocurable thermosetting resin composition of the present embodiment can be blended with a colorant. As the 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.
　赤色着色剤としてはモノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には以下のようなカラ－インデックス（Ｃ．Ｉ．；ザ　ソサイエティ　オブ　ダイヤーズ　アンド　カラリスツ（Ｔｈｅ Ｓｏｃｉｅｔｙ ｏｆ Ｄｙｅｒｓ ａｎｄ Ｃｏｌｏｕｒｉｓｔｓ）発行）番号が付されているものが挙げられる。 Examples of the red colorant 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.
　モノアゾ系：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。
　ジスアゾ系：Pigment Red 37, 38, 41。
　モノアゾレーキ系：Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1,68。 Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
　ベンズイミダゾロン系：Pigment Red 171, 175, 176, 185, 208。
　ぺリレン系：Solvent Red 135, 179、Pigment Red 123, 149, 166, 178, 179, 190, 194, 224。
　ジケトピロロピロール系：Pigment Red 254, 255, 264, 270, 272。
　縮合アゾ系：Pigment Red 220, 144, 166, 214, 220, 221, 242。
　アンスラキノン系：Pigment Red 168, 177, 216,Solvent Red 149, 150, 52, 207。
　キナクリドン系：Pigment Red 122, 202, 206, 207, 209。 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.
　青色着色剤：
　青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント（Pigment）に分類されている化合物、具体的には、下記のようなものを挙げることができる：Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60。染料系としては、Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Blue colorant:
Blue colorants 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. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
　緑色着色剤：
　緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的にはPigment Green 7, 36、Solvent Green 3, 5, 20, 28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。 Green colorant:
Similarly, 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. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
　黄色着色剤：
　黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下のものが挙げられる。
　アントラキノン系：Solvent Yellow 163、Pigment Yellow 24, 108, 193, 147, 199, 202。
　イソインドリノン系：Pigment Yellow 110, 109, 139, 179, 185。
　縮合アゾ系：Pigment Yellow 93, 94, 95, 128, 155, 166, 180。 Yellow colorant:
Examples of the yellow colorant 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.
　ベンズイミダゾロン系：Pigment Yellow 120, 151, 154, 156, 175, 181。
　モノアゾ系：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。
　ジスアゾ系：Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198。 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.
　その他、色調を調整する目的で紫、オレンジ、茶色、黒などの着色剤を加えてもよい。
　具体的に例示すれば、Pigment Violet 19, 23, 29, 32, 36, 38, 42、Solvent Violet 13, 36、C.I. 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等がある。
　これら着色剤の配合割合は、特に制限はないが、前記カルボキシル基含有樹脂１００質量部に対して、好ましくは１０質量部以下、特に好ましくは０．１～５質量部の割合で充分である。 In addition, 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.
　本実施形態の光硬化性熱硬化性樹脂組成物に用いられる分子中に複数のエチレン性不飽和基を有する化合物は、活性エネルギー線照射により、光硬化して、前記カルボキシル基含有樹脂を、アルカリ水溶液に不溶化、又は不溶化を助けるものである。 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.
　このような化合物としては、公知のポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ウレタン（メタ）アクリレート、カーボネート（メタ）アクリレート、エポキシ（メタ）アクリレートなどが使用でき、具体的には、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類；エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類；Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス－ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレオキサイド付加物、プロピレンオキサイド付加物、もしくはε－カプロラクトン付加物などの多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート、及びこれらのフェノール類のエチレンオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類；グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類；上記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類及びメラミンアクリレート、及び／又は上記アクリレートに対応する各メタクリレート類などが挙げられる。 As such a compound, known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like can be used. Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl 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 ε-caprolactone Polyvalent acrylates such as adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Multivalent acrylates of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate In addition to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or the above acrylates Corresponding methacrylates are listed.
　さらに、クレゾールノボラック型エポキシ樹脂などの多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレートなどのヒドロキシアクリレートとイソホロンジイソシアネートなどのジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物などが、挙げられる。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる Further, 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. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
　このような分子中に複数のエチレン性不飽和基を有する化合物の配合量は、前記カルボキシル基含有樹脂１００質量部に対して、５～１００質量部であることが好ましい、配合量が５質量部未満の場合、光硬化性が低下し、活性エネルギー線照射後のアルカリ現像により、パターン形成が困難となる。一方、１００質量部を超えた場合、アルカリ水溶液に対する溶解性が低下して、塗膜が脆くなる。より好ましくは、１～７０質量部である。 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.
　本実施形態の光硬化性熱硬化性樹脂組成物は、その塗膜の物理的強度等を上げるために、必要に応じて、充填剤を配合することができる。このような充填剤としては、公知の無機又は有機充填剤が使用できるが、特に硫酸バリウム、球状シリカ及びタルク、ノイブルグシリシャスアースが好ましい。さらに、白色の外観や難燃性を得るために酸化チタンや金属酸化物、水酸化アルミニウムなどの金属水酸化物を充填剤としても使用することができる。 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. As such a filler, known inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc, and Neuburg Silyce earth are particularly preferable. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can also be used as a filler.
　さらに本実施形態の光硬化性熱硬化性樹脂組成物は、指触乾燥性の改善、ハンドリング性の改善などを目的にバインダーポリマーを使用することができる。例えばポリエステル系ポリマー、ポリウレタン系ポリマー、ポリエステルウレタン系ポリマー、ポリアミド系ポリマー、ポリエステルアミド系ポリマー、アクリル系ポリマー、セルロース系ポリマー、ポリ乳酸系ポリマー、フェノキシ系ポリマーなどを用いることができる。これらのバインダーポリマーは、単独で又は２種類以上の混合物として使用することができる。 Furthermore, 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. For example, 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.
　さらに本実施形態の光硬化性熱硬化性樹脂組成物は、柔軟性の付与、硬化物の脆さを改善することなどを目的に更に他のエラストマーを使用することができる。例えばポリエステル系エラストマー、ポリウレタン系エラストマー、ポリエステルウレタン系エラストマー、ポリアミド系エラストマー、ポリエステルアミド系エラストマー、アクリル系エラストマー、オレフィン系エラストマーを用いることができる。また、種々の骨格を有するエポキシ樹脂の一部又は全部のエポキシ基を両末端カルボン酸変性型ブタジエン－アクリロニトリルゴムで変性した樹脂なども使用できる。 Furthermore, 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. For example, 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. In addition, 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.
　さらにはエポキシ含有ポリブタジエン系エラストマー、アクリル含有ポリブタジエン系エラストマー、水酸基含有ポリブタジエン系エラストマーなども使用することができる。これらのエラストマーは、単独で又は２種類以上の混合物として使用することができる。 Furthermore, 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.
　さらに、本実施形態の光硬化性熱硬化性樹脂組成物は、上記カルボキシル基含有樹脂の合成や組成物の調整のため、又は基板やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。 Furthermore, 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.
　このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などである。このような有機溶剤は、単独で又は２種以上の混合物として用いられる。 Examples of such organic solvents 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 acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.
　一般に、高分子材料の多くは、一度酸化が始まると、次々と連鎖的に酸化劣化が起き、高分子素材の機能低下をもたらすことから、本実施形態の光硬化性熱硬化性樹脂組成物には、酸化を防ぐために、発生したラジカルを無効化するようなラジカル捕捉剤又は／及び発生した過酸化物を無害な物質に分解し、新たなラジカルが発生しないようにする過酸化物分解剤などの酸化防止剤を添加することができる。 Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the photocurable thermosetting resin composition of the present embodiment is used. In order to prevent oxidation, 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.
　ラジカル捕捉剤として働く酸化防止剤としては、具体的な化合物としては、ヒドロキノン、４－ｔ－ブチルカテコール、２－ｔ－ブチルヒドロキノン、ヒドロキノンモノメチルエーテル、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、２，２－メチレン－ビス（４－メチル－６－ｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－Ｓ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン等のフェノール系、メタキノン、ベンゾキノン等のキノン系化合物、ビス（２，２，６，６－テトラメチル－４－ピペリジル）－セバケート、フェノチアジン等のアミン系化合物等などが挙げられる。 Specific examples of the antioxidant that acts as a radical scavenger include 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) - sebacate thereof include amine compounds such as phenothiazine.
　ラジカル捕捉剤は市販のものであってもよく、例えば、アデカスタブＡＯ－３０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－２０、アデカスタブＬＡ－７７、アデカスタブＬＡ－５７、アデカスタブＬＡ－６７、アデカスタブＬＡ－６８、アデカスタブＬＡ－８７（以上、旭電化社製、商品名）、ＩＲＧＡＮＯＸ１０１０、ＩＲＧＡＮＯＸ１０３５、ＩＲＧＡＮＯＸ１０７６、ＩＲＧＡＮＯＸ１１３５、ＴＩＮＵＶＩＮ　１１１ＦＤＬ、ＴＩＮＵＶＩＮ　１２３、ＴＩＮＵＶＩＮ　１４４、ＴＩＮＵＶＩＮ　１５２、ＴＩＮＵＶＩＮ　２９２、ＴＩＮＵＶＩＮ　５１００（以上、チバ・ジャパン社製、商品名）などが挙げられる。 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).
　過酸化物分解剤として働く酸化防止剤としては、具体的な化合物としてトリフェニルフォスファイト等のリン系化合物、ペンタエリスリトールテトララウリルチオプロピオネート、ジラウリルチオジプロピオネート、ジステアリル３，３’－チオジプロピオネート等の硫黄系化合物などが挙げられる。 Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.
　過酸化物分解剤は市販のものであってもよく、例えば、アデカスタブＴＰＰ（旭電化社製、商品名）、マークＡＯ－４１２Ｓ（アデカ・アーガス化学社製、商品名）、スミライザーＴＰＳ（住友化学社製、商品名）などが挙げられる。 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).
　上記の酸化防止剤は、１種を単独で又は２種以上を組み合わせて用いることができる。
　また一般に、高分子材料は光を吸収し、それにより分解・劣化を起こすことから、本実施形態の光硬化性熱硬化性樹脂組成物には、紫外線に対する安定化対策を行うために、上記酸化防止剤の他に、紫外線吸収剤を使用することができる。 Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
In general, since the polymer material absorbs light and thereby decomposes and deteriorates, 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. In addition to the inhibitor, an ultraviolet absorber can be used.
　紫外線吸収剤としては、ベンゾフェノン誘導体、ベンゾエート誘導体、ベンゾトリアゾール誘導体、トリアジン誘導体、ベンゾチアゾール誘導体、シンナメート誘導体、アントラニレート誘導体、ジベンゾイルメタン誘導体などが挙げられる。 Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
　ベンゾフェノン誘導体の具体的な例としては、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－n－オクトキシベンゾフェノン、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン及び２，４－ジヒドロキシベンゾフェノンなどが挙げられる。 Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned.
　ベンゾエート誘導体の具体的な例としては、２－エチルヘキシルサリチレート、フェニルサリチレート、ｐ－ｔ－ブチルフェニルサリチレート、２，４－ジ－ｔ－ブチルフェニル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンゾエート及びヘキサデシル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンゾエートなどが挙げられる。 Specific examples of 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.
　ベンゾトリアゾール誘導体の具体的な例としては、２－（２’－ヒドロキシ－５’－ｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニル）べンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール及び２－（２’－ヒドロキシ－３’，５’－ジ－ｔ－アミルフェニル）ベンゾトリアゾールなどが挙げられる。 Specific examples of the benzotriazole derivative 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.
　トリアジン誘導体の具体的な例としては、ヒドロキシフェニルトリアジン、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジンなどが挙げられる。 Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
　紫外線吸収剤としては市販のものであってもよく、例えば、ＴＩＮＵＶＩＮ　ＰＳ、ＴＩＮＵＶＩＮ　９９－２、ＴＩＮＵＶＩＮ　１０９、ＴＩＮＵＶＩＮ　３８４－２、ＴＩＮＵＶＩＮ　９００、ＴＩＮＵＶＩＮ　９２８、ＴＩＮＵＶＩＮ　１１３０、ＴＩＮＵＶＩＮ　４００、ＴＩＮＵＶＩＮ　４０５、ＴＩＮＵＶＩＮ　４６０、ＴＩＮＵＶＩＮ　４７９（以上、チバ・ジャパン社製、商品名）などが挙げられる。 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.
　これら紫外線吸収剤は、１種を単独で又は２種以上を組み合わせて用いることができ、上記した酸化防止剤と併用することで得られる成形物の安定化が図れる。 These 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.
　本実施形態の光硬化性熱硬化性樹脂組成物には、感度を向上するために連鎖移動剤として公知のＮフェニルグリシン類、フェノキシ酢酸類、チオフェノキシ酢酸類、メルカプトチアゾール等を用いることができる。連鎖移動剤としては、例えばメルカプト琥珀酸、メルカプト酢酸、メルカプトプロピオン酸、メチオニン、システイン、チオサリチル酸及びその誘導体等のカルボキシル基を有する連鎖移動剤；メルカプトエタノール、メルカプトプロパノール、メルカプトブタノール、メルカプトプロパンジオール、メルカプトブタンジオール、ヒドロキシベンゼンチオール及びその誘導体等の水酸基を有する連鎖移動剤；１－ブタンチオール、ブチル－３－メルカプトプロピオネート、メチル－３－メルカプトプロピオネート、２，２－（エチレンジオキシ）ジエタンチオール、エタンチオール、４－メチルベンゼンチオール、ドデシルメルカプタン、プロパンチオール、ブタンチオール、ペンタンチオール、１－オクタンチオール、シクロペンタンチオール、シクロヘキサンチオール、チオグリセロール、４，４－チオビスベンゼンチオール等である。 In the photocurable 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. . Examples of the chain transfer agent 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 Le, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.
　また、多官能性メルカプタン系化合物を用いることができ、特に限定されるものではないが、例えば、ヘキサン－１，６－ジチオール、デカン－１，１０－ジチオール、ジメルカプトジエチルエーテル、ジメルカプトジエチルスルフィド等の脂肪族チオール類、キシリレンジメルカプタン、４，４′－ジメルカプトジフェニルスルフィド、１，４－ベンゼンジチオール等の芳香族チオール類；エチレングリコールビス（メルカプトアセテート）、ポリエチレングリコールビス（メルカプトアセテート）、プロピレングリコールビス（メルカプトアセテート）、グリセリントリス（メルカプトアセテート）、トリメチロールエタントリス（メルカプトアセテート）、トリメチロールプロパントリス（メルカプトアセテート）、ペンタエリスリトールテトラキス（メルカプトアセテート）、ジペンタエリスリトールヘキサキス（メルカプトアセテート）等の多価アルコールのポリ（メルカプトアセテート）類；エチレングリコールビス（３－メルカプトプロピオネート）、ポリエチレングリコールビス（３－メルカプトプロピオネート）、プロピレングリコールビス（３－メルカプトプロピオネート）、グリセリントリス（３－メルカプトプロピオネート）、トリメチロールエタントリス（メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等の多価アルコールのポリ（３－メルカプトプロピオネート）類；１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、ペンタエリスリトールテトラキス（３－メルカプトブチレート）等のポリ（メルカプトブチレート）類を用いることができる。 Polyfunctional mercaptan compounds can be used and are not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide 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 dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), and other poly (mercaptobutyrate) s can be used.
　これらの市販品としては、例えばＢＭＰＡ、ＭＰＭ、ＥＨＭＰ、ＮＯＭＰ、ＭＢＭＰ、ＳＴＭＰ、ＴＭＭＰ、ＰＥＭＰ、ＤＰＭＰ、及びＴＥＭＰＩＣ（以上、堺化学工業社製）、カレンズＭＴ－ＰＥ１、カレンズＭＴ－ＢＤ１、及びカレンズ－ＮＲ１（以上、昭和電工社製）等を挙げることができる。 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).
　さらに、連鎖移動剤として働くメルカプト基を有する複素環化合物として、例えば、メルカプト－４－ブチロラクトン（別名：２－メルカプト－４－ブタノリド）、２－メルカプト－４－メチル－４－ブチロラクトン、２－メルカプト－４－エチル－４－ブチロラクトン、２－メルカプト－４－ブチロチオラクトン、２－メルカプト－４－ブチロラクタム、Ｎ－メトキシ－２－メルカプト－４－ブチロラクタム、Ｎ－エトキシ－２－メルカプト－４－ブチロラクタム、Ｎ－メチル－２－メルカプト－４－ブチロラクタム、Ｎ－エチル－２－メルカプト－４－ブチロラクタム、Ｎ－（２－メトキシ）エチル－２－メルカプト－４－ブチロラクタム、Ｎ－（２－エトキシ）エチル－２－メルカプト－４－ブチロラクタム、２－メルカプト－５－バレロラクトン、２－メルカプト－５－バレロラクタム、Ｎ－メチル－２－メルカプト－５－バレロラクタム、Ｎ－エチル－２－メルカプト－５－バレロラクタム、Ｎ－（２－メトキシ）エチル－２－メルカプト－５－バレロラクタム、Ｎ－（２－エトキシ）エチル－２－メルカプト－５－バレロラクタム、２－メルカプトベンゾチアゾール、２－メルカプト－５－メチルチオ－チアジアゾール、２－メルカプト－６－ヘキサノラクタム、２，４，６－トリメルカプト－ｓ－トリアジン（三協化成社製：商品名　ジスネットＦ）、２－ジブチルアミノ－４，６－ジメルカプト－ｓ－トリアジン（三協化成社製：商品名　ジスネットＤＢ）、及び２－アニリノ－４，６－ジメルカプト－ｓ－トリアジン（三協化成社製：商品名　ジスネットＡＦ）等が挙げられる。 Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5 Lerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2 , 4,6-trimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name: Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (Sankyo Chemical Co., Ltd .: trade name: Disnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd., trade name: DISNET AF) Etc. The.
　特に、光硬化性熱硬化性樹脂組成物の現像性を損なうことがない連鎖移動剤であるメルカプト基を有する複素環化合物として、メルカプトベンゾチアゾール、３－メルカプト－４－メチル－４Ｈ－１，２，４－トリアゾール、５－メチル－１，３，４－チアジアゾール－２－チオール、１－フェニル－５－メルカプト－１Ｈ－テトラゾールが好ましい。これらの連鎖移動剤は、単独又は２種以上を併用することができる。 In particular, as a 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. These chain transfer agents can be used alone or in combination of two or more.
　本実施形態の光硬化性熱硬化性樹脂組成物には、層間の密着性、又は感光性樹脂層と基材との密着性を向上させるために密着促進剤を用いることができる。具体的に例を挙げると例えば、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾチアゾール（商品名：川口化学工業社製アクセルＭ）、３－モルホリノメチル－１－フェニル－トリアゾール－２－チオン、５－アミノ－３－モルホリノメチル－チアゾール－２－チオン、２－メルカプト－５－メチルチオ－チアジアゾール、トリアゾール、テトラゾール、ベンゾトリアゾール、カルボキシベンゾトリアゾール、アミノ基含有ベンゾトリアゾール、シランカップリング剤などがある。 In the photocurable thermosetting resin composition of the present embodiment, 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.
　本実施形態の光硬化性熱硬化性樹脂組成物は、さらに必要に応じて、微粉シリカ、有機ベントナイト、モンモリロナイト、ハイドロタルサイトなどのチキソ化剤を添加することができる。チキソ化剤としての経時安定性は有機ベントナイト、ハイドロタルサイトが好ましく、特にハイドロタルサイトは電気特性に優れている。また、熱重合禁止剤や、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、防錆剤、更にはビスフェノール系、トリアジンチオール系などの銅害防止剤などのような公知の添加剤類を配合することができる。 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. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. In addition, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, and bisphenols Known additives such as copper damage preventing agents such as triazine and triazine thiol can be blended.
　熱重合禁止剤は、本実施形態の光硬化性熱硬化性樹脂組成物に含まれる重合性の化合物の熱的な重合又は経時的な重合を防止するために用いることができる。熱重合禁止剤としては、例えば、４－メトキシフェノール、ハイドロキノン、アルキル又はアリール置換ハイドロキノン、ｔ－ブチルカテコール、ピロガロール、２－ヒドロキシベンゾフェノン、４－メトキシ－２－ヒドロキシベンゾフェノン、塩化第一銅、フェノチアジン、クロラニル、ナフチルアミン、β－ナフトール、２，６－ジ－ｔ－ブチル－４－クレゾール、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、ピリジン、ニトロベンゼン、ジニトロベンゼン、ピクリン酸、４－トルイジン、メチレンブルー、銅と有機キレート剤反応物、サリチル酸メチル、及びフェノチアジン、ニトロソ化合物、ニトロソ化合物とＡｌとのキレートなどが挙げられる。 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. Examples of 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, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
　以上、説明した本実施形態の光硬化性熱硬化性樹脂組成物は、例えば有機溶剤で塗布方法に適した粘度に調整し、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布し、約６０～１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、タックフリーの塗膜を形成できる。その後、接触式（又は非接触方式）により、パターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、もしくはレーザーダイレクト露光機により直接パターン露光し、未露光部をアルカリ水溶液（例えば０．３～３％炭酸ソーダ水溶液）により現像してレジストパターンが形成される。 As described above, 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.
　さらに、熱硬化性成分を含有している組成物の場合、例えば約１４０～１８０℃の温度に加熱して熱硬化させることにより、カルボキシル基含有樹脂のカルボキシル基と、分子中に複数の環状（チオ）エーテル基を有する熱硬化性成分が反応し、耐熱性、耐薬品性、耐吸湿性、密着性、電気特性などの諸特性に優れた硬化塗膜を形成することができる。尚、熱硬化性成分を含有していない場合でも、熱処理することにより、露光時に未反応の状態で残った光硬化性成分のエチレン性不飽和結合が熱ラジカル重合し、塗膜特性が向上するため、目的・用途により、熱処理（熱硬化）してもよい。 Further, in the case of a composition containing a 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. In addition, even when it does not contain a 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.
　基材としては、予め回路形成されたプリント配線板やフレキシブルプリント配線板の他、紙－フェノール樹脂、紙－エポキシ樹脂、ガラス布－エポキシ樹脂、ガラス－ポリイミド、ガラス布／不繊布－エポキシ樹脂、ガラス布／紙－エポキシ樹脂、合成繊維－エポキシ樹脂、フッ素樹脂・ポリエチレン・ＰＰＯ・シアネートエステル等の複合材を用いた全てのグレード（ＦＲ－４等）の銅張積層板、ポリイミドフィルム、ＰＥＴフィルム、ガラス基板、セラミック基板、ウエハ板等を用いることができる。 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.
　本実施形態の光硬化性熱硬化性樹脂組成物を塗布した後に行う揮発乾燥は、熱風循環式乾燥炉、ＩＲ炉、ホットプレート、コンベクションオーブンなど（蒸気による空気加熱方式の熱源を備えたものを用いて乾燥機内の熱風を向流接触せしめる方法及びノズルより支持体に吹き付ける方式）を用いて行うことができる。 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).
　以下のように本実施形態の光硬化性熱硬化性樹脂組成物を塗布し、揮発乾燥した後、得られた塗膜に対し、露光（活性エネルギー線の照射）を行う。塗膜は、露光部（活性エネルギー線により照射された部分）が硬化する。 After applying the photocurable thermosetting resin composition of the present embodiment and evaporating and drying it as described below, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
　活性エネルギー線照射に用いられる露光機としては、直接描画装置（例えばコンピューターからのＣＡＤデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置）、メタルハライドランプを搭載した露光機、（超）高圧水銀ランプを搭載した露光機、水銀ショートアークランプを搭載した露光機、もしくは（超）高圧水銀ランプなどの紫外線ランプを使用した直接描画装置を用いることができる。活性エネルギー線としては、最大波長が３５０～４１０ｎｍの範囲にあるレーザー光を用いていればガスレーザー、固体レーザーどちらでもよい。また、その露光量は膜厚等によって異なるが、一般には５～５００ｍＪ／ｃｍ２、好ましくは５～３００ｍＪ／ｃｍ２である。上記直接描画装置としては、例えば日本オルボテック社製、ペンタックス社製等のものを使用することができ、最大波長が３５０～４１０ｎｍのレーザー光を発振する装置であればいずれの装置を用いてもよい。 As an exposure machine used for active energy ray irradiation, 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 It is possible to use 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. As 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 . As 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. .
　現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。 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.
　本実施形態の光硬化性熱硬化性樹脂組成物は、液状で直接基材に塗布する方法以外にも、予めポリエチレンテレフタレート等のフィルムにソルダーレジストを塗布乾燥して形成したソルダーレジスト層を有するドライフィルムの形態で使用することもできる。本実施形態の光硬化性熱硬化性樹脂組成物をドライフィルムとして使用する場合を以下に示す。 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.
　ドライフィルムは、キャリアフィルムと、ソルダーレジスト層と、必要に応じて用いられる剥離可能なカバーフィルムとが、この順序に積層された構造を有するものである。ソルダーレジスト層は、アルカリ現像性の光硬化性熱硬化性樹脂組成物をキャリアフィルム又はカバーフィルムに塗布乾燥して得られる層である。キャリアフィルムにソルダーレジスト層を形成した後に、カバーフィルムをその上に積層するか、カバーフィルムにソルダーレジスト層を形成し、この積層体をキャリアフィルムに積層すればドライフィルムが得られる。 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.
　キャリアフィルムとしては、２～１５０μｍの厚みのポリエステルフィルム等の熱可塑性フィルムが用いられる。 As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
　ソルダーレジスト層は、本実施形態の光硬化性熱硬化性樹脂組成物をブレードコーター、リップコーター、コンマコーター、フィルムコーター等でキャリアフィルム又はカバーフィルムに１０～１５０μｍの厚さで均一に塗布し乾燥して形成される。 For the solder resist layer, 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 μm using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
　カバーフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム等を使用することができるが、ソルダーレジスト層との接着力が、キャリアフィルムよりも小さいものが良い。 As the 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.
　ドライフィルムを用いてプリント配線板上に保護膜（永久保護膜）を作製するには、カバーフィルムを剥がし、ソルダーレジスト層と回路形成された基材を重ね、ラミネーター等を用いて張り合わせ、回路形成された基材上にソルダーレジスト層を形成する。形成されたソルダーレジスト層に対し、前記と同様に露光、現像、加熱硬化すれば、硬化塗膜を形成することができる。キャリアフィルムは、露光前又は露光後のいずれかに剥離すればよい。
［実施例］ To produce a protective film (permanent protective film) on a printed wiring board using a dry 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.
[Example]
　以下に実施例及び比較例を示して第一の実施形態にかかる光硬化性熱硬化性組成物についてより具体的に説明するが、本発明が下記実施例に限定されるものではないことはもとよりである。尚、以下において「部」及び「％」とあるのは、特に断りのない限り全て質量基準である。 The photocurable 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.
＜感光性樹脂（Ａ－１）の合成例＞
　１Ｌオートクレーブにビフェニルアラルキル樹脂(水酸基当量２３９ｇ／ｅｑ、平均３．７核体)４０１．４ｇ、水酸化カリウム４．０１ｇ、トルエン４０１．４ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１０９．３ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．２６ｇ添加して水酸化カリウムを中和した。水酸基当量３０３ｇ/ｅｑ、樹脂分５６．１％のプロピレンオキサイド付加物溶液を得た。 <Synthesis Example of Photosensitive Resin (A-1)>
A 1 L autoclave was charged with 401.4 g of a biphenyl aralkyl resin (hydroxyl equivalent: 239 g / eq, average 3.7 nucleus), 4.01 g of potassium hydroxide, and 401.4 g of toluene, and dissolved by stirring while raising the temperature to 130 ° C. Next, 109.3 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 5.26 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 303 g / eq and a resin content of 56.1% was obtained.
　得られたプロピレンオキサイド付加物溶液８９２．２ｇ、４－メトキシフェノール０．９２ｇ、トルエン８０４．６ｇ、メタクリル酸１４３．７ｇ、メタンスルホン酸３６．８ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で８時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、３０．０ｇの水が留出した。その後、室温まで冷却し、得られたメタクリレート樹脂溶液を１５％水酸化カリウム溶液１５７．６ｇで中和し、５％食塩水で１回、純水で３回洗浄した。溶液中の樹脂分は３３．２％であった。 892.2 g of the resulting propylene oxide adduct solution, 0.92 g of 4-methoxyphenol, 804.6 g of toluene, 143.7 g of methacrylic acid, and 36.8 g of methanesulfonic acid were charged into a 2 L glass flask, and a temperature of 100 to 110 ° C. The esterification reaction was carried out for 8 hours. The water produced by the reaction was azeotropically mixed with toluene, and 30.0 g of water was distilled off. Thereafter, the mixture was cooled to room temperature, and the resulting methacrylate resin solution was neutralized with 157.6 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 33.2%.
　精製したメタクリレート樹脂溶液１４５０．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート２０６．３ｇで置換し、４－メトキシフェノール０．２１ｇを添加した。得られた感光性樹脂溶液は固形分７０％、一般式（１）に示したｎ＋ｍ＝２．７であった。これを樹脂溶液Ａ－１とする。 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. The obtained photosensitive resin solution had a solid content of 70% and n + m = 2.7 shown in the general formula (1). This is designated as resin solution A-1.
＜感光性樹脂（Ａ－２）の合成例＞
　１Ｌオートクレーブにビフェニル・フェニレン共縮合樹脂（水酸基当量２１９ｇ/ｅｑ、平均４．２核体）４２０．０ｇ、水酸化カリウム４．２０ｇ、トルエン４２０．０ｇ、を仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１２４．８ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．５１ｇ添加して水酸化カリウムを中和した。水酸基当量２８２ｇ/ｅｑ、樹脂分５５．３％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of photosensitive resin (A-2)>
A 1L autoclave was charged with 420.0 g of biphenyl-phenylene co-condensation resin (hydroxyl equivalent 219 g / eq, average 4.2 nucleus), potassium hydroxide 4.20 g, and toluene 420.0 g, and stirred while raising the temperature to 130 ° C. Dissolved. Next, 124.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 5.51 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 282 g / eq and a resin content of 55.3% was obtained.
　得られたプロピレンオキサイド付加物溶液９２５．０ｇ、４－メトキシフェノール０．９５ｇ、トルエン８２６．６ｇ、メタクリル酸１５６．２ｇ、メタンスルホン酸３８．２ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で８時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、３２．７ｇの水が留出した。その後、室温まで冷却し、得られたメタクリレート樹脂溶液を１５％水酸化カリウム溶液１６３．６ｇで中和し、５％食塩水で1回、純水で３回洗浄した。溶液中の樹脂分は３３．５％であった。 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%.
　精製したメタクリレート樹脂溶液１７５０．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート２５１．３ｇで置換し、４－メトキシフェノール０．２５ｇを添加した。得られた感光性樹脂溶液は固形分７０％、一般式（１）に示したｎ＋ｍ＝３．２であった。これを樹脂溶液Ａ－２とする。 1750.0 g of the purified methacrylate resin solution was distilled off while replacing with 251.3 g of diethylene glycol monoethyl ether acetate, and 0.25 g of 4-methoxyphenol was added. The obtained photosensitive resin solution had a solid content of 70% and n + m = 3.2 shown in the general formula (1). This is designated as resin solution A-2.
＜感光性樹脂（Ａ－３）の合成例＞
　１Ｌオートクレーブに、クレゾールとハイドロキノン、４，４－ビス（クロロメチル）ビフェニルの共縮合反応から得られるビフェニルアラルキル樹脂(水酸基当量１９７ｇ／ｅｑ、平均核体数３．１)４００．３ｇ、水酸化カリウム４．０１ｇ、トルエン４０２．３ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１３２．１ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．２６ｇ添加して水酸化カリウムを中和した。水酸基当量２６１ｇ／ｅｑ、樹脂分５６．５％のプロピレンオキサイド付加物溶液を得た。 <Synthesis Example of Photosensitive Resin (A-3)>
In a 1 L autoclave, 400.3 g of biphenyl aralkyl resin (hydroxyl equivalent 197 g / eq, average number of nuclei 3.1) obtained from a co-condensation reaction of cresol, hydroquinone and 4,4-bis (chloromethyl) biphenyl, potassium hydroxide 4.01 g and 402.3 g of toluene were charged and dissolved by stirring while raising the temperature to 130 ° C. Next, 132.1 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 5.26 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 261 g / eq and a resin content of 56.5% was obtained.
　得られたプロピレンオキサイド付加物溶液８００．０ｇ、４－メトキシフェノール０．５２ｇ、トルエン７７３．９ｇ、メタクリル酸１５２．１ｇ、メタンスルホン酸２２．４ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、３１．８ｇの水が留出した。その後、室温まで冷却し、得られたメタクリレート樹脂溶液を１５％水酸化カリウム溶液８７．２ｇで中和し、５％食塩水で１回、純水で３回洗浄した。得られた精製メタクリレート樹脂溶液の樹脂分は３５．５％であった。 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 esterification reaction was carried out for 6 hours. 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%.
　精製したメタクリレート樹脂溶液１５００．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート１３３．１ｇで置換し、４－メトキシフェノール０．２０ｇを添加した。得られた感光性樹脂溶液は固形分８０％、一般式（１）に示したｎ＋ｍ＝２．１であった。これを樹脂溶液Ａ－３とする。 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. The obtained photosensitive resin solution had a solid content of 80% and n + m = 2.1 shown in the general formula (1). This is designated as Resin Solution A-3.
＜感光性樹脂（Ａ－４）の合成例＞
　１Ｌオートクレーブに、クレゾールと１，４－ビスクロロメチルベンゼンから得られるクレゾールアラルキル樹脂(水酸基当量１８８ｇ／ｅｑ、平均核体数４．６)４００．０ｇ、水酸化カリウム４．００ｇ、トルエン３９９．９ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１３８．４ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．２４ｇ添加して水酸化カリウムを中和した。水酸基当量２５２ｇ／ｅｑ、樹脂分５６．８％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of photosensitive resin (A-4)>
In a 1 L autoclave, 400.0 g of cresol aralkyl resin (hydroxyl equivalent: 188 g / eq, average number of nuclei: 4.6) obtained from cresol and 1,4-bischloromethylbenzene, 4.00 g of potassium hydroxide, 399.9 g of toluene The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 138.4 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Then, it cooled to room temperature and added 5.24g of 85% phosphoric acid to the reaction solution, and neutralized potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 252 g / eq and a resin content of 56.8% was obtained.
　得られたプロピレンオキサイド付加物溶液７８０．０ｇ、４－メトキシフェノール０．５１ｇ、トルエン７７２．６ｇ、メタクリル酸１５４．４ｇ、メタンスルホン酸２２．２ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、３２．３ｇの水が留出した。その後、室温まで冷却し、得られたメタクリレート樹脂溶液を１５％水酸化カリウム溶液８６．４ｇで中和した。さらに、５％食塩水で１回、純水で３回洗浄し、メタクリレート樹脂溶液を精製した。溶液中の樹脂分は３６．０％であった。 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. The water produced | 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%.
　精製したメタクリレート樹脂溶液１４５０．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート１３０．５ｇで置換し、４－メトキシフェノール０．２０ｇを添加した。得られた感光性樹脂溶液は固形分８０％、一般式（１）に示したｎ＋ｍ＝３．６であった。これを樹脂溶液Ａ－４とする。 1450.0 g of the purified methacrylate resin solution was distilled off while replacing toluene with 130.5 g of diethylene glycol monoethyl ether acetate, and 0.20 g of 4-methoxyphenol was added. The obtained photosensitive resin solution had a solid content of 80% and n + m = 3.6 shown in the general formula (1). This is designated as Resin Solution A-4.
＜カルボキシル基含有感光性樹脂（Ｂ－１）の合成例＞
　１Ｌオートクレーブに、オルソクレゾールと４，４－ビス(クロロメチル)ビフェニルの縮合反応により得られるビフェニルアラルキル樹脂（水酸基当量２３２ｇ/ｅｑ、平均核体数３．１）３１３．２ｇ、水酸化カリウム３．１３ｇ、トルエン３４４．１ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド８７．８ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を４．１１ｇ添加して水酸化カリウムを中和した。水酸基当量２９６ｇ/ｅｑ、樹脂分５４．８％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of carboxyl group-containing photosensitive resin (B-1)>
In a 1 L autoclave, 313.2 g of biphenyl aralkyl resin (hydroxyl equivalent 232 g / eq, average number of nuclei 3.1) obtained by condensation reaction of orthocresol and 4,4-bis (chloromethyl) biphenyl, potassium hydroxide 3. 13 g and 344.1 g of toluene were charged and dissolved while stirring while heating to 130 ° C. Next, 87.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 4.11 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 296 g / eq and a resin content of 54.8% was obtained.
　得られたプロピレンオキサイド付加物溶液７１８．０ｇ、４－メトキシフェノール０．３６ｇ、トルエン４５９．６ｇ、アクリル酸２８．８ｇ、メタンスルホン酸１２．１ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、７．２ｇの水が留出した。その後、室温まで冷却し、１５％水酸化カリウム水溶液５１．８ｇで中和した。さらに５％食塩水で１回、純水で３回洗浄し、アクリレート樹脂溶液を精製した。溶液中の樹脂分は３６．１％であった。 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. The esterification reaction was carried out for 6 hours. The water produced | 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%.
　精製したアクリレート樹脂溶液１０８３．４ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート１９６．９ｇで置換し、テトラヒドロ無水フタル酸１３３．５ｇ、４－メトキシフェノール０．２３ｇ、トリフェニルホスフィン２．２６ｇを添加し手９０～１００℃の温度で６時間反応させた。得られたカルボキシル基含有感光性樹脂溶液は固形分７０％、固形分酸価９３ｍｇＫＯＨ/ｇ、一般式（４）に示したｎ＋ｍ＝２．１であった。これを樹脂溶液Ｂ－１とする。 While distilling off 1083.4 g of the purified acrylate resin solution, 196.9 g of diethylene glycol monoethyl ether acetate, 133.5 g of tetrahydrophthalic anhydride, 0.23 g of 4-methoxyphenol, 2.26 g of triphenylphosphine Was added and reacted at a temperature of 90-100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 93 mgKOH / g, and n + m = 2.1 shown in the general formula (4). This is designated as resin solution B-1.
＜カルボキシル基含有樹脂（Ｒ－１）の合成例＞
　温度計、窒素導入装置兼アルキレンオキサイド導入装置及び撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂（昭和高分子社製、商品名「ショーノールＣ ＲＧ９５１」、ＯＨ当量：１１９．４）１１９．４ｇ 、水酸化カリウム１．１９ｇ及びトルエン１１９．４ｇを仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキサイド６３．８ｇを徐々に滴下し、１２５～１３２ ℃ 、０～４．８ｋｇ／ｃｍ2で１６時間反応させた。その後、室温まで冷却し、この反応溶液に８９ ％ リン酸１．５６ｇを添加混合して水酸化カリウムを中和し、不揮発分６２．１％、水酸基価が１８２．２ｇ／ｅｑ．であるノボラック型クレゾール樹脂のプロピレンオキサイド反応溶液を得た。これは、フェノール性水酸基１ 当量当りアルキレンオキサイドが平均１．０８モル付加しているものであった。 <Synthesis example of carboxyl group-containing resin (R-1)>
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, 119.4 g of a novolac type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol C RG951”, OH equivalent: 119.4) Then, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
　得られたノボラック型クレゾール樹脂のプロピレンオキサイド反応溶液２９３．０ｇ、アクリル酸４３．２ｇ、メタンスルホン酸１１．５３ｇ、メチルハイドロキノン０．１８ｇ及びトルエン２５２．９ｇを、撹拌機、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、１１０℃で１２時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、１２．６ｇの水が留出した。その後、室温まで冷却し、得られた反応溶液を１５％水酸化ナトリウム水溶液３５．３５ｇで中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート１１８．１ｇで置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。 293.0 g of the resulting novolak-type cresol resin propylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. 12.6 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 reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
　次に、得られたノボラック型アクリレート樹脂溶液３３２．５ｇ及びトリフェニルホスフィン１．２２ｇを、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を１０ｍｌ／分の速度で吹き込み、撹拌しながら、テトラヒドロ無水フタル酸６０ ．８ｇ を徐々に加え、９５～１０１℃ で６時間反応させた。固形物の酸価８８ｍｇＫＯＨ／ｇ 、不揮発分７１％ のカルボキシル基含有感光性樹脂を得た。これを樹脂溶液Ｒ－１とする。 Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, tetrahydrophthalic anhydride 60. 8 g was gradually added and reacted at 95 to 101 ° C for 6 hours. A carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. This is designated as resin solution R-1.
＜カルボキシル基含有樹脂（Ｒ－２）の合成例＞
　　ジエチレングリコールモノエチルエーテルアセテート６００ｇにオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ社製、ＥＰＩＣＬＯＮ Ｎ－６９５、軟化点９５℃、エポキシ当量２１４、平均官能基数７．６）１０７０ｇ（グリシジル基数（芳香環総数）：５．０モル）、アクリル酸３６０ｇ（５．０モル）、及びハイドロキノン１．５ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン４．３ｇを仕込み、１１０℃に加熱して２時間反応後、１２０℃に昇温してさらに１２時間反応を行った。得られた反応液に芳香族系炭化水素（ソルベッソ１５０）４１５ｇ、テトラヒドロ無水フタル酸４５６．０ｇ（３．０モル）を仕込み、１１０℃で４時間反応を行い、冷却後、固形分酸価８９ｍｇＫＯＨ／ｇ、固形分６５％の樹脂溶液を得た。以下、これを樹脂溶液Ｒ－２と称す。 <Synthesis example of carboxyl group-containing resin (R-2)>
Orthocresol novolak epoxy resin (600 g, diethylene glycol monoethyl ether acetate (DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. Hereinafter, this is referred to as a resin solution R-2.
　上記合成例の樹脂溶液を用い、表１に示す種々の成分、割合（質量部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで混練し、ソルダーレジスト用光硬化性熱硬化性樹脂組成物を調製した。ここで得られた樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ１５μｍ以下であった。 Using the resin solution of the above synthesis example, blended in various components and proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and photocurable thermosetting for solder resist. A functional resin composition was prepared. The degree of dispersion of the resin composition obtained here was 15 μm or less when evaluated by particle size measurement using a grindometer manufactured by Eriksen.
Figure JPOXMLDOC01-appb-T000001
 ［備考］
＊１：ビフェニルノボラック型エポキシ樹脂(NC-3000HCA75:日本化薬社製)
＊２：ビスフェノール型エポキシ樹脂(YSLV-80XY：東都化成社製)
＊３：エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム) (イルガキュアー OXE 02:チバ・ジャパン社製)
＊４：2-メルカプトベンゾチアゾール
＊５：酸化防止剤（チバ・ジャパン社製）
＊６：B-30 (堺化学社製)
＊７：SO-E3（アドマテックス社製）
＊８：ハイドロタルサイト（協和化学工業社製）
＊９：C.I.Pigment Blue 15:3
＊１０：C.I.Pigment Yellow 147
＊１１：ジエチレングリコールモノエチルエーテルアセテート
＊１２：ジペンタエリスリトールヘキサアクリレート
Figure JPOXMLDOC01-appb-T000001
 [Remarks]
* 1: Biphenyl novolac type epoxy resin (NC-3000HCA75: manufactured by Nippon Kayaku Co., Ltd.)
* 2: Bisphenol type epoxy resin (YSLV-80XY: manufactured by Toto Kasei)
* 3: Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure OXE 02: manufactured by Ciba Japan )
* 4: 2-mercaptobenzothiazole * 5: Antioxidant (manufactured by Ciba Japan)
* 6: B-30 (manufactured by Sakai Chemical Co., Ltd.)
* 7: SO-E3 (manufactured by Admatechs)
* 8: Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 9: CIPigment Blue 15: 3
* 10: CIPigment Yellow 147
* 11: Diethylene glycol monoethyl ether acetate * 12: Dipentaerythritol hexaacrylate
［実施例１～６、比較例１，２］
　表１に示す実施例及び比較例の組成物について、以下に示す評価方法にて性能評価及び特性評価を行った。評価結果を表２に示す。
　性能評価：
　＜最適露光量＞
　銅厚１８μｍの回路パターン基板を銅表面粗化処理（メック社製メックエッチボンドＣＺ－８１００）後、水洗し、乾燥した後、表１に示す実施例及び比較例の組成物をスクリーン印刷法により全面に塗布し、８０℃の熱風循環式乾燥炉で６０分間乾燥させ、約２０μｍの乾燥塗膜を得た。その後、高圧水銀灯搭載の露光装置を用いてステップタブレット（Ｋｏｄａｋ　Ｎｏ．２）を介して露光し、現像（３０℃、０．２ＭＰａ、１％炭酸ナトリウム水溶液）を９０秒で行った際残存するステップタブレットのパターンが７段の時を最適露光量とした。 [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 μm 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 μm. Then, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and a step remaining when development (30 ° C., 0.2 MPa, 1% aqueous sodium carbonate solution) is performed in 90 seconds. When the tablet pattern was 7 steps, the optimum exposure was set.
　＜最大現像ライフ＞
　表１に示す実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で乾燥膜厚約２０μｍになるように全面塗布し、８０℃で乾燥し２０分から８０分まで５分おきに基板を取り出し、室温まで放冷した。この基板に３０℃の１％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で９０秒間現像を行い、残渣が残らない最大許容乾燥時間を最大現像ライフとした。 <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 μm 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.
　特性評価：
　表１に示す実施例及び比較例の組成物を、パターン形成された銅箔基板上にスクリーン印刷で乾燥膜厚約２０μｍになるように全面塗布し、８０℃で３０分乾燥し、室温まで放冷した。この基板に高圧水銀灯を搭載した露光装置を用いて最適露光量でソルダーレジストパターンを露光し、３０℃の１％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で９０秒間現像を行い、レジストパターンを得た。この基板を、ＵＶコンベア炉にて積算露光量１０００ｍＪ／ｃｍ２の条件で紫外線照射した後、１５０℃で６０分加熱して硬化した。得られたプリント基板（評価基板）に対して以下のように特性を評価した。 Characterization:
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 μm by screen printing, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa. Obtained. 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.
　＜耐酸性＞
　評価基板を１０体積％Ｈ２ＳＯ４水溶液に室温で３０分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープピールによる剥がれを確認した。
　 ○：変化が認められないもの
　 △：ほんの僅か変化しているもの
　 ×：塗膜に膨れあるいは膨潤脱落があるもの <Acid resistance>
The evaluation substrate was immersed in a 10% by volume H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to the tape peel was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off
　＜耐アルカリ性＞
　評価基板を１０体積％ＮａＯＨ水溶液に室温で３０分間浸漬し、染み込みや塗膜の溶け出しを目視にて確認し、さらにテープピールによる剥がれを確認した。
　 ○：変化が認められないもの
　 △：ほんの僅か変化しているもの
　 ×：塗膜に膨れあるいは膨潤脱落があるもの <Alkali resistance>
The evaluation substrate was immersed in a 10% by volume NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed. Further, peeling due to the tape peel was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off
　＜はんだ耐熱性＞
　ロジン系フラックスを塗布した評価基板を、予め２６０℃に設定したはんだ槽に浸漬し、変性アルコールでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれについて評価した。判定基準は以下のとおりである。
　 ○：１０秒間浸漬を３回以上繰り返しても剥がれが認められない
　 △：１０秒間浸漬を３回以上繰り返すと少し剥がれる
　 ×：１０秒間浸漬を３回以内にレジスト層に膨れ、剥がれがある <Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more. Δ: A little peeling occurs when the immersion for 10 seconds is repeated 3 times or more. X: The resist layer swells and peels within 3 times for 10 seconds.
　＜耐無電解金めっき性＞
　評価基板について、市販品の無電解ニッケルめっき浴及び無電解金めっき浴を用いて、ニッケル５μｍ、金０．０５μｍの条件で開口８０μmのボールパットにめっき処理を行った。メッキされた評価基板において、テープピーリングにより、レジスト層の剥がれの有無やめっきのしみ込みの有無を評価した後、テープピーリングによりレジスト層の剥がれの有無を評価した。判定基準は以下のとおりである。
　○：めっき後にしみ込みが見られず、テープピーリング後に剥がれはない
　△：めっき後に白化が確認されるが、テープピーリング後の剥がれはない
　×：めっき後に剥がれが確認される <Electroless gold plating resistance>
The evaluation substrate was plated on a ball pad having an opening of 80 μm under the conditions of nickel 5 μm and gold 0.05 μm using commercially available electroless nickel plating bath and electroless gold plating bath. In the plated evaluation substrate, 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耐性＞
　耐無電解金めっき性の評価と同様に無電解金めっきを施した評価基板を、ＰＣＴ装置（エスペック社製ＨＡＳＴ ＳＹＳＴＥＭ ＴＰＣ－４１２ＭＤ）を用いて、１２１℃、飽和、０．２ＭＰａの条件で種々の時間処理し、塗膜の状態によりＰＣＴ耐性を評価した。判定基準は以下のとおりである。
　○：３００時間試験経過後、膨れ、剥がれ、変色、溶出のないもの
　△：１６８時間試験経過時、膨れ、剥がれ、変色、溶出のないもの
　×：１６８時間試験経過時、膨れ、剥がれ、変色、溶出が見られるもの <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 Δ: When 168 hours testing elapsed, no swelling, peeling, discoloration, no dissolution ×: After 168 hours testing, swelling, peeling, discoloration, Elution is seen
　＜冷熱衝撃耐性＞
　□抜き、○抜きパターンを形成したソルダーレジスト硬化塗膜を有する評価基板を作製した。得られた評価基板を冷熱衝撃試験器（エタック社製）で－５５℃／３０分～１５０℃／３０分を１サイクルとして１０００サイクルの耐性試験を行った。試験後、処理後の硬化膜を目視により観察し、クラックの発生状況を下記の基準にて判断した。
　○：クラック発生率３０％未満
　△：クラック発生率３０～５０％
　×：クラック発生率５０％以上 <Cold shock resistance>
The evaluation board | substrate which has a soldering resist cured coating film in which (square) extraction and (circle) extraction pattern were formed was produced. The obtained evaluation substrate was subjected to a 1000 cycle durability test using a thermal shock tester (manufactured by ETAC) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged according to the following criteria.
○: Crack generation rate of less than 30% △: Crack generation rate of 30-50%
×: Crack occurrence rate of 50% or more
　＜ＨＡＳＴ特性＞
　クシ型電極（ライン／スペース＝３０ミクロン／３０ミクロン）が形成されたＢＴ基板に、ソルダーレジスト硬化塗膜を形成し、評価基板を作成した。この評価基板を、１３０℃、湿度８５％の雰囲気下の高温高湿槽に入れ、電圧１２Ｖを荷電し、種々の時間、槽内ＨＡＳＴ試験を行った。種々の時間経過時の槽内絶縁抵抗値を下記の判断基準に従い評価した。
○：３００時間経過後、１０８Ω以上
△：１６８時間経過時、１０８Ω以上
×：１６８時間経過時、１０８Ω以下 <HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 30 microns / 30 microns) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high-temperature, high-humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the internal HAST test was done for various time. The insulation resistance value in the tank at various times was evaluated according to the following criteria.
○: After 300 hours, 10 8 Ω or more Δ: When 168 hours have elapsed, 10 8 Ω or more ×: When 168 hours have elapsed, 10 8 Ω or less
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　＜ドライフィルム評価＞　
　［実施例７～１２］
　表１に示す配合割合で調製した実施例１～６の各組成物をメチルエチルケトンにて希釈し、ＰＥＴフィルム上に塗布して８０℃で３０分乾燥し、厚さ２０μｍの感光性樹脂組成物層を形成した。さらにその上にカバーフィルムを貼り合わせてドライフィルムを作製し、それぞれを実施例７～１２とした。 <Dry film evaluation>
[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 μm. Formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 7 to 12, respectively.
　上記のようにして得られたドライフィルムからカバーフィルムを剥がし、パターン形成された銅箔基板に、フィルムを熱ラミネートし、次いで、上記の塗膜特性評価に用いた基板と同様の条件で露光した。露光後、キャリアフィルムを剥がし、３０℃の１％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で９０秒間現像を行い、レジストパターンを得た。この基板を、ＵＶコンベア炉にて積算露光量１０００ｍＪ／ｃｍ２の条件で紫外線照射した後、１５０℃で６０分加熱して硬化した。得られた硬化皮膜を有する試験基板について、上記の評価方法にて性能評価及び特性評価を行った。評価結果を表３に示す。 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. . After the exposure, 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. About the test board | 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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２、表３に示す結果から明らかなように、本発明の光硬化性熱硬化性樹脂組成物は半導体パッケージ用ソルダーレジストに必要とされるＰＣＴ耐性、冷熱衝撃耐性、ＨＡＳＴ特性を兼ね備え、非常に信頼性の高いソルダーレジスト硬化塗膜が得られることが明らかとなり、光硬化性熱硬化性樹脂組成物として有用であることが認められた。 As is apparent from the results shown in Tables 2 and 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.
　次に、第二の実施形態にかかる光硬化性熱硬化性樹脂組成物について詳細に説明する。なお、第二の実施形態にかかる光硬化性熱硬化性樹脂組成物に用いられる光重合開始剤、任意成分及びパターン形成方法は、上記した第一の実施形態にかかる光硬化性熱硬化性樹脂組成物と同じであるため、第一の実施形態にかかる光硬化性熱硬化性樹脂組成物と異なる成分について主に説明する。
　第二の実施形態にかかる光硬化性熱硬化性樹脂組成物は、一般式（４）～(７)に示す構造を有するカルボキシル基含有感光性樹脂及び光重合開始剤を含有することを特徴としている。 Next, the photocurable thermosetting resin composition according to the second embodiment will be described in detail. In addition, the photoinitiator used for the photocurable thermosetting resin composition concerning 2nd embodiment, an arbitrary component, and the pattern formation method are the photocurable thermosetting resins concerning 1st embodiment mentioned above. Since it is the same as the composition, the components different from the photocurable thermosetting resin composition according to the first embodiment will be mainly described.
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.
Figure JPOXMLDOC01-appb-C000019
 （式（４）中、Ｒ１は下記式（５）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～４．０、ｎ＝０～４．０、ｍ＝０～４．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
Figure JPOXMLDOC01-appb-C000019
 (In the formula (4), 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)
Figure JPOXMLDOC01-appb-C000020
 （式（５）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（６）あるいは（７）の基または水素を示し、ｋ＝０．３～１０．０である。）
Figure JPOXMLDOC01-appb-C000020
 (In Formula (5), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (6) or (7), and k = 0.3 to 10.0)
Figure JPOXMLDOC01-appb-C000021
 （式（６）中、Ｒ５は水素またはメチル基を示す。）
Figure JPOXMLDOC01-appb-C000021
 (In formula (6), R 5 represents hydrogen or a methyl group.)
Figure JPOXMLDOC01-appb-C000022
 　（式(７)中のＸは酸無水物残基を表す。）
Figure JPOXMLDOC01-appb-C000022
 (X in the formula (7) represents an acid anhydride residue.)
　一般式（４）～（７）で示される構造を有するカルボキシル基含有感光性樹脂は、第一の実施形態にかかる一般式（１）～（３）で示される構造を有する感光性樹脂と同様に、フェノール樹脂とアルキレンオキサイド又はシクロカーボネートとを反応付加による鎖延長によって可撓性、伸びに優れている。また、アルキレンオキサイド又はシクロカーボネートの付加反応によって生じた末端水酸基に、不飽和基含有モノカルボン酸の付加及び多塩基酸無水物の付加が行われ、不飽和基やカルボキシル基が同一側鎖上に存在せず、かつ、それぞれ側鎖の末端に位置するため、反応性に優れている。さらに、主鎖から離れた末端カルボキシル基の存在により、優れたアルカリ現像性を有する。 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. In addition, 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.
　　また、上記カルボキシル基含有感光性樹脂は、実質的に親水性のアルコール性水酸基を含まないため、耐吸湿性に優れている。一般的に水酸基の存在は、水素結合による密着性の向上など優れた特徴も有しているが、著しく耐湿性を低下させることが知られている。従って、実質的に水酸基を含まないことにより、耐湿性を向上させることができる。そして、耐湿性の向上により、ＰＣＴ耐性の向上が可能となる。 Further, the carboxyl group-containing photosensitive resin is excellent in moisture absorption resistance because it does not substantially contain a hydrophilic alcoholic hydroxyl group. In general, 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.
　また、上記カルボキシル基含有感光性樹脂の前駆体のフェノール骨格を考えた場合、通常のフェノール、あるいはクレゾール型ノボラック樹脂と比較して水酸基当量が大きいことが特徴として挙げられる。即ち、第二の実施形態にかかるカルボキシル基含有感光性樹脂の前駆体から誘導される硬化物は、一般的なノボラック樹脂類と比較して良好な可とう性を有する。これに伴い、一般的なノボラック樹脂類と比較して、本実施形態のカルボキシル基含有感光性樹脂の前駆体から誘導された組成物は、得られる硬化物の冷熱衝撃耐性とＰＣＴ耐性を向上させることが可能である。 Further, when considering the phenol skeleton of the precursor of the carboxyl group-containing photosensitive resin, 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.
　従って、第二の実施形態にかかる光硬化性熱硬化性樹脂組成物は、第一の実施形態にかかる光硬化性熱硬化性樹脂組成物と同様、作業性に優れると共に、その塗膜の選択的露光、現像及び仕上げ硬化によって、密着性、耐薬品性、無電解金めっき耐性、冷熱衝撃耐性、ＰＣＴ耐性、電気絶縁性等に優れた硬化皮膜を得ることができる。 Therefore, 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.
　一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂は、上記［１］、［２］と同様の方法で得られた感光性樹脂に、多塩基酸無水物を反応させて得られる。
　従って、一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂に用いられるフェノール樹脂、アルキレンオキサイド、シクロカーボネート化合物及び不飽和基含有モノカルボン酸は、第一の実施形態に係る一般式（１）～（３）に示す構造を有する感光性樹脂と同様である。 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).
　多塩基酸無水物としては、例えばメチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、３，６－エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸等の脂環式二塩基酸無水物； 無水コハク酸、無水マレイン酸、無水イタコン酸、オクテニル無水コハク酸、ペンタドデセニル無水コハク酸、無水フタル酸、無水トリメリット酸等の脂肪族又は芳香族二塩基酸無水物、あるいはビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物等の脂肪族又は芳香族四塩基酸二無水物が挙げられ、これらのうち１種又は２種以上を使用することができる。 Examples of the polybasic acid anhydride 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, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride Acid, benzofu Aliphatic or aromatic tetrabasic acid dianhydride, such as non-tetracarboxylic acid dianhydride and the like, can be used one or two or more of these.
　一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂に用いられるアルキレンオキサイド又はシクロカーボネート化合物の付加量としては、フェノール性水酸基１当量当たり、０．３～１０モルの範囲であることが好ましい。付加量が上記範囲より少ない場合、後述する不飽和基含有モノカルボン酸や多塩基酸無水物との反応が起こり難くなり、感光性及び希アルカリ水溶液に対する溶解性が低下する。一方、付加量が上記範囲を超えた場合、生成するエーテル結合により、耐水性が低下し、電気絶縁性、ＨＡＳＴ耐性等が低下する。より好ましくは０．８ ～ ５モルの範囲であり、さらに好ましくは１．０ ～３モルの範囲である。 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.
　一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂は、上記した感光性樹脂と同様にフェノール樹脂を出発原料として得られる。塩素イオン不純物がほとんど含まれないフェノール樹脂は容易に入手することができることから、得られるカルボキシル基含有感光性樹脂における塩素イオン不純物濃度を抑えることができる。 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.
　このようなカルボキシル基含有感光性樹脂の塩素イオン不純物含有量は１００ｐｐｍ以下であることが好ましい。より好ましくは５０ｐｐｍ以下、更に好ましくは３０ｐｐｍ以下である。 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.
　また、このような方法により、実質的に水酸基を含まないカルボキシル基含有感光性樹脂を得ることができる。このように、カルボキシル基含有感光性樹脂における塩素イオン不純物を抑え、実質的に水酸基を含まないことにより、優れた絶縁信頼性、ＰＣＴ耐性を発現することが可能となる。 Also, by such a method, a carboxyl group-containing photosensitive resin substantially free of hydroxyl groups can be obtained. As described above, it is possible to exhibit excellent insulation reliability and PCT resistance by suppressing chlorine ion impurities in the carboxyl group-containing photosensitive resin and substantially not including a hydroxyl group.
　一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂は、優れたフィルム形成性能やフィルム物性を発現させるため、ある程度高分子量化されている。一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂は一般式（４）に示したｎ＋ｍが１．５～４．０の範囲であることが好ましい。ｎ＋ｍが１．５以下であると精密に制御された構造を有するカルボキシル基含有感光性樹脂が得られない。一方、４．０以上であるとアルカリ現像による溶解が困難になる場合があり、現像残渣の発生が懸念される。一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂の最適なｎは２．５～４．０程度である。 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. In the carboxyl group-containing photosensitive resin having the structure represented by the general formulas (4) to (7), n + m represented by the general formula (4) is preferably in the range of 1.5 to 4.0. When n + m is 1.5 or less, a carboxyl group-containing photosensitive resin having a precisely controlled structure cannot be obtained. On the other hand, if it is 4.0 or more, dissolution by alkali development may be difficult, and there is a concern about development residue. 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.
　本実施形態の一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂は、バックボーン・ポリマーの側鎖に多数の遊離のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。また、その酸価は、５０～２００ｍｇＫＯＨ／ｇの範囲であることが好ましい。酸価が５０ｍｇＫＯＨ／ｇ未満であるとアルカリ現像が困難となり、一方、２００ｍｇＫＯＨ／ｇを超えると現像液による露光部の溶解が進むために必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となる。より好ましくは５０～１５０ｍｇＫＯＨ／ｇである。 Since 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.
　また、一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に１，０００～２０，０００の範囲にあるものが好ましい。重量平均分子量が１，０００未満であると、タックフリー性能が劣ることがあり、露光後の塗膜の耐湿性が悪く現像時に膜減りが生じ、解像度が大きく劣ることがある。一方、重量平均分子量が２０，０００を超えると、現像性が著しく悪くなることがあり、貯蔵安定性が劣ることがある。より好ましくは、１，０００～１０，０００である。 Further, 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.
　このようなカルボキシル基含有感光性樹脂の配合量は、全組成物中に、２０～６０質量％であることが好ましい。上記範囲より少ない場合、塗膜強度が低下したりする。一方、上記範囲より多い場合、粘性が高くなったり、塗布性等が低下する。より好ましくは３０～５０質量％である。 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.
　また、第二の実施形態にかかる光硬化性熱硬化性樹脂組成物には、現像性、タック性等の諸特性のバランスを調整するため、一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂の他に、上記したような公知のカルボキシル含有樹脂を併用してもかまわない。
［実施例］ In addition, 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. In addition to the carboxyl group-containing photosensitive resin having, a known carboxyl-containing resin as described above may be used in combination.
[Example]
　以下に実施例及び比較例を示して第二の実施形態にかかる光硬化性熱硬化性組成物についてより具体的に説明するが、本発明が下記実施例に限定されるものではないことはもとよりである。尚、以下において「部」及び「％」とあるのは、特に断りのない限り全て質量基準である。 The photocurable 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.
　本実施例に用いられるカルボキシル基含有感光性樹脂Ｂ－１、カルボキシル基含有樹脂Ｒ－１及びＲ－２は、第一の実施形態にかかる実施例と同一のものである。 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.
＜カルボキシル基含有感光性樹脂（Ｂ－２）の合成例＞
　１Ｌオートクレーブに、オルソクレゾールと４，４－ビス(クロロメチル)ビフェニル、４，４－ビス(クロロメチル)ベンゼンの共縮合反応により得られるビフェニル・フェニレン共縮合樹脂（水酸基当量２１５ｇ／ｅｑ、平均３．７核体）３７０．０ｇ、水酸化カリウム３．７０ｇ、トルエン３７０．０ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１１１．９ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を４．８５ｇ添加して水酸化カリウムを中和した。水酸基当量２７８ｇ／ｅｑ、樹脂分５６．９％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of carboxyl group-containing photosensitive resin (B-2)>
To a 1 L autoclave, a biphenyl-phenylene co-condensation resin (hydroxyl equivalent 215 g / eq, average 3) obtained by co-condensation reaction of orthocresol with 4,4-bis (chloromethyl) biphenyl and 4,4-bis (chloromethyl) benzene .7 nuclei) 370.0 g, potassium hydroxide 3.70 g, and toluene 370.0 g were charged and stirred and dissolved while heating to 130 ° C. Next, 111.9 g of propylene oxide was gradually dropped and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 4.85 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 278 g / eq and a resin content of 56.9% was obtained.
　得られたプロピレンオキサイド付加物溶液８００．０ｇ、４－メトキシフェノール０．４２ｇ、トルエン５６３．９ｇ、アクリル酸４６．４ｇ、メタンスルホン酸１４．１ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、１１．６ｇの水が留出した。その後、室温まで冷却し、１５％水酸化カリウム水溶液６０．４ｇで中和した。さらに５％食塩水で１回、純水で３回洗浄し、アクリレート樹脂溶液を精製した。溶液中の樹脂分は３７．１％であった。 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. 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 37.1%.
　精製したアクリレート樹脂溶液１２７０．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート２６３．５ｇで置換し、無水テトラヒドロフタル酸１４３．６ｇ、４－メトキシフェノール０．４４ｇ、トリフェニルホスフィン２．２０ｇを添加して９０～１００℃の温度で６時間反応させた。得られたカルボキシル基含有感光性樹脂溶液は固形分７０％、固形分酸価８６ｍｇＫＯＨ／ｇ、一般式（４）に示したｎ＋ｍ＝２．７であった。これを樹脂溶液Ｂ－２とする。 While purifying 1270.0 g of the purified acrylate resin solution with toluene, 263.5 g of diethylene glycol monoethyl ether acetate was substituted, 143.6 g of tetrahydrophthalic anhydride, 0.44 g of 4-methoxyphenol, 2.20 g of triphenylphosphine And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 86 mgKOH / g, and n + m = 2.7 shown in the general formula (4). This is designated as resin solution B-2.
＜カルボキシル基含有感光性樹脂（Ｂ－３）の合成例＞
　１Ｌオートクレーブに、クレゾールとハイドロキノン、４，４－ビス（クロロメチル）ビフェニルの共縮合反応から得られるビフェニルアラルキル樹脂(水酸基当量１９７ｇ／ｅｑ、平均核体数３．１)４００．３ｇ、水酸化カリウム４．０１ｇ、トルエン４０２．３ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１３２．１ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．２６ｇ添加して水酸化カリウムを中和した。水酸基当量２６１ｇ／ｅｑ、樹脂分５６．５％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of carboxyl group-containing photosensitive resin (B-3)>
In a 1 L autoclave, 400.3 g of biphenyl aralkyl resin (hydroxyl equivalent 197 g / eq, average number of nuclei 3.1) obtained from a co-condensation reaction of cresol, hydroquinone and 4,4-bis (chloromethyl) biphenyl, potassium hydroxide 4.01 g and 402.3 g of toluene were charged and dissolved by stirring while raising the temperature to 130 ° C. Next, 132.1 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Thereafter, the mixture was cooled to room temperature, and 5.26 g of 85% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 261 g / eq and a resin content of 56.5% was obtained.
　得られたプロピレンオキサイド付加物溶液９０９．７ｇ、４－メトキシフェノール０．４９ｇ、トルエン６６４．３ｇ、アクリル酸５６．８ｇ、メタンスルホン酸１４．７ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、１４．２ｇの水が留出した。その後、室温まで冷却し、得られたアクリレート樹脂溶液を１５％水酸化カリウム溶液５７．２ｇで中和し、５％食塩水で１回、純水で３回洗浄し、アクリレート樹脂溶液を精製した。溶液中の樹脂分は３３．８％であった。 909.7 g of the resulting propylene oxide adduct solution, 0.49 g of 4-methoxyphenol, 664.3 g of toluene, 56.8 g of acrylic acid, and 14.7 g of methanesulfonic acid were charged into a 2 L glass flask, and the temperature was 100 to 110 ° C. The esterification reaction was carried out for 6 hours. 14.2 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 57.2 g of 15% potassium hydroxide solution, washed once with 5% brine and three times with pure water to purify the acrylate resin solution. . The resin content in the solution was 33.8%.
　精製したアクリレート樹脂溶液１５２７．５ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート２９２．４ｇで置換し、テトラヒドロ無水フタル酸１６６．６ｇ、４－メトキシフェノール０．２９ｇ、トリフェニルホスフィン１．９５ｇを添加して９０～１００℃の温度で６時間反応させた。得られたカルボキシル基含有感光性樹脂溶液は固形分７０％、固形分酸価９０ｍｇＫＯＨ／ｇ、一般式（４）に示したｎ＋ｍ＝２．１であった。これを樹脂溶液Ｂ－３とする。 While purifying the toluene of 1527.5 g of the purified acrylate resin solution, 292.4 g of diethylene glycol monoethyl ether acetate was substituted, 166.6 g of tetrahydrophthalic anhydride, 0.29 g of 4-methoxyphenol, 1.95 g of triphenylphosphine And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 90 mgKOH / g, and n + m = 2.1 shown in the general formula (4). This is designated as resin solution B-3.
＜カルボキシル基含有感光性樹脂（Ｂ－４）の合成例＞
　　上記感光性樹脂（Ａ－４）で得られたプロピレンオキサイド付加物溶液９２０．０ｇ、４－メトキシフェノール０．５１ｇ、トルエン７０４．９ｇ、アクリル酸７１．０ｇ、メタンスルホン酸１５．３ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、１７．７ｇの水が留出した。その後、室温まで冷却し、得られたアクリレート樹脂溶液を１５％水酸化カリウム溶液５９．６ｇで中和し、５％食塩水で１回、純水で３回洗浄し、アクリレート樹脂溶液を精製した。溶液中の樹脂分は３６．２％であった。 <Synthesis example of carboxyl group-containing photosensitive resin (B-4)>
92 L of propylene oxide adduct solution obtained with the above photosensitive resin (A-4), 0.51 g of 4-methoxyphenol, 704.9 g of toluene, 71.0 g of acrylic acid, and 15.3 g of methanesulfonic acid were added to 2 L glass. The flask was charged and esterified at a temperature of 100 to 110 ° C. for 6 hours. 17.7 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 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%.
　精製したアクリレート樹脂溶液１５５０．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート３０９．９ｇで置換し、テトラヒドロ無水フタル酸１６２．０ｇ、４－メトキシフェノール０．３１ｇ、トリフェニルホスフィン２．０７ｇを添加して９０～１００℃の温度で６時間反応させた。得られたカルボキシル基含有感光性樹脂溶液は固形分７０％、固形分酸価８２ｍｇＫＯＨ／ｇ、一般式（４）に示したｎ＋ｍ＝３．６であった。これを樹脂溶液Ｂ－４とする。 While purifying 1550.0 g of purified acrylate resin solution with toluene, 309.9 g of diethylene glycol monoethyl ether acetate was substituted. Tetrahydrophthalic anhydride 162.0 g, 4-methoxyphenol 0.31 g, triphenylphosphine 2.07 g And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 82 mgKOH / g, and n + m = 3.6 shown in the general formula (4). This is designated as resin solution B-4.
＜カルボキシル基含有感光性樹脂（Ｂ－５）の合成例＞
　１Ｌオートクレーブに、クレゾールと１，４－ビスクロロメチルベンゼンから得られるクレゾールアラルキル樹脂(水酸基当量１８０ｇ／ｅｑ、平均核体数３．３)４００．０ｇ、水酸化カリウム４．００ｇ、トルエン４０２．１ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１４４．６ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．２４ｇ添加して水酸化カリウムを中和した。水酸基当量２４３ｇ／ｅｑ、樹脂分５７．５％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of carboxyl group-containing photosensitive resin (B-5)>
In a 1 L autoclave, 400.0 g of cresol aralkyl resin (hydroxyl equivalent: 180 g / eq, average number of nuclei: 3.3) obtained from cresol and 1,4-bischloromethylbenzene, 4.00 g of potassium hydroxide, 402.1 g of toluene The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 144.6 g of propylene oxide was gradually added dropwise and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Then, it cooled to room temperature and added 5.24g of 85% phosphoric acid to the reaction solution, and neutralized potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 243 g / eq and a resin content of 57.5% was obtained.
　得られたプロピレンオキサイド付加物溶液９２０．０ｇ、４－メトキシフェノール０．５２ｇ、トルエン７３７．２ｇ、アクリル酸７８．５ｇ、メタンスルホン酸１５．６ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、１９．６ｇの水が留出した。その後、室温まで冷却し、得られたアクリレート樹脂溶液を１５％水酸化カリウム溶液６０．７ｇで中和し、５％食塩水で１回、純水で３回洗浄し、アクリレート樹脂溶液を精製した。溶液中の樹脂分は３７．０％であった。 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. Thereafter, 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%.
精製したアクリレート樹脂溶液１５５０．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート３１５．０ｇで置換し、テトラヒドロ無水フタル酸１６１．６ｇ、４－メトキシフェノール０．３２ｇ、トリフェニルホスフィン２．１０ｇを添加して９０～１００℃の温度で６時間反応させた。得られたカルボキシル基含有感光性樹脂溶液は固形分７０％、固形分酸価８０ｍｇＫＯＨ／ｇ、一般式（４）に示したｎ＋ｍ＝２．３であった。これを樹脂溶液Ｂ－５とする。 While purifying 1550.0 g of toluene in the purified acrylate resin solution, 315.0 g of diethylene glycol monoethyl ether acetate was substituted, 161.6 g of tetrahydrophthalic anhydride, 0.32 g of 4-methoxyphenol, 2.10 g of triphenylphosphine And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 80 mgKOH / g, and n + m = 2.3 shown in the general formula (4). This is designated as Resin Solution B-5.
　＜カルボキシル基含有感光性樹脂（Ｂ－６）の合成例＞
　１Ｌオートクレーブに、クレゾールと１，４－ビスクロロメチルベンゼンから得られるクレゾールアラルキル樹脂(水酸基当量１９０ｇ／ｅｑ、平均核体数５．４)４００．０ｇ、水酸化カリウム４．００ｇ、トルエン４００．０ｇを仕込み１３０℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド１３７．０ｇを徐々に滴下し、１２５～１３０℃、０．１５～０．４０ＭＰａで１０時間反応させた。その後、室温まで冷却し、反応溶液に８５％リン酸を５．２４ｇ添加して水酸化カリウムを中和した。水酸基当量２５４ｇ／ｅｑ、樹脂分５７．５％のプロピレンオキサイド付加物溶液を得た。 <Synthesis example of carboxyl group-containing photosensitive resin (B-6)>
In a 1 L autoclave, 400.0 g of cresol aralkyl resin (hydroxyl equivalent: 190 g / eq, average number of nuclei: 5.4) obtained from cresol and 1,4-bischloromethylbenzene, 4.00 g of potassium hydroxide, 400.0 g of toluene The solution was stirred and dissolved while raising the temperature to 130 ° C. Next, 137.0 g of propylene oxide was gradually dropped and reacted at 125 to 130 ° C. and 0.15 to 0.40 MPa for 10 hours. Then, it cooled to room temperature and added 5.24g of 85% phosphoric acid to the reaction solution, and neutralized potassium hydroxide. A propylene oxide adduct solution having a hydroxyl group equivalent of 254 g / eq and a resin content of 57.5% was obtained.
　得られたプロピレンオキサイド付加物溶液９００．０ｇ、４－メトキシフェノール０．５０ｇ、トルエン６９４．２ｇ、アクリル酸６９．２ｇ、メタンスルホン酸１５．０ｇを２Ｌガラスフラスコに仕込み、１００～１１０℃の温度で６時間エステル化反応を行った。反応により生成した水はトルエンとの共沸混合物として、１７．３ｇの水が留出した。その後、室温まで冷却し、得られたアクリレート樹脂溶液を１５％水酸化カリウム溶液５８．４ｇで中和し、５％食塩水で１回、純水で３回洗浄し、アクリレート樹脂溶液を精製した。溶液中の樹脂分は３６．５％であった。 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%.
精製したアクリレート樹脂溶液１５００．０ｇのトルエンを留去しつつ、ジエチレングリコールモノエチルエーテルアセテート３０１．７ｇで置換し、テトラヒドロ無水フタル酸１５６．４ｇ、４－メトキシフェノール０．３０ｇ、トリフェニルホスフィン２．０１ｇを添加して９０～１００℃の温度で６時間反応させた。得られたカルボキシル基含有感光性樹脂溶液は固形分７０％、固形分酸価８１ｍｇＫＯＨ／ｇ、一般式（４）に示したｎ＋ｍ＝４．４であった。これを樹脂溶液Ｂ－６とする。 While distilling off 1500.0 g of the purified acrylate resin solution, 301.7 g of diethylene glycol monoethyl ether acetate, 156.4 g of tetrahydrophthalic anhydride, 0.30 g of 4-methoxyphenol, 2.01 g of triphenylphosphine And reacted at a temperature of 90 to 100 ° C. for 6 hours. The obtained carboxyl group-containing photosensitive resin solution had a solid content of 70%, a solid content acid value of 81 mgKOH / g, and n + m = 4.4 shown in the general formula (4). This is designated as Resin Solution B-6.
　［実施例１３～２０、比較例３～６］
　上記合成例の樹脂溶液を用い、表４に示す種々の成分、割合（質量部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで混練し、ソルダーレジスト用感光性樹脂組成物を調製した。ここで得られた感光性樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ１５μｍ以下であった。
　なお、表４において、比較例４，６の組成物は、表１における比較例１，２とそれぞれ同様の組成物である。 [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 μm or less.
In Table 4, the compositions of Comparative Examples 4 and 6 are the same compositions as Comparative Examples 1 and 2 in Table 1, respectively.
Figure JPOXMLDOC01-appb-T000004
 ［備考］
＊１～＊１２：表１［備考］に同じ。
Figure JPOXMLDOC01-appb-T000004
 [Remarks]
* 1 to * 12: Same as Table 1 [Remarks].
　表４に示す実施例及び比較例の組成物について性能評価及び特性評価を行った。評価結果を表５に示す。なお、タック性以外の評価方法については、第一の実施形態の実施例と同様であるため、説明は割愛する。 Performance evaluation and characteristic evaluation were performed on the compositions of Examples and Comparative Examples shown in Table 4. The evaluation results are shown in Table 5. Since the evaluation methods other than the tackiness are the same as those in the example of the first embodiment, the description thereof is omitted.
　性能評価：
　＜タック性＞
　それぞれの光硬化性樹脂組成物をパターン形成された銅箔基板上にスクリーン印刷で前面塗布し、８０℃の熱風循環式乾燥炉で３０分間乾燥させ、室温まで放冷した。この基板にＰＥＴ製ネガフィルムを当て、ＯＲＣ社製（ＨＭＷ－ＧＷ２０）で１分間減圧条件下で圧着させ、その後、ネガフィルムを剥がしたときのフィルムの張り付き状態を評価した。
　○：フィルムを剥がすときに、僅かに抵抗があり、塗膜に僅かに跡が確認できる。
　△：フィルムを剥がすときに、僅かに抵抗があり、塗膜にはっきり跡がついている。
　×：フィルムを剥がすときに、大きな抵抗があり、塗膜にはっきり跡がついている。 Performance evaluation:
<Tackiness>
Each photocurable resin composition was coated on the front surface of a patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded with ORC (HMW-GW20) under reduced pressure conditions for 1 minute. Thereafter, the state of the film when it was peeled off was evaluated.
○: When the film is peeled off, there is a slight resistance, and a trace can be confirmed on the coating film.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When peeling a film, there exists big resistance and the coating film has a trace.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　［実施例２１～２８］
＜ドライフィルム評価＞
　表４に示す配合割合で調製した実施例１３～２０の各組成物をメチルエチルケトンにて希釈し、ＰＥＴフィルム上に塗布して８０℃で３０分乾燥し、厚さ２０μｍの感光性樹脂組成物層を形成した。さらにその上にカバーフィルムを貼り合わせてドライフィルムを作製し、それぞれを実施例２１～２８とした。 [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 μm. Formed. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 21 to 28, respectively.
　上記のようにして得られたドライフィルムからカバーフィルムを剥がし、パターン形成された銅箔基板に、フィルムを熱ラミネートし、次いで、上記の塗膜特性評価に用いた基板と同様の条件で露光した。露光後、キャリアフィルムを剥がし、３０℃の１％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で９０秒間現像を行い、レジストパターンを得た。この基板を、ＵＶコンベア炉にて積算露光量１０００ｍＪ／ｃｍ２の条件で紫外線照射した後、１５０℃で６０分加熱して硬化した。得られた硬化皮膜を有する試験基板について、上記の評価方法にて性能評価及び特性評価を行った。評価結果を表６に示す。 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. . After the exposure, 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. About the test board | 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.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表５、表６に示す結果から明らかなように、第二の実施形態にかかる光硬化性熱硬化性樹脂組成物は、第一の実施形態にかかる光硬化性熱硬化性樹脂組成物と同様に、半導体パッケージ用ソルダーレジストに必要とされるＰＣＴ耐性、冷熱衝撃耐性、ＨＡＳＴ特性を兼ね備え、非常に信頼性の高いソルダーレジスト硬化塗膜が得られることが明らかとなり、光硬化性熱硬化性樹脂組成物として有用であることが認められた。 As is clear from the results shown in Tables 5 and 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. In addition, it has been clarified that 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.

Claims (5)

  1. 　カルボキシル基含有樹脂、下記一般式（１）～（３）に示す構造を有する感光性樹脂および光重合開始剤を含有することを特徴とする光硬化性熱硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000023
     （式（１）中、Ｒ１は下記式（２）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～６．０、ｎ＝０～６．０、ｍ＝０～６．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
    Figure JPOXMLDOC01-appb-C000024
     （式（２）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（３）の基または水素を示し、ｋ＝０．３～１０．０である。）
    Figure JPOXMLDOC01-appb-C000025
     （式（３）中、Ｒ５は水素またはメチル基を示す。）     A photocurable 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.
    Figure JPOXMLDOC01-appb-C000023
     (In the formula (1), 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)
    Figure JPOXMLDOC01-appb-C000024
     (In formula (2), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (3), and k = 0.3 to 10.0.)
    Figure JPOXMLDOC01-appb-C000025
     (In formula (3), R 5 represents hydrogen or a methyl group.)
  2. 　下記一般式（４）～（７）に示す構造を有するカルボキシル基含有感光性樹脂および光重合開始剤を含有することを特徴とする光硬化性熱硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000026
     （式（４）中、Ｒ１は下記式（５）の基を示し、Ｒ２はメチル基またはＯＲ１基を示し、ｎ＋ｍ＝１．５～４．０、ｎ＝０～４．０、ｍ＝０～４．０、ｌ＝０～３、ｎ：ｍ＝１００：０～０：１００である。）
    Figure JPOXMLDOC01-appb-C000027
     （式（５）中、Ｒ３は水素またはメチル基を示し、Ｒ４は下記（６）あるいは（７）の基または水素を示し、ｋ＝０．３～１０．０である。）
    Figure JPOXMLDOC01-appb-C000028
     （式（６）中、Ｒ５は水素またはメチル基を示す。）
    Figure JPOXMLDOC01-appb-C000029
     （式(７)中のＸは酸無水物残基を表す。）     A photocurable thermosetting resin composition comprising a carboxyl group-containing photosensitive resin having a structure represented by the following general formulas (4) to (7) and a photopolymerization initiator.
    Figure JPOXMLDOC01-appb-C000026
     (In the formula (4), 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)
    Figure JPOXMLDOC01-appb-C000027
     (In Formula (5), R 3 represents hydrogen or a methyl group, R 4 represents a group or hydrogen of the following (6) or (7), and k = 0.3 to 10.0)
    Figure JPOXMLDOC01-appb-C000028
     (In formula (6), R 5 represents hydrogen or a methyl group.)
    Figure JPOXMLDOC01-appb-C000029
     (X in the formula (7) represents an acid anhydride residue.)
  3. 　請求項１又は請求項２に記載の光硬化性熱硬化性樹脂組成物を、フィルム上に塗布乾燥して得られることを特徴とする光硬化性熱硬化性のフィルム。 A photocurable thermosetting film obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 on a film.
  4. 　請求項１又は請求項２に記載の光硬化性熱硬化性樹脂組成物、又は請求項３に記載のフィルムを、活性エネルギー線照射及び／又は加熱により硬化させて得られることを特徴とする硬化物。 Curing characterized by being obtained by curing the photocurable thermosetting resin composition according to claim 1 or 2 or the film according to claim 3 by irradiation with active energy rays and / or heating. object.
  5. 　請求項１又は請求項２に記載の光硬化性熱硬化性樹脂組成物、又は請求項３に記載のフィルムを、活性エネルギー線照射及び／又は加熱により硬化させて得られることを特徴とする硬化物を具備するプリント配線板。 Curing characterized by being obtained by curing the photocurable thermosetting resin composition according to claim 1 or 2 or the film according to claim 3 by irradiation with active energy rays and / or heating. A printed wiring board comprising objects.
PCT/JP2011/001924 2010-03-31 2011-03-30 Photo-curable thermosetting resin composition WO2011122027A1 (en)

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