WO2023051718A1 - 固化性树脂组合物、层叠体、固化物及电子部件 - Google Patents

固化性树脂组合物、层叠体、固化物及电子部件 Download PDF

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WO2023051718A1
WO2023051718A1 PCT/CN2022/122716 CN2022122716W WO2023051718A1 WO 2023051718 A1 WO2023051718 A1 WO 2023051718A1 CN 2022122716 W CN2022122716 W CN 2022122716W WO 2023051718 A1 WO2023051718 A1 WO 2023051718A1
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photopolymerization initiator
group
resin composition
curable resin
mass
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PCT/CN2022/122716
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English (en)
French (fr)
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工藤知哉
蒋铮
吕川
许红金
浦国斌
加藤贤治
刘洪兵
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太阳油墨（苏州）有限公司
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Priority to CN202280048170.XA priority Critical patent/CN117642697A/zh
Priority to KR1020247009897A priority patent/KR20240063917A/ko
Publication of WO2023051718A1 publication Critical patent/WO2023051718A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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

Definitions

  • the present invention relates to a curable resin composition, a laminate having the curable resin composition as a resin layer, a cured product formed from the laminate, and an electronic component having the cured product.
  • a photosensitive resin composition including a compound having a carboxyl group but not having photosensitivity, an epoxy resin, and an oxime ester-based photopolymerization initiator as described in Patent Document 1 is currently used.
  • Patent Document 1 Japanese Patent Laid-Open No. 2012-098470
  • the photosensitive resin composition as in Patent Document 1 has insufficient surface curability after exposure, and may not exhibit sufficient performance due to scratches on the surface until heat curing after pattern exposure.
  • outgassing occurs due to heat treatment at a high temperature, causing a problem of contamination of the surroundings. Therefore, an insulating material that satisfies both surface hardening and suppression of outgassing is required.
  • the present invention provides a curable resin composition or a laminate capable of obtaining a cured product that can achieve both surface hardening and outgassing suppression, as well as insulation reliability, soldering heat resistance, and other properties.
  • the present invention is as follows.
  • a curable resin composition comprising (A) carboxyl-containing resin, (B) inorganic filler, (C) thermosetting resin, (D) photopolymerization initiator,
  • the compounding quantity of the said (D-b) photopolymerization initiator represented by formula (1) is 0.1 mass % or more and 10 mass % or less with respect to the compounding quantity of the said (D-a) acylphosphine photopolymerization initiator .
  • R 23 represents hydrogen atom, alkyl, alkoxy, phenyl, naphthyl
  • R 21 and R 22 independently represent hydrogen atom, alkyl, alkoxy, halogen atom, phenyl, naphthyl, Anthracenyl, pyridyl, benzofuryl, benzothienyl;
  • Ar represents a single bond, or an alkylene group, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, anthracene group, thienylene group, furylene group, 2 , 5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-stilbene-diyl; n represents a number from 0 to 1.
  • a laminate comprising the curable resin composition according to any one of 1 to 5 as a resin layer.
  • a curable resin composition or a laminate capable of obtaining a cured product that can achieve both surface hardening and outgassing suppression, as well as insulation reliability and soldering heat resistance.
  • the present invention relates to a curable resin composition
  • a curable resin composition comprising (A) carboxyl-containing resin, (B) inorganic filler, (C) thermosetting resin, (D) photopolymerization initiator,
  • the compounding quantity of the said (D-b) photopolymerization initiator represented by formula (1) is 0.1 mass % or more and 10 mass % or less with respect to the compounding quantity of the said (D-a) acylphosphine photopolymerization initiator
  • R 23 represents hydrogen atom, alkyl, alkoxy, phenyl, naphthyl
  • R 21 and R 22 independently represent hydrogen atom, alkyl, alkoxy, halogen atom, phenyl, naphthyl, Anthracenyl, pyridyl, benzofuryl, benzothienyl;
  • Ar represents a single bond, or an alkylene group, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, anthracene group, thienylene group, furylene group, 2 , 5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-stilbene-diyl; n represents a number from 0 to 1.
  • Carboxyl group-containing resin can have alkali developability by the carboxyl group contained.
  • (A) carboxyl group-containing resin various conventionally well-known carboxyl group-containing resins which have a carboxyl group in a molecule
  • carboxyl group-containing resin examples include compounds (any one of oligomers and polymers) listed below.
  • (meth)acrylate refers to the term which collectively refers to acrylate, methacrylate, and these mixtures, and the same applies to other similar expressions.
  • aliphatic diisocyanate branched chain aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and other diisocyanates, and carboxyl-containing diisocyanates such as dimethylol propionic acid and dimethylol butyric acid Alcohol compounds, polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, phenolic Carboxyl group-containing polyurethane resin obtained by polyaddition reaction of diol compounds such as hydroxyl group and alcoholic hydroxyl group compound.
  • carboxyl-containing diisocyanates such as dimethylol propionic acid and dimethylol butyric acid Alcohol compounds, polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-
  • diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and polycarbonate polyols, polyether polyols, and polyester polyols , polyolefin polyol, acrylic polyol, bisphenol A series alkylene oxide adduct diol, compound having phenolic hydroxyl group and alcoholic hydroxyl group, etc.
  • a terminal carboxyl group-containing polyurethane resin formed by reacting the terminal of a polyurethane resin with an acid anhydride.
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.
  • 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, such as p-hydroxyphenethyl alcohol, and a compound containing (meth)acrylic acid, etc.
  • the monocarboxylic acid reaction of unsaturated groups, the alcoholic hydroxyl group of the obtained reaction product reacts with polyacid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride. resin.
  • a carboxyl group-containing resin having at least any one of an amide structure and an imide structure.
  • Glycidyl (meth)acrylate, ⁇ -methyl glycidyl (meth)acrylate, and methacrylic acid 3 are further added to the carboxyl group-containing resin described in (1) to (13) above, Carboxyl group-containing resins such as 4-epoxycyclohexyl methyl ester and other compounds having one epoxy group and one or more (meth)acryloyl groups in the molecule.
  • the carboxyl group-containing resin is not particularly limited as long as it has a carboxyl group in the molecule, and the resin skeleton is not particularly limited, but preferably does not have a phenolic skeleton from the viewpoint of further improving insulation reliability and reflectance.
  • the carboxyl group-containing resin does not contain a phenol skeleton, coloring due to thermal deterioration is less likely to occur, and thus the reflectance tends to increase.
  • the phenolic skeleton refers to a skeleton derived from an aromatic compound having one or more hydroxyl groups directly bonded to an aromatic ring.
  • carboxyl group-containing resins it is preferable to contain at least one of the carboxyl group-containing resins described in (1), (7), (8), (10), (11), and (14) above.
  • the carboxyl group-containing resin described in (14) containing the above (1) or obtained by using (1) is particularly preferable from the viewpoint of easily reducing the chlorine concentration and further improving insulation reliability.
  • Carboxyl group-containing resin may be used individually by 1 type, and may use the mixture which combined 2 or more types.
  • the acid value of the carboxyl group-containing resin is preferably in the range of 20 to 120 mgKOH/g, more preferably in the range of 30 to 100 mgKOH/g.
  • the weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is usually preferably 2,000 to 150,000.
  • the weight average molecular weight is 2000 or more, the non-tackiness of a dry coating film, the moisture resistance of the coating film after exposure, and resolution are favorable.
  • a weight average molecular weight is 150000 or less, developability and storage stability are favorable. More preferably, it is 5,000 to 100,000.
  • the compounding quantity of a carboxyl group-containing resin is preferably 5-80 mass % with respect to the total solid content of curable resin composition, More preferably, it is 10-70 mass %, Especially preferably, it is 12-60 mass %.
  • the curable resin composition of this invention contains (B) an inorganic filler.
  • the inorganic fillers may be used alone or in combination of two or more.
  • the compounding amount of the inorganic filler is preferably in the range of 20 to 65% by mass, more preferably in the range of 25 to 60% by mass, particularly preferably in the range of 35 to 55% by mass, based on the total solid content of the curable resin composition. scope.
  • the compounding quantity of an inorganic filler is 35 mass % or more, it exists in the tendency for the curable resin composition excellent in surface curability, reflectance, soldering heat resistance, and insulation reliability to be obtained.
  • the compounding quantity of an inorganic filler is 55 mass % or less, it exists in the tendency for the curable resin composition excellent in defoaming property and a resolution to be obtained.
  • Examples of (B) inorganic fillers include titanium oxide, silicon dioxide, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, Silicon nitride, aluminum nitride, etc.
  • at least any one of titanium oxide, silicon dioxide, and barium sulfate is preferably contained, which can suppress curing shrinkage of the curable resin composition and improve properties such as adhesion, hardness, and reflectance.
  • titanium oxide usable in the curable resin composition of the present invention titanium oxide produced by the sulfuric acid method or the chlorine method, rutile-type titanium oxide, anatase-type titanium oxide, or hydrated metal oxide-based titanium oxide can be used.
  • Surface treatment titanium oxide for surface treatment based on organic compounds. Titanium oxide is classified into rutile type and anatase type according to the crystal structure. Among them, rutile-type titanium oxide is preferable. Anatase-type titanium oxide has higher whiteness than rutile-type titanium oxide, so it is commonly used. However, anatase-type titanium oxide has photocatalytic activity, and thus may cause discoloration of the resin in the curable resin composition. On the other hand, although the whiteness of rutile type titanium oxide is slightly inferior to that of anatase type, it has almost no photoactivity, so a stable cured product can be obtained.
  • the compounding amount of titanium oxide relative to the curable resin composition is preferably 1% by mass to 50% by mass, more preferably 1.5% by mass to 30% by mass, particularly preferably 2% by mass to 25% by mass.
  • the average particle diameter of the inorganic filler is preferably 50 ⁇ m or less, more preferably 0.1 to 25 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
  • the average particle diameter refers to the average particle diameter of a single inorganic filler or an inorganic filler dispersion.
  • a nanofiller having an average particle diameter of 100 nm or less may be used in combination.
  • the average particle diameter of the inorganic filler is a volume average particle diameter (D50) including not only the particle diameter of primary particles but also the particle diameter of secondary particles (aggregate).
  • the aforementioned average particle diameter can be measured using a measuring device based on a laser diffraction method such as Microtrac MT3300EXII manufactured by MicrotracBEL Corp., or a measuring device based on a dynamic light scattering method such as Nanotrac Wave II UT151 manufactured by MicrotracBEL Corp., depending on the average particle diameter. .
  • the (B) inorganic filler may be a surface-treated filler (surface-treated filler).
  • the surface treatment of the inorganic filler is not particularly limited, and surface treatment based on coupling agents such as silane-based, titanate-based, aluminate-based, zircoaluminate-based, etc., alumina treatment, etc. that do not introduce organic fillers can be used.
  • Well-known and customary methods such as surface treatment of groups.
  • (B) inorganic filler a commercial item can be used.
  • rutile-type titanium oxide for example, Taipaque R-820, Taipaque R-830, Taipaque R-930, Taipaque R-550, Taipaque R-630, Taipaque R-680 can be used.
  • anatase-type titanium oxide known ones can be used as the anatase-type titanium oxide.
  • anatase-type titanium oxide TITON A-110, TITON TCA-123E, TITON A-190, TITON A-197, TITON SA-1, TITON SA-1L (manufactured by Sakai Chemical Industry Co., Ltd.) can be used ; TA-100, TA-200, TA-300, TA-400, TA-500, TP-2 (manufactured by Fuji Titanium Industry Co., Ltd.); TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA -5.
  • TITANIX JA-C manufactured by Teika Co., Ltd.
  • KA-10, KA-15, KA-20, KA-30 manufactured by Titanium Industry Co., Ltd.
  • Taipaque A-100, Taipaque A-220, Taipaque W-10 manufactured by Ishihara Sangyo Co., Ltd.
  • silica products examples include SE-40 manufactured by Tokuyama Co., Ltd., MSV25G manufactured by Ronsen, MLV-2114 manufactured by Ronsen, SO-E5 manufactured by ADMATECHS, and SO-E2 manufactured by ADMATECHS.
  • the curable resin composition of this invention contains (C) thermosetting resin.
  • thermosetting resin epoxy resin, blocked isocyanate compound, amino resin, maleimide compound, benzoxazine resin, carbodiimide resin, cyclocarbonate compound, oxygen heterocycle Butane compounds, episulfide resins, melamine derivatives, etc.
  • Thermosetting resin may be used individually by 1 type, and may use it in combination of 2 or more types.
  • thermosetting resin it contains Epoxy resins are suitable.
  • Epoxy resins for example, known and commonly used epoxy resins such as bisphenol A type, bisphenol F type, aminophenol type, and phenol novolac type epoxy resins can be used suitably.
  • epoxy resins can be used individually or in combination of 2 or more types in curable resin composition of this invention.
  • either a liquid epoxy resin or a solid epoxy resin may be used.
  • thermosetting resins include, for example, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055 manufactured by DIC Corporation, Nippon Steel Chemical & Materials Co., Ltd.
  • Bisphenol A type epoxy resins such as Epotote YD-011, YD-013, YD-127, YD-128 manufactured by the company, and NPEL-128E (all trade names) manufactured by Nan Ya Plastics Co., Ltd.; manufactured by Mitsubishi Chemical Corporation Brominated epoxy resins such as jERYL903, EPICLON152 and EPICLON165 manufactured by DIC Corporation, Epotote YDB-400 and YDB-500 (both trade names) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; jER152 and jER154 manufactured by Mitsubishi Chemical Corporation , EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC Corporation, Epotote YDCN-701, YDCN-704 manufactured by Nippon Steel Chemical & Materials Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., Novolac-type epoxy resins such as EOCN-1025, EOCN-
  • Bisphenol F-type epoxy resins such as Epotote YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by the company; Epotote ST-2004, ST-2007, ST- 3000 (both trade names) and other hydrogenated bisphenol A epoxy resins; jER604 manufactured by Mitsubishi Chemical Corporation, Epotote YH-434 manufactured by Nippon Steel Chemical & Materials Co., Ltd., Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd.
  • Glycidylamine-type epoxy resins such as Glycidylamine type epoxy resins, both are brand names); Cycloaliphatic epoxy resins such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industry Co., Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, Nippon Kayaku Trihydroxyphenylmethane-type epoxy resins such as EPPN-501 and EPPN-502 (both trade names) manufactured by Mitsubishi Chemical Corporation; YL-6056, YX-4000, and YL-6121 (both trade names ) and other xylenol type or biphenol type epoxy resins or their mixtures; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation, and EXA-1514 manufactured by DIC Corporation (all Bisphenol S type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; jER YL
  • thermosetting resin 1-50 mass % normally with respect to the total solid content of curable resin composition, More preferably, it is 5-35 mass %.
  • the curable resin composition of this invention contains (D-a) an acyl phosphine photopolymerization initiator, and (D-b) a photopolymerization initiator represented by formula (1).
  • acylphosphine photopolymerization initiator a monoacylphosphine photopolymerization initiator and a bisacylphosphine photopolymerization initiator are mentioned, for example.
  • bis-(2,6-dichlorobenzoyl)phenylphosphine oxide bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-( 2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethyl Oxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethyl Oxybenzoyl)-2,5-d
  • the acylphosphine photopolymerization initiator preferably includes a photopolymerization initiator having three or more acylphosphine skeletons represented by the following formula (2) (trifunctional or higher acylphosphine photopolymerization initiator).
  • A represents independently of each other a single bond, O, S or NR 3 ;
  • G is the residue of a polyfunctional compound (core) G-(AH) m+n , wherein each of AH represents an alcoholic hydroxyl group or an amino group or a thiol group;
  • n and n satisfy that m+n is a number between 3 and 10;
  • n is a number between 3 and 8;
  • R 1 and R 2 are independently C 1 -C 18 alkyl, C 6 -C 12 aryl and C 5 -C 12 cycloalkyl, each of which can be unbroken or broken by the following groups: 1 More than one oxygen and/or sulfur atom and/or one or more substituted or unsubstituted imino groups, or R and R can be independently of each other five to six members containing oxygen and/or nitrogen and/or sulfur atoms Heterocyclic group, wherein, aforementioned R 1 and R 2 are each optionally substituted by aryl, alkyl, aryloxy, alkoxy, heteroatom and/or heterocyclic group;
  • Y is O or S
  • R 3 is hydrogen or C 1 -C 4 alkyl
  • the photopolymerization initiator of formula (2) does not contain a photocurable ethylenically unsaturated group.
  • m+n is a number between 3-8, more preferably a number between 3-6.
  • m is a number between 3-6, More preferably, it is a number between 3-5.
  • G-(AH) m+n is a polyhydric (polyhydric) compound selected from the group consisting of monomeric polyols, oligomer polyols, polymer polyols and mixtures thereof .
  • G-(AH) m+n is a polythiol compound.
  • G-(AH) m+n is a linear or branched polyamine.
  • G-(AH) m+n is a compound containing different functional groups, for example, a compound containing an amino group and a hydroxyl group.
  • G- is a residue obtained by removing a hydroxyl group and/or an amino group and/or a mercapto group in G-(AH) m+n listed above.
  • G-(AH) m+n has a number average molecular weight of 1500 or less, more preferably 800 or less, further preferably 500 or less.
  • the compound of formula (2) has alcoholic hydroxyl group and/or amino group and/or mercapto group.
  • Table 1 shows typical trifunctional or higher acylphosphine photopolymerization initiators included in formula (2).
  • PI-3, PI-4, PI-10, PI-11, PI-12, PI-14, and PI-17 are particularly preferred.
  • Examples of commercially available products include Omnipol TP manufactured by IGM RESINS B.V., and these acylphosphine-based photopolymerization initiators can be used alone or in combination of two or more.
  • a, b, c, and d in Table 1 are each independent numbers, and are appropriately selected so that the number average molecular weight of the trifunctional or higher acylphosphine photopolymerization initiator becomes a desired value.
  • Such a trifunctional or higher acylphosphine photopolymerization initiator can be produced by the method described in Japanese Patent No. 6599446, for example.
  • the curable resin composition of this invention contains the photoinitiator described in (D-b) formula (1) further as said (D) photoinitiator.
  • (D-a) an acylphosphine-based photopolymerization initiator and (D-b) a photopolymerization initiator as described in formula (1) curability excellent in surface curability, reflectance, soldering heat resistance, and insulation reliability can be obtained resin composition.
  • R 23 represents hydrogen atom, alkyl, alkoxy, phenyl, naphthyl
  • R 21 and R 22 independently represent hydrogen atom, alkyl, alkoxy, halogen atom, phenyl, naphthyl, Anthracenyl, pyridyl, benzofuryl, benzothienyl;
  • Ar represents a single bond, or an alkylene group, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, anthracene group, thienylene group, furylene group, 2 , 5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-stilbene-diyl; n represents a number from 0 to 1.
  • the alkyl group represented by R 23 is preferably an alkyl group having 1 to 17 carbon atoms.
  • the alkoxy group represented by R 23 is preferably an alkoxy group having 1 to 8 carbon atoms.
  • the phenyl group represented by R 23 may have a substituent, and the substituent includes, for example, an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group , an alkylamino group (preferably, the alkyl group has 1 to 8 carbon atoms), or a dialkylamino group (preferably, the alkyl group has 1 to 8 carbon atoms), and the like.
  • the substituent includes, for example, an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group , an alkylamino group (preferably, the alkyl group has 1 to 8 carbon atoms), or a dialkylamino group (preferably, the alkyl group has 1 to 8 carbon atoms), and the like.
  • the naphthyl group represented by R 23 may have a substituent, and examples of the substituent include the same groups as the above-mentioned substituents that the phenyl group represented by R 23 may have.
  • the alkyl group represented by R 21 and R 22 is preferably an alkyl group having 1 to 17 carbon atoms.
  • the alkoxy group represented by R 21 and R 22 is preferably an alkoxy group having 1 to 8 carbon atoms.
  • the phenyl group represented by R 21 and R 22 may have a substituent, and examples of the substituent include: an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), ), amino, alkylamino (preferably the number of carbon atoms in the alkyl group is 1 to 8), or dialkylamino group (the number of carbon atoms in the alkyl group is preferably 1 to 8), etc.
  • the naphthyl groups represented by R 21 and R 22 may have a substituent, and examples of the substituent include the same groups as the above-mentioned substituents that the phenyl group represented by R 21 and R 22 may have.
  • R 21 and R 23 are each independently methyl or ethyl, R 22 is methyl or phenyl, Ar is a single bond, phenylene, naphthylene or thienylene, n is 0.
  • any one of the compounds represented by the following formula (2) or formula (3) is more preferable.
  • the photoinitiator described in formula (1) can be used individually by 1 type or in combination of 2 or more types.
  • the compounding quantity of the photoinitiator described in (D-b) formula (1) exists in the range of 0.1-10 mass % with respect to the compounding quantity of (D-a) acylphosphine photoinitiator. Preferably it exists in the range of 0.2-8 mass %, More preferably, it exists in the range of 0.25-7.5 mass %.
  • (D-b)/(D-a) is within the above range, the surface curability and resolution of the curable resin composition become favorable, and the reflectance, soldering heat resistance, and insulation reliability of the cured film also improve.
  • the total compounding ratio of the (D-a) acylphosphine photopolymerization initiator and (D-b) the photopolymerization initiator described in the formula (1) is preferably 0.5 to 30% by mass relative to the total solid content of the curable resin composition. range, more preferably within the range of 1 to 20% by mass, particularly preferably within the range of 2 to 15% by mass. When this compounding quantity exists in the said range, the surface curability and resolution of a curable resin composition will become favorable, and the reflectance, soldering heat resistance, and insulation reliability of the cured film will also improve.
  • the curable resin composition of the present invention may further contain another photoinitiator different from the photoinitiator of the above-mentioned (D-a) acylphosphine-based photoinitiator and the photoinitiator described in the above-mentioned (D-b) formula (1).
  • this other photopolymerization initiator for example, benzophenone series, acetophenone series, aminoacetophenone series, benzoin ether series, benzil ketal series, oxime ether series, oxime ester series, hydroxyketone series, titanocene Department of known and customary compounds.
  • Examples of commercially available products include IRGACURE OXE01 and IRGACURE OXE02 manufactured by BASF JAPAN LTD.; Omnirad907, Omnirad369, and Omnirad379 manufactured by IGM RESINS B.V.; N-1919 and NCI-831 manufactured by ADEKA CORPORATION; TR-PBG-304 made by limited company, etc.
  • the curable resin composition of this invention can further compound the (E) polymerizable monomer which has an ethylenically unsaturated group in a molecule
  • the compounding quantity of a polymerizable monomer is the range of 5-40 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resins.
  • the compounding quantity of a photopolymerizable monomer is 5 mass parts or more, the photocurability imparting effect will become favorable.
  • it is 40 mass parts or less the dry-to-touch property of a coating film will become favorable.
  • pigments for coloring may be further added as needed.
  • antioxidants ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, adhesion aids, crosslinking agents and other known additives.
  • an organic solvent can be used for the synthesis of the above-mentioned (A) carboxyl group-containing resin, the adjustment of the curable resin composition, or the viscosity adjustment at the time of coating on a substrate or a first film.
  • the solvent examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum-based 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 ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, di Glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate
  • the curable resin composition of the present invention may be in the form of a laminate including: a first film; and a resin layer formed of the above-mentioned curable resin composition formed on the first film.
  • the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and the curable resin composition of the present invention is diluted with a chip coater, a knife coater, a lip coater, a rod coater, an extrusion machine, etc. Press coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc.
  • the resin layer can be obtained.
  • the coating film thickness is not particularly limited, but is normally selected so that the thickness of the resin layer after drying is within a range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
  • the peelable second film for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used, as long as the adhesive force between the resin layer and the second film when the second film is peeled What is necessary is just to use the 2nd film smaller than the adhesive force of a resin layer and a 1st film.
  • the curable resin composition of this invention is apply
  • the cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the laminate of the present invention, and has solder heat resistance, outgassing resistance, and insulation reliability.
  • the printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or the resin layer of the laminate.
  • the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the above-mentioned organic solvent, and the method is used such as dip coating, flow coating, roll coating, bar coating, etc.
  • the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ° C to form a non-sticky resin layer.
  • the resin layer is formed on the base material by peeling off the first film after sticking to the base material with a laminator or the like so that the resin layer is in contact with the base material.
  • paper phenolic resins paper epoxy resins, glass cloth epoxy resins, glass Polyimide resin, glass cloth/non-woven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin/polyethylene/polyphenylene ether resin, polyphenylene oxide/cyanic acid Copper-clad laminates for high-frequency circuits such as ester resins, copper-clad laminates of all grades (FR-4, etc.), and metal substrates, polyimide films, polyethylene terephthalic acid, etc. Ethylene glycol ester film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.
  • PEN polyethylene naphthalate
  • the volatilization and drying after coating the curable resin composition of the present invention can be carried out by using a hot air circulation drying oven, IR oven, hot plate, convection oven, etc. (using a heat source equipped with an air heating method using steam) device, the method of convective contact with the hot air in the dryer and the method of blowing it to the support by using a nozzle), so as to carry out.
  • a hot air circulation drying oven IR oven, hot plate, convection oven, etc. (using a heat source equipped with an air heating method using steam) device, the method of convective contact with the hot air in the dryer and the method of blowing it to the support by using a nozzle), so as to carry out.
  • the resin layer After the resin layer is formed on the substrate, it is selectively exposed to active energy rays through a photomask formed with a predetermined pattern, and the unexposed part is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% by weight of sodium carbonate aqueous solution). , forming a cured pattern. Furthermore, after irradiating active energy rays to the cured product, heat curing (for example, 100 to 220° C.), or irradiating active energy rays after heat curing, or only by heat curing to finally completely cure (main curing), thereby forming a dense A cured film with excellent properties such as compatibility and hardness.
  • a dilute alkaline aqueous solution for example, 0.3 to 3% by weight of sodium carbonate aqueous solution.
  • the exposure machine used for the above-mentioned active energy ray irradiation as long as it is equipped with an LED light source lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, etc.
  • Devices such as laser direct imaging devices that use CAD data from a computer to draw images in a direct laser fashion.
  • the exposure wavelength of the direct-drawing device is preferably in the range of 380 to 450 nm.
  • the amount of exposure used for image formation varies depending on the film thickness and the like, but can be generally set within a range of 10 to 1500 mJ/cm 2 , preferably within a range of 20 to 1000 mJ/cm 2 .
  • developing method dipping method, spraying method, spraying method, brushing method, etc.
  • developing solution potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia , amines, etc. in alkaline aqueous solution.
  • the curable resin composition of the present invention is suitable for forming a cured film on an electronic component of an electronic device that requires miniaturization and high performance, and is particularly suitable for forming a cured film on a printed circuit board that requires miniaturization and high density. It is suitable for forming a permanent coating, and is further suitable for forming a solder resist layer, an interlayer insulating layer, and a cover layer.
  • D-1 Omnipol TP trifunctional or higher acylphosphine oxide-based photopolymerization initiator (structure of PI-3 in Table 1 above), manufactured by IGM RESINS B.V. (solid content 100%)
  • the weight average molecular weight (Mw) of the resin solution thus obtained was 15,000, the solid content was 39%, and the acid value of the solid content was 79.8 mgKOH/g.
  • triphenylphosphine was injected
  • the solid content of the resin solution thus obtained was 64%, and the acid value of the solid content was 89 mgKOH/g.
  • the curable resin compositions of the above-mentioned examples and comparative examples were coated on the entire surface by screen printing on a copper-clad laminate pretreated by polishing and grinding, and dried at 80° C. in a hot air circulation drying oven. After 30 minutes, it was cooled to room temperature to form a resin layer with a thickness of 40 ⁇ m.
  • a DI exposure machine equipped with an LED light source (Ledia 6 manufactured by SCREEN Co., Ltd.), and perform full-surface exposure with a 385nm light source output of 100% and an exposure amount of 1000mJ/ cm2 , using a 1% by mass sodium carbonate aqueous solution at 30°C , Image development was performed for 50 seconds under the condition of a spray pressure of 0.15 MPa. Then, the resin layer was cured for 60 minutes (post-curing) in the hot-air circulation type drying oven adjusted to 150 degreeC, and the board
  • curable resin compositions of the above-mentioned examples and comparative examples were coated on the entire surface of the FR-4 substrate pretreated by polishing and grinding by screen printing, dried at 80° C. for 30 minutes, and cooled to room temperature to form A resin layer with a thickness of 40 ⁇ m.
  • the upper surface (exposed surface) of the above composition after drying is formed with a line/space (L/S) of 30 ⁇ m/30 ⁇ m, 40 ⁇ m/40 ⁇ m, 50 ⁇ m/50 ⁇ m, 60 ⁇ m/60 ⁇ m, 70 ⁇ m/70 ⁇ m , 80 ⁇ m/80 ⁇ m, 90 ⁇ m/90 ⁇ m, 100 ⁇ m/100 ⁇ m, and 200 ⁇ m/200 ⁇ m patterns were overlaid with a negative film, using an LED exposure machine (Ledia6 manufactured by SCREEN Co., Ltd.) with a 385nm light source output power of 100% and an exposure amount of 1000mJ/ cm2 . The negative exposes the resin layer.
  • L/S line/space
  • the process of applying the curable resin compositions of the above-mentioned Examples and Comparative Examples to the dried double-sided printed board in a direction parallel to the pattern so that the cured film thickness becomes 120 ⁇ m by the screen printing method was carried out.
  • the entire face of the pre-treated face After leaving still at room temperature for 30 minutes, it dried at 80 degreeC for 30 minutes in the hot-air circulation type drying oven, and produced the defoaming property evaluation board
  • the defoaming property evaluation substrate was observed with a 20-magnification optical microscope, the number of bubbles between circuits was counted, and the defoaming property was evaluated as follows based on the number of bubbles.
  • the curable resin compositions of the above-mentioned examples and comparative examples were coated on the entire surface by screen printing on a copper-clad laminate pretreated by polishing and grinding, and dried at 80° C. in a hot air circulation drying oven. After 30 minutes, it was cooled to room temperature to form a resin layer with a thickness of 40 ⁇ m.
  • a DI exposure machine equipped with an LED light source (Ledia 6 manufactured by SCREEN Co., Ltd.), and perform full-surface exposure with a 385nm light source output of 100% and an exposure amount of 1000mJ/ cm2 , using a 1% by mass sodium carbonate aqueous solution at 30°C , Image development was performed for 50 seconds under the condition of a spray pressure of 0.15 MPa.
  • the pencil hardness of the surface of the obtained resin layer was measured based on JISK5600-5-4. The evaluation criteria are as follows.
  • the pencil hardness of the surface of the cured product of evaluation substrate A was measured and evaluated according to JIS K 5600-5-4.
  • the evaluation criteria are as follows.
  • the pencil hardness was 6H or more in any of the cured products of Examples and Comparative Examples (described as ⁇ in Tables 2 and 3).
  • the minimum design line width remaining on the substrate was visually confirmed, and the resolution was evaluated according to the following criteria.
  • the minimum design line width exceeds 70 ⁇ m and is 90 ⁇ m or less.
  • the reflectance at 450 nm of the obtained cured product was measured using a spectrophotometer CM-2600d manufactured by Konica Minolta Corporation, and evaluation was performed in accordance with the following criteria.
  • the reflectance is less than 70%
  • rosin-based flux was applied to the surface of the cured product, and then immersed in a solder bath at 260° C. for 20 seconds. After dipping, it is naturally cooled until the substrate reaches room temperature, and dipped in a solder bath again. After dipping several times, the appearance after cleaning the flux with denatured alcohol was observed visually, and it evaluated according to the following evaluation criteria.
  • a powder sample was collected from the formed cured product, placed in a thermal desorption unit (TDU) manufactured by GERSTEL Co., Ltd., heated at a heat extraction temperature of 260°C for 10 minutes, and cooled with liquid nitrogen at -60°C. Collect the exhaust components that occur.
  • the collected exhaust components were separated and analyzed with a gas chromatograph-mass spectrometer (6890N/5973N) manufactured by Agilent Technologies, and quantified in terms of n-dodecane.
  • the exhaust gas in Example 1 was set as 100% by mass, according to the following criteria Make an evaluation.
  • Exhaust gas component exceeds 150% by mass and is 200% by mass or less
  • the curable resin composition of the aforementioned examples and comparative examples is coated on the entire surface by screen printing, and then heated by hot air circulation. Drying was carried out at 80° C. for 30 minutes in a drying oven to form a resin layer with a thickness of 40 ⁇ m. Next, it was heated at 150° C. for 60 minutes in a hot-air circulation drying oven to form a cured product of the resin layer, thereby producing an insulation reliability evaluation substrate.
  • the evaluation substrate was placed in a high-temperature and high-humidity tank under an atmosphere of 85°C and a humidity of 85%, and a voltage of 3.5V was applied to conduct an insulation reliability test in the tank.
  • the in-slot insulation resistance value of the cured product when various times elapsed was evaluated in accordance with the following criteria.
  • the insulation resistance value is 10 7 ⁇ or more, but after 800 hours, the insulation resistance value is less than 10 7 ⁇
  • the insulation resistance value was less than 10 7 ⁇ after 500 hours.
  • Example 1 As can be seen from Table 2 and Table 3, compared with Comparative Example 1 comprising only a photopolymerization initiator other than (D-a) and a photopolymerization initiator of (D-b), the photopolymerization initiator comprising (D-a) and (D-b)
  • the resolution, soldering heat resistance, outgassing resistance, and insulation reliability of Example 1 were significantly improved for both photopolymerization initiators.
  • Pencil hardness after pattern exposure of Example 1 containing both the photopolymerization initiator (D-a) and the photopolymerization initiator (D-b) compared to Comparative Example 2 containing only the photopolymerization initiator (D-a) reflectivity, soldering heat resistance and insulation reliability have been greatly improved.
  • the curable resin composition of the present invention is excellent in resolution, defoaming, and surface curability, and that outgassing is suppressed, and its cured product is also excellent in insulation reliability, soldering heat resistance, and the like.
  • the curable resin composition can efficiently produce insulating materials satisfying higher-level requirements, and is very suitable for electronic equipment requiring miniaturization and high performance.

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Abstract

提供一种兼顾表面固化性和排气的抑制，且兼具绝缘可靠性、焊接耐热性等各项特性的固化性树脂组合物、层叠体、固化物及电子部件。该固化性树脂组合物包含(A)含羧基树脂、(B)无机填料、(C)热固性树脂、(D)光聚合引发剂，作为前述(D)光聚合引发剂，包含(D-a)酰基膦系光聚合引发剂和(D-b)具有特定结构的光聚合引发剂，相对于所述(D-a)酰基膦系光聚合引发剂的配混量，所述(D-b)具有特定结构的光聚合引发剂的配混量为0.1质量％以上且10质量％以下。

Description

固化性树脂组合物、层叠体、固化物及电子部件 技术领域
本发明涉及固化性树脂组合物、具有该固化性树脂组合物作为树脂层的层叠体、由该层叠体形成的固化物和具有该固化物的电子部件。
背景技术
近年来，伴随着小型化、高性能化的要求，电子机器中搭载的半导体芯片的高密度化、高功能化不断发展，安装半导体芯片的印刷电路板也要求小型高密度化。其结果是，最近印刷电路板中所用的绝缘材料也进一步要求细微化、高性能化。
作为这样的绝缘材料，目前使用如专利文献1所记载的包含具有羧基而不具备感光性的化合物、环氧树脂和肟酯系光聚合引发剂的感光性树脂组合物等。
现有技术文献
专利文献
专利文献1：日本特开2012-098470号公报
发明内容
发明要解决的问题
然而，如专利文献1那样的感光性树脂组合物在曝光后的表面固化性不充分，存在图案曝光后直到进行热固化处理期间的表面划伤，无法发挥充分的性能的担心。根据所使用的光聚合引发剂的种类，通过高温下的热处理而发生排气，产生污染周围的问题。因此，需要兼顾表面固化性和排气的抑制的绝缘材料。
以及，对于绝缘可靠性、焊接耐热性等各项特性，也需要相比现有的感光性树脂组合物能够满足更高水准要求的绝缘材料。
本发明提供一种能够得到能兼顾表面固化性和排气的抑制，且兼具绝缘可靠性、焊接耐热性等各项特性的固化物的固化性树脂组合物或层叠体。
经过发明人积极地研究，发现通过在固化物树脂组合物中，作为光聚合引发剂，同时配混酰基膦系光聚合引发剂和具有如式(1)所示的特定结构的光聚合引发剂，从而能够解决上述全部技术问题，从而完成了本发明。
即，本发明如下所述。
1.一种固化性树脂组合物，其包含(A)含羧基树脂、(B)无机填料、(C)热固性树脂、(D)光聚合引发剂，
作为前述(D)光聚合引发剂，包含(D-a)酰基膦系光聚合引发剂和(D-b)如式(1)所示的光聚合引发剂，
相对于所述(D-a)酰基膦系光聚合引发剂的配混量，所述(D-b)如式(1)所示的光聚合引发剂的配混量为0.1质量％以上且10质量％以下。
Figure PCTCN2022122716-appb-000001
式中，R 23表示氢原子、烷基、烷氧基、苯基、萘基；R 21、R 22分别独立地表示氢原子、烷基、烷氧基、卤原子、苯基、萘基、蒽基、吡啶基、苯并呋喃基、苯并噻吩基；
Ar表示单键、或碳数1～10的亚烷基、亚乙烯基、亚苯基、亚联苯基、亚吡啶基、亚萘基、亚蒽基、亚噻吩基、亚呋喃基、2,5-吡咯-二基、4,4’-茋-二基、4,2’-茋-二基；n表示0～1的数。
2.根据1所述的固化性树脂组合物，其特征在于，相对于固化性树脂组合物的总固体成分量，所述(B)无机填料的配混量为35质量％以上且55质量％以下。
3.根据1所述的固化性树脂组合物，其特征在于，作为所述(B)无机填料，包含氧化钛。
4.根据1所述的固化性树脂组合物，其特征在于，作为(D-a)酰基膦系光聚合引发剂，包含3官能以上的酰基膦系光聚合引发剂。
5.根据1～4中任一项所述的固化性树脂组合物，其特征在于，前述(A)含羧基树脂不具有酚骨架。
6.一种层叠体，其特征在于，具有1～5中任一项所述的固化性树脂组合物作为树脂层。
7.一种固化物，其特征在于，通过使1～5中任一项所述的固化性树脂组合物固化而成，或者通过使6所述的层叠体的树脂层固化而成。
8.一种电子部件，其具有7所述的固化物。
本发明的效果
通过本发明，可以提供一种能够得到能兼顾表面固化性和排气的抑制，且兼具绝缘可靠性、焊接耐热性等各项特性的固化物的固化性树脂组合物或层叠体。
具体实施方式
以下，详细说明本发明的实施方式。
本发明涉及一种固化性树脂组合物，其包含(A)含羧基树脂、(B)无机填料、(C)热固性树脂、(D)光聚合引发剂，
作为前述(D)光聚合引发剂，包含(D-a)酰基膦系光聚合引发剂和(D-b)如式(1)所示的光聚合引发剂，
相对于所述(D-a)酰基膦系光聚合引发剂的配混量，所述(D-b)如式(1)所示的光聚合引发剂的配混量为0.1质量％以上且10质量％以下
Figure PCTCN2022122716-appb-000002
式中，R 23表示氢原子、烷基、烷氧基、苯基、萘基；R 21、R 22分别独立地表示氢原子、烷基、烷氧基、卤原子、苯基、萘基、蒽基、吡啶基、苯并呋喃基、苯并噻吩基；
Ar表示单键、或碳数1～10的亚烷基、亚乙烯基、亚苯基、亚联苯基、亚吡啶基、亚萘基、亚蒽基、亚噻吩基、亚呋喃基、2,5-吡咯-二基、4,4’-茋-二基、4,2’-茋-二基；n表示0～1的数。
以下对本发明的固化性树脂组合物的各成分进行详细说明。
(A)含羧基树脂
含羧基树脂能够通过所含的羧基而具有碱显影性。作为(A)含羧基树脂，可以使用在分子中具有羧基的以往公知的各种含羧基树脂。从固化性、耐显影性的方面出发，特别优选在分子中除了羧基以外，还具有烯属不饱和键的含羧基感光性树脂，也可以仅使用不具有烯属不饱和键的含羧基树脂。
作为含羧基树脂的具体例，可以举出以下中列举的化合物(低聚物和聚合物中的任意者)。需要说明的是，本说明书中，(甲基)丙烯酸酯是指，统称丙烯酸酯、甲基丙烯酸酯和它们的混合物的术语，对于其他类似的表现也同样。
(1)通过(甲基)丙烯酸等不饱和羧酸、与苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸低级烷基酯、异丁烯等含不饱和基团的化合物的共聚而得到的含羧基树脂。
(2)利用脂肪族二异氰酸酯、支链脂肪族二异氰酸酯、脂环式二异氰酸酯、芳香族二异氰酸酯等二异氰酸酯、和二羟甲基丙酸、二羟甲基丁酸等含羧基的二元醇化合物、以及聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烃系多元醇、丙烯酸类多元醇、双酚A系环氧烷加成物二醇、具有酚性羟基和醇性羟基的化合物等二醇化合物的加聚反应而得到的含羧基的聚氨酯树脂。
(3)利用脂肪族二异氰酸酯、支链脂肪族二异氰酸酯、脂环式二异氰酸酯、芳香族二异氰酸酯等二异氰酸酯化合物、和聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多元醇、聚烯烃系多元醇、丙烯酸类多元醇、双酚A系环氧烷加成物二醇、具有酚性羟基和醇性羟基的化合物等二醇化合物的加聚反应而得到聚氨酯树脂，使该聚氨酯树脂的末端与酸酐反应而成的含末端羧基聚氨酯树脂。
(4)利用二异氰酸酯、和双酚A型环氧树脂、氢化双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、联二甲酚型环氧树脂、联苯酚型环氧树脂等2官能环氧树脂的(甲基)丙烯酸酯或其部分酸酐改性物、含羧基的二元醇化合物、以及二醇化合物的加聚反应而得到的含羧基的聚氨酯树脂。
(5)上述(2)或(4)的树脂的合成中加入(甲基)丙烯酸羟基烷基酯等分子中具有1个羟基和1个以上(甲基)丙烯酰基的化合物而进行了末端(甲基)丙烯酰化的含羧基的聚氨酯树脂。
(6)上述(2)或(4)的树脂的合成中加入异佛尔酮二异氰酸酯和季戊四醇三丙烯酸酯的等摩 尔反应物等、分子中具有1个异氰酸酯基和1个以上(甲基)丙烯酰基的化合物而进行了末端(甲基)丙烯酰化的含羧基的聚氨酯树脂。
(7)使多官能环氧树脂与(甲基)丙烯酸反应，在存在于侧链的羟基上加成苯二甲酸酐、四氢苯二甲酸酐、六氢苯二甲酸酐等二元酸酐而成的含羧基树脂。
(8)使进一步用表氯醇将2官能环氧树脂的羟基环氧化而成的多官能环氧树脂与(甲基)丙烯酸反应，在生成的羟基上加成二元酸酐而成的含羧基树脂。
(9)使多官能氧杂环丁烷树脂与二羧酸反应，在生成的伯羟基上加成二元酸酐而成的含羧基的聚酯树脂。
(10)使1分子中具有多个酚性羟基的化合物与环氧乙烷、环氧丙烷等环氧烷反应而得到反应产物，使该反应产物与含不饱和基团的单羧酸反应，使由此得到的反应产物与多元酸酐反应而得到的含羧基树脂。
(11)使1分子中具有多个酚性羟基的化合物与碳酸亚乙酯、碳酸亚丙酯等环状碳酸酯化合物反应而得到反应产物，使该反应产物与含不饱和基团的单羧酸反应，使由此得到的反应产物与多元酸酐反应而得到的含羧基树脂。
(12)使1分子中具有多个环氧基的环氧化合物与对羟基苯乙醇等1分子中具有至少1个醇性羟基和1个酚性羟基的化合物、和(甲基)丙烯酸等含不饱和基团的单羧酸反应，使得到的反应产物的醇性羟基与马来酸酐、四氢苯二甲酸酐、偏苯三酸酐、均苯四酸酐、己二酸酐等多元酸酐反应而得到的含羧基树脂。
(13)具有酰胺结构和酰亚胺结构中的至少任意一者的含羧基树脂。
(14)在上述(1)～(13)等中记载的含羧基树脂上进一步加成(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸α-甲基缩水甘油酯、甲基丙烯酸3,4-环氧环己基甲酯等分子中具有1个环氧基和1个以上(甲基)丙烯酰基的化合物而成的含羧基树脂。
(A)含羧基树脂只要是分子中具有羧基的树脂即可，对树脂骨架没有特别限定，从绝缘可靠性、反射率的进一步改善的观点出发，优选不具有酚骨架。含羧基树脂内不含酚骨架的情况下，不易发生由热劣化导致的着色，因此有反射率提高的倾向。
酚骨架是指，源自具有1个或多个与芳香环直接键合的羟基的芳香族类化合物的骨架。
上述含羧基树脂中，优选包含上述(1)、(7)、(8)、(10)、(11)、(14)中记载的含羧基树脂中的至少任1种。从容易实现氯浓度降低、进一步提高绝缘可靠性的观点出发，特别优选包含上述(1)或使用(1)得到的(14)中记载的含羧基树脂。
(A)含羧基树脂可以单独使用1种，也可以使用组合2种以上而成的混合物。
(A)含羧基树脂的酸值优选处于20～120mgKOH/g的范围、更优选为30～100mgKOH/g的范围。通过将(A)含羧基树脂的酸值设为上述范围，良好的碱显影成为可能，能够形成良好的固化物的图案。
(A)含羧基树脂的重均分子量根据树脂骨架而异，通常优选为2000～150000。重均分子量为2000以上的情况下，干燥涂膜的不粘性、曝光后的涂膜的耐湿性、分辨率良好。另一方面，重均分子量为150000以下的情况下，显影性和贮藏稳定性良好。更优选为5000～100000。
(A)含羧基树脂的配混量相对于固化性树脂组合物的总固体成分优选为5～80质量％、更优选为10～70质量％、特别优选为12～60质量％。
(B)无机填充剂
本发明的固化性树脂组合物包含(B)无机填充剂。(B)无机填充剂可以单独使用1种，也可以组合使用2种以上。
(B)无机填充剂的配混量相对于固化性树脂组合物的总固体成分优选为20～65质量％的范围、更优选为25～60质量％的范围，特别优选35～55质量％的范围。(B)无机填充剂的配混量为35质量％以上时，有获得表面固化性、反射率、焊接耐热性、绝缘可靠性优异的固化性树脂组合物的倾向。(B)无机填充剂的配混量为55质量％以下时，有获得脱泡性、分辨率更加优异的固化性树脂组合物的倾向。
作为(B)无机填充剂，例如有可列举出氧化钛、二氧化硅、硫酸钡、钛酸钡、诺伊堡硅土、滑石、粘土、碳酸镁、碳酸钙、氧化铝、氢氧化铝、氮化硅、氮化铝等。其中，优选包含氧化钛、二氧化硅、硫酸钡之中的至少任一种，能够抑制固化性树脂组合物的固化收缩，改善密合性、硬度、反射率等特性。其中，从反射率的观点出发，特别优选至少包含氧化钛。
作为本发明的固化性树脂组合物中可使用的氧化钛，可以使用通过硫酸法、氯法制造的氧化钛、金红石型氧化钛、锐钛矿型氧化钛、或实施了基于水合金属氧化物的表面处理、基于有机化合物的表面处理的氧化钛。氧化钛根据晶体结构而被分类为金红石型和锐钛矿型。它们之中，优选金红石型氧化钛。锐钛矿型氧化钛与金红石型相比白色度更高，因而常用。但是，锐钛矿型氧化钛具有光催化活性，因此有时引起固化性树脂组合物中的树脂的变色。与此相对，金红石型氧化钛尽管白色度稍差于锐钛矿型，但几乎不具有光活性，因此能够得到稳定的固化物。
(B)无机填充剂包含氧化钛的情况下，从实现由氧化钛带来的反射率提高效果的观点、提高表面固化性的观点出发，氧化钛的配混量相对于固化性树脂组合物的总固体成分量优选为1质量％以上且50质量％以下、更优选为1.5质量％以上且30质量％以下，特别优选2质量％以上且25质量％以下。
(B)无机填充剂的平均粒径优选为50μm以下、更优选为平均粒径0.1～25μm、特别优选为平均粒径0.2～10μm。此处，平均粒径是指，单独的无机填充剂或无机填充剂分散液的平均粒径。另外，也可以在一部分中组合使用平均粒径100nm以下的纳米填料。此处，本说明书中，无机填充剂的平均粒径是不仅包括一次颗粒的粒径、还包括二次颗粒(聚集体)的粒径在内的体积平均粒径(D50)。前述平均粒径可以与平均粒径相应地使用MicrotracBEL Corp.制的Microtrac MT3300EXII等基于激光衍射法的测定装置、MicrotracBEL Corp.制的Nanotrac Wave II UT151)等基于动态光散射法的测定装置来进行测定。
另外，(B)无机填充剂也可以为经表面处理的填料(表面处理填料)。(B)无机填充剂的表面处理没有特别限定，可以使用基于硅烷系、钛酸酯系、铝酸酯系、锆铝酸酯系等的偶联剂的表面处理、氧化铝处理等不导入有机基团的表面处理等公知惯用的方法。
作为(B)无机填充剂，可以使用市售品。作为氧化钛的市售品，作为市售的金红石型氧化钛，例如可以使用：Taipaque R-820、Taipaque R-830、Taipaque R-930、Taipaque R-550、Taipaque R-630、Taipaque R-680、Taipaque R-670、Taipaque R-780、Taipaque R-850、Taipaque CR-50、Taipaque CR-57、Taipaque CR-Super70、Taipaque CR-80、Taipaque CR-90、Taipaque CR-93、Taipaque CR-95、Taipaque  CR-97、Taipaque CR-60、Taipaque CR-63、Taipaque CR-67、Taipaque CR-58、Taipaque CR-85、Taipaque UT771(石原产业株式会社制)；Ti-Pure R-100、Ti-Pure R-101、Ti-Pure R-102、Ti-Pure R-103、Ti-Pure R-104、Ti-Pure R-105、Ti-Pure R-108、Ti-Pure R-900、Ti-Pure R-902、Ti-Pure R-960、Ti-Pure R-706、Ti-Pure R-931(DuPont Co.,Ltd.制)；R-25、R-21、R-32、R-7E、R-5N、R-61N、R-62N、R-42、R-45M、R-44、R-49S、GTR-100、GTR-300、D-918、TCR-29、TCR-52、FTR-700(以上堺化学工业株式会社制)等。
上述中，优选使用通过氯法制造的Taipaque CR-50、Taipaque CR-57、Taipaque CR-80、Taipaque CR-90、Taipaque CR-93、Taipaque CR-95、Taipaque CR-97、Taipaque CR-60、Taipaque CR-63、Taipaque CR-67、Taipaque CR-58、Taipaque CR-85、Taipaque UT771(石原产业株式会社制)；Ti-Pure R-100、Ti-Pure R-101、Ti-Pure R-102、Ti-Pure R-103、Ti-Pure R-104、Ti-Pure R-105、Ti-Pure R-108、Ti-Pure R-900、Ti-Pure R-902、Ti-Pure R-960、Ti-Pure R-706、Ti-Pure R-931(DuPont Co.,Ltd.制)。
另外，作为锐钛矿型氧化钛，可以使用公知的物质。作为市售的锐钛矿型氧化钛，可以使用TITON A-110、TITON TCA-123E、TITON A-190、TITON A-197、TITON SA-1、TITON SA-1L(堺化学工业株式会社制)；TA-100、TA-200、TA-300、TA-400、TA-500、TP-2(富士钛工业株式会社制)；TITANIX JA-1、TITANIX JA-3、TITANIX JA-4、TITANIX JA-5、TITANIX JA-C(Teika Co.,Ltd.制)；KA-10、KA-15、KA-20、KA-30(钛工业株式会社制)；Taipaque A-100、Taipaque A-220、Taipaque W-10(石原产业株式会社制)等。
作为硫酸钡的市售品，可以列举堺化学工业株式会社制B-30、B-31、B-32、B-33、B-34、B-35、B-35T等。
作为二氧化硅的市售品，可以列举Tokuyama Co.,Ltd.制SE-40、龙森制MSV25G、龙森制MLV-2114、ADMATECHS制SO-E5、ADMATECHS制SO-E2等。
(C)热固化性树脂
本发明的固化性树脂组合物包含(C)热固化性树脂。作为(C)热固化性树脂，可以使用环氧树脂、封端异氰酸酯化合物、氨基树脂、马来酰亚胺化合物、苯并恶嗪树脂、碳二亚胺树脂、环碳酸酯化合物、氧杂环丁烷化合物、环硫树脂、三聚氰胺衍生物等。(C)热固化性树脂可以单独使用1种，也可以组合使用2种以上。
作为(C)热固化性树脂，从获得表面固化性优异、抑制排气发生、且固化物的绝缘可靠性、焊接耐热性之类的物性也优异的固化性树脂组合物的观点出发，含有环氧树脂是合适的。作为环氧树脂，例如可以适宜使用双酚A型、双酚F型、氨基酚型、苯酚酚醛清漆型的环氧树脂等公知惯用的环氧树脂。
需要说明的是，本发明的固化性树脂组合物中，可以将这些环氧树脂单独使用，或者组合使用2种以上。另外，可以使用液态环氧树脂，也可以使用固体的环氧树脂。
作为(C)热固化性树脂的市售品，可列举出例如三菱化学株式会社制的jER828、jER834、jER1001、jER1004、DIC株式会社制的EPICLON840、EPICLON850、EPICLON1050、EPICLON2055、日铁化学&材料株式会社制的Epotote YD-011、YD-013、YD-127、YD-128、Nan Ya Plastics公司制的NPEL-128E(均为商品名)等双酚A型环氧树脂；三菱化学株式会社制的jERYL903、DIC株式会社制 的EPICLON152、EPICLON165、日铁化学&材料株式会社制的Epotote YDB-400、YDB-500(均为商品名)等溴化环氧树脂；三菱化学株式会社制的jER152、jER154、DIC株式会社制的EPICLON N-730、EPICLON N-770、EPICLON N-865、日铁化学&材料株式会社制的Epotote YDCN-701、YDCN-704、日本化药株式会社制的EPPN-201、EOCN-1025、EOCN-100，EOCN-104S、RE-306(均为商品名)等酚醛清漆型环氧树脂；DIC株式会社制的EPICLON830、三菱化学株式会社制的jER807、日铁化学&材料株式会社制的Epotote YDF-170、YDF-175、YDF-2004(均为商品名)等双酚F型环氧树脂；日铁化学&材料株式会社制的Epotote ST-2004、ST-2007、ST-3000(均为商品名)等氢化双酚A型环氧树脂；三菱化学株式会社制的jER604、日铁化学&材料株式会社制的Epotote YH-434、住友化学株式会社制的Sumiepoxy ELM-120(均为商品名)等缩水甘油胺型环氧树脂；Daicel Chemical Industry Co.,Ltd.制的Celoxide2021(商品名)等脂环式环氧树脂；三菱化学株式会社制的YL-933、日本化药株式会社制的EPPN-501、EPPN-502(均为商品名)等三羟基苯基甲烷型环氧树脂；三菱化学株式会社制的YL-6056、YX-4000、YL-6121(均为商品名)等联二甲苯酚型或联苯酚型环氧树脂或它们的混合物；日本化药株式会社制的EBPS-200、株式会社ADEKA制的EPX-30、DIC株式会社制的EXA-1514(均为商品名)等双酚S型环氧树脂；三菱化学株式会社制的jER157S(商品名)等双酚A酚醛清漆型环氧树脂；三菱化学株式会社制的jER YL-931(商品名)等四羟苯基乙烷型环氧树脂；日产化学株式会社制的TEPIC(商品名)等杂环式环氧树脂；日本油脂株式会社制的Blemmer DGT(商品名)等邻苯二甲酸二缩水甘油酯树脂；日铁化学&材料株式会社制的ZX-1063(商品名)等四缩水甘油基二甲苯酚乙烷(tetraglycidyl xylenoyl ethane)树脂；日铁化学&材料株式会社制的ESN-190、ESN-360、DIC株式会社制的HP-4032、EXA-4750、EXA-4700(均为商品名)等含萘基环氧树脂；DIC株式会社制的HP-7200、HP-7200H(均为商品名)等具有二环戊二烯骨架的环氧树脂；日本油脂株式会社制的CP-50S、CP-50M(均为商品名)等甲基丙烯酸缩水甘油酯共聚系环氧树脂；环己基马来酰亚胺与甲基丙烯酸缩水甘油酯的共聚环氧树脂等，这些环氧化合物可以单独使用或组合使用2种以上。
(C)热固化性树脂的配混量相对于固化性树脂组合物的总固体成分通常为1～50质量％、更优选为5～35质量％。
(D)光聚合引发剂
本发明的固化性树脂组合物包含(D-a)酰基膦系光聚合引发剂和(D-b)如式(1)所示的光聚合引发剂。通过配混(D-a)酰基膦系光聚合引发剂，能够得到分辨率优异、其固化物的焊接耐热性优异、排气耐性和绝缘可靠性均优异的固化性树脂组合物。
作为(D-a)酰基膦系光聚合引发剂，可以列举例如，单酰基膦系光聚合引发剂和双酰基膦系光聚合引发剂。具体可以列举双-(2,6-二氯苯甲酰基)苯基氧化膦、双-(2,6-二氯苯甲酰基)-2,5-二甲基苯基氧化膦、双-(2,6-二氯苯甲酰基)-4-丙基苯基氧化膦、双-(2,6-二氯苯甲酰基)-1-萘基氧化膦、双-(2,6-二甲氧基苯甲酰基)苯基氧化膦、双-(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦、双-(2,6-二甲氧基苯甲酰基)-2,5-二甲基苯基氧化膦、双-(2,4,6-三甲基苯甲酰基)苯基氧化膦、2,6-二甲氧基苯甲酰基二苯基氧化膦、2,6-二氯苯甲酰基二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基次膦酸甲酯、2-甲基苯甲酰基二苯基氧化膦、新戊酰基苯基次膦酸异丙基酯、2,4,6-三甲基苯甲酰基二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基次膦酸乙酯、(2,6-二甲氧基苯甲酰基)-2,4,4-戊基氧化膦等。
(D-a)酰基膦系光聚合引发剂优选包含下述式(2)所示的具有3个以上的酰基膦骨架的光聚合引发剂(3官能以上的酰基膦系光聚合引发剂)。
Figure PCTCN2022122716-appb-000003
式中，
A彼此独立地表示单键、O、S或NR 3；
G是多官能化合物(核芯)G-(A-H) m+n的残基，其中A-H各自表示醇性羟基或氨基或硫醇基；
m及n满足m+n为3～10之间的数；
m为3～8之间的数；
R 1及R 2彼此独立地是C 1-C 18的烷基、C 6-C 12的芳基及C 5-C 12的环烷基，各自可以不断开或被如下基团断开：1个以上的氧和/或硫原子和/或1个以上的取代或未取代亚氨基，或者R 1及R 2可以彼此独立地是含有氧和/或氮和/或硫原子的五至六元杂环基，其中，前述R 1及R 2各自任选被芳基、烷基、芳氧基、烷氧基、杂原子和/或杂环基团取代；
R 2可以为R 1-(C＝O)-；
Y为O或S；
R 3为氢或C 1～C 4的烷基；
其中，式(2)的光聚合引发剂不含光固化性烯属不饱和基团。
优选的是，式(2)中，m+n为3～8之间的数、更优选为3～6之间的数。例如，式(2)中，m为3～6之间的数、更优选为3～5之间的数。
式(2)中，A为氧时，G-(A-H) m+n为多羟基(多元羟基)化合物，选自由单体多元醇、低聚物多元醇和聚合物多元醇及其混合物组成的组。A为硫时，G-(A-H) m+n为多硫醇化合物。式(I)中，A为氮时，G-(A-H) m+n为线型或支链多胺。A为氧和/或氮和/或硫的混合时，G-(A-H) m+n为包含不同官能团的化合物、例如包含氨基及羟基的化合物。A为单键时，G-为上述列举的G-(A-H) m+n中除去羟基和/或氨基和/或巯基后的残基。
优选的是G-(A-H) m+n具有1500以下、更优选800以下、进一步优选500以下的数均分子量。
当n不为0时，式(2)的化合物具有醇性羟基和/或氨基和/或巯基。
将式(2)中包括的代表性的3官能以上的酰基膦系光聚合引发剂示于表1。这些当中，特别优选PI-3、PI-4、PI-10、PI-11、PI-12、PI-14、PI-17。通过包含这种3官能以上的酰基膦系光聚合引发剂，能够得到排气受到抑制、绝缘可靠性更加优异的固化物。
作为市售品，可以列举例如IGM RESINS B.V.公司制造的Omnipol TP等，这些酰基膦系光聚合引发剂可以单独地或者组合2种以上使用。
表1
Figure PCTCN2022122716-appb-000004
Figure PCTCN2022122716-appb-000005
Figure PCTCN2022122716-appb-000006
Figure PCTCN2022122716-appb-000007
表1中的a、b、c和d分别为独立的数，为了使3官能以上的酰基膦系光聚合引发剂的数均分子量为期望值而适当选择。
这种3官能以上的酰基膦系光聚合引发剂例如可以通过日本特许6599446号中记载的方法来制造。
本发明的固化性树脂组合物进一步包含(D-b)式(1)所记载的光聚合引发剂作为前述(D)光聚合引发剂。通过组合(D-a)酰基膦系光聚合引发剂和(D-b)如式(1)所记载的光聚合引发剂，能够得到表面固化性、反射率、焊接耐热性和绝缘可靠性优异的固化性树脂组合物。
Figure PCTCN2022122716-appb-000008
式中，R 23表示氢原子、烷基、烷氧基、苯基、萘基；R 21、R 22分别独立地表示氢原子、烷基、烷氧基、卤原子、苯基、萘基、蒽基、吡啶基、苯并呋喃基、苯并噻吩基；
Ar表示单键、或碳数1～10的亚烷基、亚乙烯基、亚苯基、亚联苯基、亚吡啶基、亚萘基、亚蒽基、亚噻吩基、亚呋喃基、2,5-吡咯-二基、4,4’-茋-二基、4,2’-茋-二基；n表示0～1的数。
作为R 23所示的烷基，优选碳原子数1～17的烷基。
作为R 23所示的烷氧基，优选碳原子数1～8的烷氧基。
R 23所示的苯基可以具有取代基，作为该取代基，例如可举出：烷基(优选碳原子数为1～17)、烷氧基(优选碳原子数为1～8)、氨基、烷基氨基(优选烷基的碳原子数为1～8)或二烷基氨基(优选烷基的碳原子数为1～8)等。
R 23所示的萘基可以具有取代基，作为该取代基，可举出：与R 23所示的苯基可以具有的上述取代基相同的基团。
作为R 21和R 22所示的烷基，优选碳原子数1～17的烷基。
作为R 21和R 22所示的烷氧基，优选碳原子数1～8的烷氧基。
R 21和R 22所示的苯基可以具有取代基，作为该取代基，例如可举出：烷基(优选碳原子数为1～17)、烷氧基(优选碳原子数为1～8)、氨基、烷基氨基(优选烷基的碳原子数为1～8)或二烷基氨基(优选烷基的碳原子数为1～8)等。
R 21和R 22所示的萘基可以具有取代基，作为该取代基，可举出：与R 21和R 22所示的苯基可以具有的上述取代基相同的基团。
进而，式(1)中，优选R 21、R 23各自独立地为甲基或乙基，R 22为甲基或苯基，Ar为单键、亚苯基、亚萘基或亚噻吩基，n为0。
作为式(1)所示的化合物，更优选下述式(2)或式(3)所示的化合物中的任一种。
Figure PCTCN2022122716-appb-000009
作为(D-b)式(1)所记载的光聚合引发剂的市售品，可以列举例如日本化学工业所公司制造的TOE-04-A3。
(D-b)式(1)所记载的光聚合引发剂可以单独使用1种或组合2种以上而使用。
相对于(D-a)酰基膦系光聚合引发剂的配混量，(D-b)式(1)所记载的光聚合引发剂的配混量为0.1～10质量％的范围内。优选0.2～8质量％的范围内、更优选0.25～7.5质量％的范围内。若(D-b)/(D-a)在上述范围内，则固化性树脂组合物的表面固化性和分辨率变得良好，其固化膜的反射率、焊接耐热性和绝缘可靠性也提高。
相对于固化性树脂组合物的总固体成分，(D-a)酰基膦系光聚合引发剂和(D-b)式(1)所记载的光聚合引发剂的总配混例优选为0.5～30质量％的范围内、更优选为1～20质量％的范围内、特别优选为2～15质量％的范围内。该配混量处于上述范围内时，固化性树脂组合物的表面固化性和分辨率变得良好，其固化膜的反射率、焊接耐热性和绝缘可靠性也提高。
本发明的固化性树脂组合物还可以进一步包含与上述(D-a)酰基膦系光聚合引发剂和上述(D-b)如式(1)所记载的光聚合引发剂不同的其他的光聚合引发剂。作为该其他的光聚合引发剂。例如可举出：二苯甲酮系、苯乙酮系、氨基苯乙酮系、苯偶姻醚系、苯偶酰缩酮系、肟醚系、肟酯系、羟基酮系、二茂钛系等公知惯用的化合物。
作为市售品，可举出例如BASF JAPAN LTD.制的IRGACURE OXE01、IRGACURE OXE02；IGM RESINS B.V.公司制造的Omnirad907、Omnirad369、Omnirad379；ADEKA CORPORATION制的N-1919、NCI-831；常州强力电子新材料有限公司制的TR-PBG-304等。
(E)聚合性单体
本发明的固化性树脂组合物还可以进一步配混分子中具有烯属不饱和基团的(E)聚合性单体。
作为这样的聚合性单体，可以使用例如惯用公知的聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、碳酸酯(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯，具体而言，可以举出丙烯酸-2-羟乙酯、丙烯酸-2-羟丙酯等丙烯酸羟基烷基酯类；乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等二醇的二丙烯酸酯类；N,N-二甲基丙烯酰胺、N-羟甲基丙烯酰胺、N,N-二甲基氨基丙基丙烯酰胺等丙烯酰胺类；丙烯酸N,N-二甲基氨基乙酯、丙烯酸N,N-二甲基氨基丙酯等丙烯酸氨基 烷基酯类；己二醇、三羟甲基丙烷、季戊四醇、二季戊四醇、三羟乙基异氰脲酸酯等多元醇或它们的环氧乙烷加成物、环氧丙烷加成物、或ε-己内酯加成物等的多元丙烯酸酯类；苯氧基丙烯酸酯、双酚A二丙烯酸酯、及这些酚类的环氧乙烷加成物或环氧丙烷加成物等的多元丙烯酸酯类；甘油二缩水甘油醚、甘油三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三缩水甘油异氰脲酸酯等缩水甘油醚的多元丙烯酸酯类；不限于上述，可以举出将聚醚多元醇、聚碳酸酯二元醇、羟基末端聚丁二烯、聚酯多元醇等多元醇直接丙烯酸酯化、或者借助二异氰酸酯进行氨基甲酸酯丙烯酸酯化而得到的丙烯酸酯类及三聚氰胺丙烯酸酯、及与上述丙烯酸酯对应的各种甲基丙烯酸酯类中的至少任1种等。
包含聚合性单体的情况下，相对于(A)含羧基树脂100质量份，聚合性单体的配混量为5～40质量份的范围是合适的。光聚合性单体的配混量为5质量份以上时，光固化性赋予效果变得良好。另一方面，为40质量份以下时，涂膜的指触干燥性变得良好。
添加剂
本发明的固化性树脂组合物中，可以进一步根据需要添加着色用颜料、消泡剂、表面张力调整剂、偶联剂、流平剂、敏化剂、脱模剂、润滑剂、增塑剂、抗氧化剂、紫外线吸收剂、阻燃剂、阻聚剂、增稠剂、密合助剂、交联剂等公知的添加剂。
有机溶剂
本发明的固化性树脂组合物中，出于上述(A)含羧基树脂的合成和固化性树脂组合物的调整，或者涂布于基板、第一膜时的粘度调整等目的，可以使用有机溶剂。
作为溶剂，可列举出酮类、芳香族烃类、二醇醚类、二醇醚乙酸酯类、酯类、醇类、脂肪族烃、石油系溶剂等。更具体而言，可列举出有甲乙酮、环己酮等酮类；甲苯、二甲苯、四甲基苯等芳香族烃类；溶纤剂、甲基溶纤剂、丁基溶纤剂、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇单甲醚、二丙二醇单甲醚、二丙二醇二乙醚、三乙二醇单乙醚等二醇醚类；乙酸乙酯、乙酸丁酯、二甘醇乙醚乙酸酯、二丙二醇甲醚乙酸酯、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丁醚乙酸酯等酯类；乙醇、丙醇、乙二醇、丙二醇等醇类；辛烷、癸烷等脂肪族烃；石油醚、石脑油、氢化石脑油、溶剂石脑油等石油系溶剂等。这些有机溶剂可以单独使用或以2种以上的混合物的形式使用。
层叠体
本发明的固化性树脂组合物也可以形成层叠体的形态，所述层叠体具备：第一膜；和，形成于该第一膜上的由上述固化性树脂组合物所形成的树脂层。进行层叠体化时，将本发明的固化性树脂组合物用上述有机溶剂稀释调整至适当的粘度，用缺角轮涂布机、刮刀涂布机、唇口涂布机、棒涂机、挤压涂布机、逆式涂布机、传递辊涂布机、凹版涂布机、喷涂机等以均匀的厚度涂布于第一膜上，通常在50～130℃的温度下进行1～30分钟干燥，可以得到树脂层。对于涂布膜厚，没有特别限制，通常以干燥后的树脂层的厚度成为1～150μm、优选10～60μm的范围内的方式适宜选择。
在第一膜上形成本发明的固化性树脂组合物的树脂层后，进而，出于防止灰尘附着在树脂层的表面等目的，优选在树脂层的表面层叠可剥离的第二膜。作为可剥离的第二膜，例如可以使用聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、经表面处理的纸等，只要是将第二膜剥离时树脂层与第二膜的粘接力小于树脂层与第一膜的粘接力的第二膜即可。
需要说明的是，本发明中，可以通过在上述第二膜上涂布本发明的固化性树脂组合物并干燥， 从而形成树脂层，并在其表面层叠第一膜。即，本发明中，在制造层叠体时，作为涂布本发明的固化性树脂组合物的薄膜，可以使用第一膜和第二膜中的任意者。
固化物
本发明的固化物是将上述本发明的固化性树脂组合物或上述本发明的层叠体的树脂层固化而得到的，兼具焊接耐热性、排气耐性和绝缘可靠性。
印刷电路板
本发明的印刷电路板具有由本发明的固化性树脂组合物或层叠体的树脂层得到的固化物。作为本发明的印刷电路板的制造方法，例如，将本发明的固化性树脂组合物用上述有机溶剂调整为适于涂布方法的粘度，利用浸涂法、流涂法、辊涂法、棒涂法、丝网印刷法、幕涂法等方法涂布在基材上后，在60～100℃的温度下使组合物中所含的有机溶剂挥发干燥(临时干燥)，从而形成不粘性树脂层。另外，层叠体的情况下，利用层压机等以树脂层与基材接触的方式粘贴在基材上后，将第一膜剥离，从而在基材上形成树脂层。
作为上述基材，除了预先由铜等进行了电路形成的印刷电路板、挠性印刷线路板之外，还可以举出：使用了纸酚醛树脂、纸环氧树脂、玻璃布环氧树脂、玻璃聚酰亚胺树脂、玻璃布/无纺布环氧树脂、玻璃布/纸环氧树脂、合成纤维环氧树脂、氟树脂/聚乙烯/聚苯醚树脂、聚亚苯基氧化物/氰酸酯树脂等的高频电路用敷铜箔层积板等材质的、全部等级(FR-4等)的敷铜箔层积板；以及，金属基板、聚酰亚胺薄膜、聚对苯二甲酸乙二醇酯薄膜、聚萘二甲酸乙二醇酯(PEN)薄膜、玻璃基板、陶瓷基板、晶圆板等。
涂布本发明的固化性树脂组合物后进行的挥发干燥可以通过如下方式进行：利用热风循环式干燥炉、IR炉、热板、对流式烘箱等(使用具备利用蒸汽的空气加热方式的热源的装置，使干燥机内的热风对流接触的方法和利用喷嘴吹送到支撑体上的方式)，从而进行。
在基材上形成树脂层后，通过形成有规定图案的光掩模，选择性地利用活性能量射线进行曝光，将未曝光部利用稀碱水溶液(例如0.3～3重量％碳酸钠水溶液)进行显影，形成固化物的图案。进而，对固化物照射活性能量射线后，进行加热固化(例如100～220℃)，或在加热固化后照射活性能量射线，或仅凭借加热固化使其最终完全固化(正式固化)，从而形成密合性、硬度等各特性优异的固化膜。
作为上述活性能量射线照射中使用的曝光机，只要为搭载LED光源灯、高压水银灯、超高压水银灯、金属卤化物灯、水银短弧光灯等的照射紫外线的装置即可，进而也可以使用直描装置(例如利用来自计算机的CAD数据以直接激光方式描绘图像的激光直接成像装置)。作为直描装置的曝光波长，优选380～450nm的范围。用于图像形成的曝光量根据膜厚等而不同，通常可以设为10～1500mJ/cm 2、优选可以设为20～1000mJ/cm 2的范围内。
作为上述显影方法，可以利用浸渍法、喷淋法、喷涂法、刷涂法等，作为显影液，可以使用氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、磷酸钠、硅酸钠、氨、胺类等的碱性水溶液。
本发明的固化性树脂组合物适合用于在要求小型化、高性能化的电子机器的电子部件上形成固化膜、特别适合用于在要求小型高密度化的印刷电路板上形成固化膜，更适合用于形成永久覆膜，进一步适合用于形成阻焊层、层间绝缘层、覆盖层。
以下示出实施例和比较例，对本发明进行具体说明，但本发明当然不限定于下述实施例。需要说明的是，以下“份”和“％”在没有特别说明的情况下均为质量基准。
<固化性树脂组合物的配制>
按表2～3所示的配比配混、搅拌各成分，用三辊混炼机混炼分散，从而得到实施例1～110比较例1～4的固化性树脂组合物。其中，表2、3的配混量表示清漆换算的配混量。
表2
Figure PCTCN2022122716-appb-000010
表3
Figure PCTCN2022122716-appb-000011
*1(D-a)、(D-b)的合计量，不含其他的光聚合引发剂
*2由于(D-a)的含量为0，实际(D-b)/(D-a)的结果为∞
表2～3所示各成分的详细信息如下所示。
A-1合成例1的含羧基树脂溶液(固体成分39％)
A-2合成例2的含羧基树脂溶液(固体成分64％)
B-1 CR-97、石原产业株式会社、氧化钛(固体成分100％)
B-2 SiO 2(固体成分100％)Admatechs株式会社制SO-E2
B-3 BaSO 4(固体成分100％)堺化学工业株式会社制BARIACE B-30
C-1 NPEL-128E、Nan Ya Plastics公司制、双酚A型环氧树脂(固体成分100％)
C-2 N-770-75EA、DIC公司制、苯酚酚醛清漆型的多官能环氧树脂(固体成分75％)
D-1 Omnipol TP、3官能以上的酰基氧化膦系光聚合引发剂(上述表1的PI-3的结构)、IGM RESINS B.V.公司制(固体成分100％)
D-2 Omnirad 819、双酰基氧化膦系光聚合引发剂、IGM RESINS B.V.公司制(固体成分100％)
D-3 TOE-04-A3、日本化学工业所公司制造的式(2)的光聚合引发剂(固体成分100％)
D-4 Omnirad 369、α-氨基苯酮系光聚合引发剂、IGM RESINS B.V.公司制(固体成分100％)
D-5 IRGACURE OXE02、BASF JAPAN LTD.制造的肟酯系光聚合引发剂(固体成分100％)
合成例1(不具有酚骨架含羧基树脂的合成)
在具备温度计、搅拌机、滴液漏斗和回流冷凝器的烧瓶中将作为溶剂的二丙二醇单甲醚900.0份加热至110℃，用3小时滴加甲基丙烯酸174.0份、ε-己内酯改性甲基丙烯酸(平均分子量314)174.0份、甲基丙烯酸甲酯77.0份、二丙二醇单甲醚222.0份、以及作为聚合催化剂的过氧化2-乙基己酸叔丁酯(日本油脂株式会社制Perbutyl O)12.0份的混合物，进而在110℃下搅拌3小时，使聚合催化剂失活，得到树脂溶液。
将该树脂溶液冷却后，添加Daicel公司制Cyclomer A200(甲基丙烯酸3,4-环氧环己基甲酯)289.0份、三苯基膦3.0份、对苯二酚单甲醚1.3份，升温至100℃，进行搅拌，从而进行环氧基的开环加成反应，得到不具有酚骨架的含羧基树脂溶液。
由此得到的树脂溶液的重均分子量(Mw)为15000、且固体成分为39％、固形物的酸值为79.8mgKOH/g。
合成例2(含有酚骨架的含羧基树脂的合成)
在二乙二醇单乙醚乙酸酯600g中投入邻甲酚酚醛清漆型环氧树脂〔DIC株式会社制、EPICLON N-695、软化点95℃、环氧当量214、平均官能团数7.6〕1070g(缩水甘油基数(芳香环总数)：5.0摩尔)、丙烯酸360g(5.0摩尔)、以及对苯二酚1.5g，加热搅拌至100℃，均匀溶解。
接着，投入三苯基膦4.3g，加热至110℃并反应2小时后，升温至120℃，进而进行12小时反应。在得到的反应液中投入芳香族系烃(Solvesso150)415g、四氢邻苯二甲酸酐456.0g(3.0摩尔)，在110℃下进行4小时反应，冷却，得到不具有酚骨架的含羧基树脂溶液。
由此得到的树脂溶液的固体成分为64％、固体成分的酸值为89mgKOH/g。
评价基板的制作
1.评价基板A的制作
将上述实施例和比较例的固化性树脂组合物通过丝网印刷而整面涂布到通过抛光研磨进行了前处理的敷铜箔层积板上，用热风循环式干燥炉在80℃下干燥30分钟，冷却至室温，形成厚度40μm的树脂层。对于树脂层，使用搭载LED光源的DI曝光机(SCREEN公司制Ledia6)，以385nm光源输出功率100％且1000mJ/cm 2的曝光量进行整面曝光，使用30℃的1质量％的碳酸钠水溶液，以喷雾压力 0.15MPa的条件进行50秒显影。然后，用调整至150℃的热风循环式干燥炉使树脂层固化60分钟(后固化)，得到评价基板A。
2.评价基板B的制作
将上述实施例和比较例的固化性树脂组合物通过丝网印刷而整面涂布到通过抛光研磨进行了前处理的FR-4基板上，在80℃下干燥30分钟，冷却至室温，形成厚度40μm的树脂层。对于树脂层的表面，将干燥后的上述组合物的上表面(露出面)用形成有线/间隔(L/S)为30μm/30μm、40μm/40μm、50μm/50μm、60μm/60μm、70μm/70μm、80μm/80μm、90μm/90μm、100μm/100μm、200μm/200μm的图案的负片覆盖，使用LED曝光机(SCREEN公司制Ledia6)，以385nm光源输出功率100％且1000mJ/cm 2的曝光量隔着负片对树脂层进行曝光。然后，使用30℃的1质量％的碳酸钠水溶液，以喷雾压力0.15MPa的条件进行50秒显影。然后，用调整至150℃的热风循环式干燥炉使树脂层固化60分钟(后固化)，得到评价基板B。
特性实验
(1)脱泡性
在具有铜厚105μm、L/S为40μm/300μm、电路长度为2cm的直线图案的双面印刷基板的一个面上，进行抛光研磨作为前处理，然后，水洗并使水充分干燥。
接着，将上述实施例和比较例的固化性树脂组合物通过丝网印刷法以固化后的膜厚成为120μm的方式、沿与图案平行的方向涂布于干燥后的双面印刷基板的进行过前处理的面的整面。在室温下静置30分钟后，用热风循环式干燥炉在80℃下干燥30分钟，制作脱泡性评价基板。对脱泡性评价基板用20倍的光学显微镜进行观察，计数电路与电路之间的气泡数，根据气泡数如下评价脱泡性。
◎：100μm以上的气泡为5个以下
〇：100μm以上的气泡超过5个且为10个以下
(2)曝光后的铅笔硬度
将上述实施例和比较例的固化性树脂组合物通过丝网印刷而整面涂布到通过抛光研磨进行了前处理的敷铜箔层积板上，用热风循环式干燥炉在80℃下干燥30分钟，冷却至室温，形成厚度40μm的树脂层。对于树脂层，使用搭载LED光源的DI曝光机(SCREEN公司制Ledia6)，以385nm光源输出功率100％且1000mJ/cm 2的曝光量进行整面曝光，使用30℃的1质量％的碳酸钠水溶液，以喷雾压力0.15MPa的条件进行50秒显影。根据JIS K 5600-5-4测定得到的树脂层表面的铅笔硬度。评价基准如下。
◎：铅笔硬度4H以上
〇：铅笔硬度2H以上且低于4H
×：铅笔硬度低于2H
图案曝光后的铅笔硬度越高，意味着固化性树脂组合物的表面固化性越优异
(3)热固化后的铅笔硬度
根据JIS K 5600-5-4测定评价基板A的固化物表面的铅笔硬度。评价基准如下。对于实施例和比较例的任一固化物而言，铅笔硬度均为6H以上(在表2、3中记载为◎)。
(4)分辨率
对于评价基板B，目视确认基板上残留的最小设计线宽，据此按照以下的基准进行分辨率的评价。
◎：在最小设计线宽70μm以下残留线
〇：在最小设计线宽超过70μm且为90μm以下残留线
×：设计线宽超过90μm的情况下也完全未残留线
(5)反射率
对于评价基板A，使用柯尼卡美能达公司制分光测色计CM-2600d测定所得到的固化物的450nm下的反射率，按照下述判断基准进行评价。
◎：反射率75％以上
〇：反射率70％以上且不足75％
×：反射率不足70％
(6)焊接耐热性
对于评价基板A，向固化物表面涂布松香系助焊剂后，在260℃的焊料槽中浸渍20秒。浸渍后，自然冷却至基板达到室温，再次向焊料槽中浸渍。进行数次浸渍后，目视观察用变性酒精清洗助焊剂后的外观，按照以下的评价基准进行评价。
◎：即使进行4次以上在焊料槽中的浸渍，也未观察到固化物的剥离。
〇：即使进行2次以上在焊料槽中的浸渍，也未观察到固化物的剥离，但是在进行4次以上时观察到树脂层的剥离。
×：在进行2次在焊料槽中的浸渍时，观察到固化物的剥离。
(7)排气耐性
对于评价基板A，从形成的固化物采集粉末样品，放入到GERSTEL株式会社制热脱附装置(TDU)后，以260℃的热提取温度加热10分钟，分别用液氮在-60℃下收集所发生的排气成分。收集的排气成分用Agilent Technologies公司制气相色谱-质谱仪(6890N/5973N)进行分离分析，以正十二烷换算定量，将实施例1的排气量设为100质量％，按照以下的基准进行评价。
◎：排气成分为150质量％以下
〇：排气成分超过150质量％且为200质量％以下
×：排气成分超过200质量％
(8)绝缘可靠性
将形成有L/S＝100μm/100μm的梳型电极的基板通过抛光研磨进行前处理后，通过丝网印刷整面涂布前述实施例及比较例的固化性树脂组合物后，用热风循环式干燥炉在80℃下干燥30分钟，形成厚度40μm的树脂层。接着，用热风循环式干燥炉在150℃下加热60分钟，形成树脂层的固化物，制作绝缘可靠性评价基板。将评价基板放入85℃、湿度85％的气氛下的高温高湿槽，施加电压3.5V，进行槽内绝缘可靠性试验。对于固化物经过各种时间时的槽内绝缘电阻值，按照下述判断基准进行评价。
◎：经过800小时后为10 7Ω以上
〇：经过500小时后绝缘电阻值为10 7Ω以上，但经过800小时时绝缘电阻值不足10 7Ω
×：经过500小时时绝缘电阻值不足10 7Ω。
由表2、表3可见，与仅包含(D-a)以外的光聚合引发剂和(D-b)的光聚合引发剂的比较例1相比，包含(D-a)的光聚合引发剂和(D-b)的光聚合引发剂这两者的实施例1的分辨率、焊接耐热 性、排气耐性和绝缘信赖性得到大幅改善。与仅含(D-a)的光聚合引发剂的比较例2相比，包含(D-a)的光聚合引发剂和(D-b)的光聚合引发剂这两者的实施例1的图案曝光后的铅笔硬度、反射率、焊接耐热性和绝缘信赖性得到大幅改善。与仅包含(D-a)的光聚合引发剂和(D-b)以外的光聚合引发剂的比较例4相比，包含(D-a)的光聚合引发剂和(D-b)的光聚合引发剂这两者的实施例10的曝光后的铅笔硬度、反射率、焊接耐热性和绝缘信赖性得到大幅改善。与包含(D-a)的光聚合引发剂和(D-b)的光聚合引发剂这两者，但(D-b)/(D-a)超过10质量％的比较例3相比，(D-b)/(D-a)为0.25质量％的实施例9的分辨率、反射率、焊接耐热性和绝缘信赖性得到大幅改善。
此外，(A)含羧基树脂包含不具有酚骨架的含羧基树脂时，反射率和绝缘可靠性有进一步提高的倾向(实施例1与实施例10)。无机填料的配混量在适合范围内时，图案曝光后的铅笔硬度、反射率、焊接耐热性和绝缘信赖性有进一步提高的倾向(实施例1～3与实施例4、5)，或者脱泡性、分辨率有进一步提高的倾向(实施例1～3与实施例6、7)。含有氧化钛时，反射率有进一步提高的倾向(实施例1与实施例8)。(D-a)包含3官能以上的酰基膦系光聚合引发剂时，脱泡性、分辨率、排气耐性和绝缘可靠性有进一步提高的倾向(实施例1与实施例9)。
由上述这些结果可知，本发明的固化性树脂组合物的分辨率、脱泡性和表面固化性优异，排气得到抑制，其固化物的绝缘可靠性、焊接耐热性等也优异。由该固化性树脂组合物可以高效率地制造满足更高水准要求的绝缘材料，非常适合要求小型化、高性能化的电子机器。

Claims (8)

  1. 一种固化性树脂组合物，其包含(A)含羧基树脂、(B)无机填料、(C)热固性树脂、(D)光聚合引发剂，
    作为前述(D)光聚合引发剂，包含(D-a)酰基膦系光聚合引发剂和(D-b)如式(1)所示的光聚合引发剂，
    相对于所述(D-a)酰基膦系光聚合引发剂的配混量，所述(D-b)如式(1)所示的光聚合引发剂的配混量为0.1质量％以上且10质量％以下
    Figure PCTCN2022122716-appb-100001
    式中，R 23表示氢原子、烷基、烷氧基、苯基、萘基；R 21、R 22分别独立地表示氢原子、烷基、烷氧基、卤原子、苯基、萘基、蒽基、吡啶基、苯并呋喃基、苯并噻吩基；
    Ar表示单键、或碳数1～10的亚烷基、亚乙烯基、亚苯基、亚联苯基、亚吡啶基、亚萘基、亚蒽基、亚噻吩基、亚呋喃基、2,5-吡咯-二基、4,4’-茋-二基、4,2’-茋-二基；n表示0～1的数。
  2. 根据权利要求1所述的固化性树脂组合物，其特征在于，相对于固化性树脂组合物的总固体成分量，所述(B)无机填料的配混量为35质量％以上且55质量％以下。
  3. 根据权利要求1所述的固化性树脂组合物，其特征在于，作为所述(B)无机填料，包含氧化钛。
  4. 根据权利要求1所述的固化性树脂组合物，其特征在于，作为(D-a)酰基膦系光聚合引发剂，包含3官能以上的酰基膦系光聚合引发剂。
  5. 根据权利要求1～4中任一项所述的固化性树脂组合物，其特征在于，前述(A)含羧基树脂不具有酚骨架。
  6. 一种层叠体，其特征在于，具有权利要求1～5中任一项所述的固化性树脂组合物作为树脂层。
  7. 一种固化物，其特征在于，通过使权利要求1～5中任一项所述的固化性树脂组合物固化而成，或者通过使权利要求6所述的层叠体的树脂层固化而成。
  8. 一种电子部件，其具有权利要求7所述的固化物。
PCT/CN2022/122716 2021-09-30 2022-09-29 固化性树脂组合物、层叠体、固化物及电子部件 WO2023051718A1 (zh)

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CN104678701A (zh) * 2013-12-02 2015-06-03 太阳油墨制造株式会社 感光性树脂组合物、干膜、固化物和印刷电路板
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