WO2016015398A1 - Composition de résine thermodurcissable durcie à la lumière, film sec, produit durci et carte de circuit imprimé - Google Patents

Composition de résine thermodurcissable durcie à la lumière, film sec, produit durci et carte de circuit imprimé Download PDF

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Publication number
WO2016015398A1
WO2016015398A1 PCT/CN2014/090861 CN2014090861W WO2016015398A1 WO 2016015398 A1 WO2016015398 A1 WO 2016015398A1 CN 2014090861 W CN2014090861 W CN 2014090861W WO 2016015398 A1 WO2016015398 A1 WO 2016015398A1
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Prior art keywords
carboxyl group
containing resin
resin
manufactured
resin composition
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PCT/CN2014/090861
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English (en)
Chinese (zh)
Inventor
槙田昇平
山本修一
浦国斌
董思原
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太阳油墨（苏州）有限公司
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Priority to KR1020167031307A priority Critical patent/KR102352422B1/ko
Priority to JP2016566197A priority patent/JP6669668B2/ja
Publication of WO2016015398A1 publication Critical patent/WO2016015398A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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

Definitions

  • the present invention relates to a photocurable thermosetting resin composition which is soluble in an aqueous alkali solution, a dry film and a cured product thereof, and a printed circuit board having a cured product formed using the same. More specifically, the present invention relates to a resin composition capable of forming a cured product having light reflectivity and applied to a substrate to form a printed wiring board, a dry film thereof, and a cured product obtained by curing the cured product, and A printed circuit board that functions as a reflector such as an LED or an EL having the cured product.
  • a reflector having light reflectivity is used.
  • the reflector is a reflector that is light-reflective on the substrate itself, and a resin composition having light reflectivity is applied onto the substrate, and is cured by light or the like to form a cured product. (Piece, etc.), thus made a reflector (see Japanese Patent Laid-Open 2011-017010).
  • the resin composition used in such use usually uses titanium oxide as an inorganic filler. Further, in order to increase the reflectance, a method of making the content of titanium oxide as large as possible is employed. However, when the content of titanium oxide is increased as described above, there is a problem that the toughness of the cured coating film obtained from the resin composition is lowered and cracks are generated. On the other hand, for example, the curable resin composition for a solder resist needs to satisfy the solder heat resistance.
  • the inventors conducted intensive studies. First, in order to eliminate cracks, it is considered to use a carboxyl group-containing resin having a bisphenol skeleton as a soft skeleton. However, since the bisphenol type carboxyl group-containing resin is not high in heat resistance, the solder heat resistance of the cured coating film is lowered. On the other hand, the novolac type carboxyl group-containing resin has high solder heat resistance, but lacks flexibility, and cannot suppress crack generation.
  • the present inventors have found that by uniformly compounding a bisphenol type carboxyl group-containing resin and a novolak type carboxyl group-containing resin, it is possible to suppress crack generation without lowering solder heat resistance even when the content of titanium oxide is large. Cured product.
  • the present invention is a photocurable thermosetting resin composition
  • a photocurable thermosetting resin composition comprising: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, and (D) heat.
  • the curable component, (E) titanium oxide, the (A) carboxyl group-containing resin comprises (A-1) a bisphenol type carboxyl group-containing resin and (A-2) a novolak type carboxyl group-containing resin, and the (A-1) bisphenol
  • the mass ratio of the carboxyl group-containing resin to the (A-2) novolac type carboxyl group-containing resin that is, the (A-1) bisphenol type carboxyl group-containing resin/the (A-2) novolac type carboxyl group-containing resin is 20/ Range of 80 to 60/40.
  • the present invention is a photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition onto a film and drying it.
  • the present invention is a cured product obtained by photocuring and thermally curing the photocurable thermosetting resin composition or the dry film.
  • the present invention is a printed circuit board having the aforementioned cured product.
  • the printed circuit board with cured product of the invention can also Used as a reflector.
  • the present invention is characterized in that it contains photocuring of (A) carboxyl group-containing resin, (B) photopolymerization initiator, (C) photosensitive monomer, (D) thermosetting component, and (E) titanium oxide.
  • the (A) carboxyl group-containing resin comprises (A-1) a bisphenol type carboxyl group-containing resin and (A-2) a novolac type carboxyl group-containing resin, and the (A-1) bisphenol type is contained.
  • the mass ratio of the carboxyl resin to the (A-2) novolak type carboxyl group-containing resin is 20/80 to The range of 60/40.
  • the mass ratio of the (A-1) bisphenol type carboxyl group-containing resin to the (A-2) novolak type carboxyl group-containing resin is set to a specific range, even if the content of (E) titanium oxide is large In the case of the crack, the generation of cracks can be suppressed, and the welding heat resistance is excellent. Further, since the photocurable thermosetting resin composition of the present invention can have a large content of (E) titanium oxide, a white cured coating film having high reflectance can be obtained.
  • the reflectance of the cured coating film is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.
  • the (A-1) bisphenol type carboxyl group-containing resin and the (A-2) novolak type carboxyl group-containing resin can be used in the molecule for imparting alkali developability.
  • a well-known resin of a carboxyl group From the viewpoint of photocurability and development resistance, a carboxyl group-containing resin having an ethylenically unsaturated double bond in a molecule is particularly preferable. Further, it is more preferred that the unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. Specific examples are shown below.
  • Examples of the (A-1) bisphenol type carboxyl group-containing resin include:
  • A-1-1) 2-functional epoxy resin such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and (methyl) a carboxyl group-containing photosensitive resin obtained by reacting acrylic acid and adding a polybasic acid anhydride to the produced hydroxyl group;
  • Examples of the (A-2) novolac type carboxyl group-containing resin include:
  • a phenol novolac type epoxy resin A cresol novolak type epoxy resin, a bisphenol A cresol novolak type epoxy resin, a dicyclopentadiene cresol novolac type epoxy resin, etc.
  • the polyfunctional epoxy resin reacts with (meth)acrylic acid to add a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the hydroxyl group present in the side chain.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride
  • a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of the above polyfunctional epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid to form a polyhydroxy acid anhydride to form a hydroxyl group. And the obtained carboxyl group-containing photosensitive resin;
  • a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as a novolac resin, and the obtained hydroxyl group is a partial ester of (meth)acrylate.
  • a carboxyl group-containing photosensitive resin obtained by reacting a remaining hydroxyl group with a polybasic acid anhydride;
  • a carboxyl group-containing photosensitive resin obtained by a compound having one epoxy group and one or more (meth)acryloyl groups in a molecule such as a glyceride.
  • cresol novolac type carboxyl group-containing resin is preferable because it is superior in solder heat resistance to the phenol novolac type carboxyl group-containing resin.
  • (meth) acrylate herein refers to the terms collectively referred to as acrylate, methacrylate, and a mixture thereof, and the following other similar expressions are also the same.
  • the carboxyl group-containing resin is utilized because it has a large amount of free carboxyl groups in the side chain of the main chain polymer. Development of an aqueous alkali solution is possible.
  • the acid value of the (A) carboxyl group-containing resin is preferably 40 to 200 mgKOH/g.
  • the acid value of the carboxyl group-containing resin is from 40 mgKOH/g to 200 mgKOH/g, the adhesion of the coating film can be obtained, the alkali development becomes easy, and the dissolution of the exposed portion by the developer is suppressed, and the line is not fine. Above the necessary level, the drawing of the normal resist pattern becomes easy. More preferably, it is 45-120 mgKOH/g.
  • the weight average molecular weight of the (A) carboxyl group-containing resin varies depending on the resin skeleton, and is usually preferably from 2,000 to 150,000. When it is in the range of 2,000 to 150,000, the non-stick property is good, and the moisture resistance of the coating film after the exposure is good, and film formation is less likely to occur during development. Further, in the range of the above weight average molecular weight, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000 to 100,000.
  • (A-1) Mass ratio of bisphenol type carboxyl group-containing resin to (A-2) novolak type carboxyl group-containing resin ((A-1) bisphenol type carboxyl group-containing resin / (A-2) novolak type carboxyl group-containing resin ) is in the range of 20/80 to 60/40.
  • the crack resistance is lowered, which is not preferable.
  • the solder heat resistance is lowered, which is not preferable.
  • the mass ratio of the (A-1) bisphenol type carboxyl group-containing resin to the (A-2) novolak type carboxyl group-containing resin is preferably 30/70 to 60/40, particularly preferably 30/70 to 50/50.
  • the total amount of the (A) carboxyl group-containing resin is 100 parts by mass
  • the total amount of the (A-1) bisphenol type carboxyl group-containing resin and the (A-2) novolak type carboxyl group-containing resin is 40 to 100 parts by mass, more preferably 50 to 100 parts by mass.
  • the total amount of the bisphenol-type carboxyl group-containing resin and the (A-2) novolac type carboxyl group-containing resin is 40 parts by mass or more, the solder heat resistance and the crack resistance are good.
  • the content rate of the (A) carboxyl group-containing resin in the photocurable resin composition is not particularly limited.
  • the (A) carboxyl group-containing resin may contain a (A-1) bisphenol type carboxyl group-containing resin and (A-2) novolak type carboxyl group-containing resin in a range that does not inhibit the curing of the present invention.
  • the (A) carboxyl group-containing resin may further contain a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and an unsaturated group-containing compound, a carboxyl group-containing urethane resin obtained by reacting a diisocyanate with a diol compound, or the like.
  • an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, and an ⁇ -aminoacetophenone-based photopolymerization initiator can be suitably used.
  • oxime ester-based photopolymerization initiator For the oxime ester-based photopolymerization initiator, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like are exemplified.
  • a photopolymerization initiator having two oxime ester groups in the molecule may be suitably used, and specifically, an oxime ester compound having a carbazole structure may be mentioned.
  • the commercially available product of the alkyl phenyl ketone photopolymerization initiator may, for example, be an ⁇ -hydroxyalkyl phenyl ketone type such as IRGACURE 184, Dalocure 1173, IRGACURE 2959 or IRGACURE 127 manufactured by BASF Japan Ltd.
  • ⁇ -aminoacetophenone-based photopolymerization initiator examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1,2- Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- 1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like.
  • IRGACURE907, IRGACURE369, IRGACURE379, etc. by BASF Japan Ltd. are mentioned.
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl).
  • LUCIRIN TPO by BASF Corporation, IRGACURE 819 by BASF Japan Ltd., etc. are mentioned.
  • a titanocene-based photopolymerization initiator such as IRGACURE 389 or IRGACURE 784 manufactured by BASF Japan Ltd. can be suitably used.
  • the amount of the photopolymerization initiator to be added is preferably 0.1 to 25 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.
  • the compounding amount is 0.1 to 25 parts by mass, photocurability and resolution are excellent, and adhesion and PCT resistance are also improved, and electroless gold plating resistance is further obtained.
  • the compounding amount is 25 parts by mass or less, the effect of reducing the exhaust gas can be obtained, and further, the light absorption on the surface of the coating film can be suppressed to be severe, and the deep curability can be lowered.
  • a photoinitiator or a sensitizer can be used in addition to the photopolymerization initiator.
  • the photopolymerization initiator, photoinitiation aid, and sensitizer which can be suitably used in the photocurable thermosetting resin composition include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxantate.
  • photopolymerization initiators can be used singly or in the form of a mixture of two or more.
  • the total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the (A) carboxyl group-containing resin. When it is 35 parts by mass or less, it is possible to suppress a decrease in deep curability due to light absorption thereof.
  • the (C) photosensitive monomer a compound having two or more ethylenically unsaturated groups in a molecule, a compound obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a polyhydric alcohol, and a glycidyl group-containing compound are used.
  • Examples of the compound having two or more ethylenically unsaturated groups in the molecule include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; and hexanediol.
  • Polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanurate or their ethylene oxide adducts or propylene oxide adducts; phenoxy Polyacrylates such as acrylates, bisphenol A diacrylates, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, three a polyacrylate of glycidyl ether such as methylolpropane triglycidyl ether or triglycidyl isocyanurate; and melamine acrylate, and/or each methacrylate corresponding to the above acrylate .
  • Examples of the compound obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a polyhydric alcohol include, for example, Ethylene Alcohol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, butanediol diacrylate, pentanediol Diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolethane triacrylate, tetramethylol methane tetraacrylate And glycerin diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc., and/or each methacryl
  • examples of the compound obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a glycidyl group-containing compound include ethylene glycol diglycidyl ether diacrylate and diethylene glycol diglycidyl ether diacrylate.
  • trimethylolpropane triglycidyl ether triacrylate bisphenol A glycidyl ether diacrylate, diglycidyl diglycidyl diacrylate, glycerol polyglycidyl ether polyacrylate, and the like; 2-bis(4-acryloyloxydiethoxyphenyl)propane, 2,2-bis-(4-acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-acryloyloxyl A propyl acrylate, and/or each methacrylate corresponding to the above acrylate.
  • These photosensitive monomers can be used singly or in combination of two or more.
  • the compounding amount of the photosensitive monomer is preferably 5 to 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 15 parts by mass to 85 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. of.
  • the photocurability improves, pattern formation becomes easy, and the intensity
  • thermosetting component a blocked isocyanate compound, an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, or the like can be used.
  • a well-known thermosetting resin such as a functional oxetane compound, an episulfide resin, or a melamine derivative.
  • a particularly preferable thermosetting component is a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter simply referred to as a cyclic (thio)ether group) in one molecule.
  • a cyclic (thio)ether group hereinafter simply referred to as a cyclic (thio)ether group
  • These thermosetting components having a cyclic (thio)ether group are commercially available in many types, and various types can be imparted depending on the structure. Sex.
  • the thermosetting component having two or more cyclic (thio)ether groups in the molecule is any one of a cyclic ether group or a cyclic thioether group having two or more three, four or five-membered rings in the molecule.
  • the compound having two or more groups may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1); and having at least two or more oxetane in the molecule.
  • Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Nippon Epoxy Resin Co., Ltd., and EPICLON 840, EPICLON 850, EPICLON 1050, and EPICLON 2055 manufactured by Dainippon Ink and Chemicals, Inc.
  • TEPIC Tetrahydrofurane resin
  • diglycidyl phthalate resin such as BLEMMER DDT manufactured by Nippon Oil & Fats Co., Ltd.
  • tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Toshiro Kasei Co., Ltd.
  • Ethylene-based epoxy resin such as HP-4032, EXA-4750, EXA-4700, manufactured by Nippon Steel Chemical Co., Ltd., ESN-190, ESN-360, and Nippon Ink Chemical Industry Co., Ltd.
  • An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H
  • a glycidyl methacrylate copolymer epoxy resin such as CP-50S or CP-50M manufactured by Nippon Oil & Fats Co., Ltd.
  • epoxy resins may be used singly or in combination of two or more.
  • a novolac type epoxy resin a modified novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol type epoxy resin, or a mixture thereof is particularly preferable.
  • the polyfunctional oxetane compound (D-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or 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)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, their oligomers or copolymers, etc.
  • oxetane, and oxetane with novolac resin poly(p-hydroxystyrene), Cardo type bisphenol, calixarene, resorcinol calixarene, or sesquisilane
  • An etherified product of a resin having a hydroxyl group such as oxyalkylene.
  • a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may, for example, be mentioned.
  • YL7000 bisphenol A type episulfide resin
  • D-3 episulfide resin having two or more cyclic thioether groups in the molecule.
  • D-3 episulfide resin
  • YSLV-120TE and the like.
  • the amount of the (D) thermosetting component to be added is 10 to 100 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin.
  • the amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents per equivalent of the carboxyl group of the carboxyl group-containing resin (A). More preferably, it is the range of 0.8-2.0 equivalent.
  • titanium oxide by a sulfuric acid method, a chlorine method, a rutile type or an anatase type titanium oxide, and surface treatment using a surface treatment of a hydrated metal oxide or surface treatment with an organic compound can be used. Wait.
  • rutile-type titanium oxide is more preferable.
  • Anatase type titanium oxide is often used because it has a high whiteness compared to the rutile type.
  • anatase-type titanium oxide has photocatalytic activity, it sometimes causes discoloration of the resin in the photocurable resin composition.
  • the rutile-type titanium oxide is slightly inferior in whiteness to the anatase type, it has almost no photoactivity, and thus a stable coating film can be obtained.
  • rutile-type titanium oxide As the rutile-type titanium oxide, a known rutile-type titanium oxide can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by FUJI TITANIUM INDUSTRY CO, LTD., R-550, R-580, R-630 manufactured by Ishihara Sangyo Co., Ltd., R-820, CR-50, CR-60, CR-90, CR-97, KR-270, KR-310, KR-380, etc. manufactured by Titan Kogyo, Ltd. Among these rutile-type titanium oxides, titanium oxide treated with surface hydrated alumina or aluminum hydroxide is particularly preferable from the viewpoint of dispersibility, storage stability, and flame retardancy.
  • the compounding amount of the (E) titanium oxide is preferably 50 to 300 parts by mass, more preferably 150 to 300 parts by mass, even more preferably 200 to 300 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.
  • the compounding amount is 50 parts by mass or more, a good reflectance can be obtained.
  • the toughness of the cured coating film is good.
  • an imidazole having a primary average particle diameter of 15 ⁇ m or less is preferable.
  • An imidazole derivative such as 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole.
  • 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ product name of all imidazole type compounds manufactured by Shikoku Chemicals Co., Ltd., etc.
  • the imidazole having a reaction initiation temperature of 100 ° C or more is used. Further, it may be used alone or in combination of two or more.
  • the ratio of the amount of the (F) heat-curing catalyst to the usual amount is sufficient.
  • it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.
  • a (G) filler other than titanium oxide may be blended as needed in order to increase the physical strength of the coating film and the like.
  • a (G) filler a commonly known inorganic or organic filler can be used, and barium sulfate, spherical silica, and talc are particularly preferably used.
  • a metal hydroxide such as a metal oxide or aluminum hydroxide may be used as the extender pigment filler.
  • the compounding amount of these (G) fillers is preferably 150 parts by mass or less, more preferably 5 to 100 parts by mass, particularly preferably 10 to 70 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.
  • the amount of the filler (G) is 150 parts by mass or less, the viscosity of the composition does not become too high, the printability is good, and the occurrence of deterioration in toughness of the cured product or the like can be suppressed.
  • the photocurable thermosetting resin composition of the present invention can use a binder polymer in order to improve the dryness of the touch, improve the handleability, and the like.
  • a binder polymer for example, a polyester-based polymer, a urethane-based polymer, a polyester urethane-based polymer, a polyamide-based polymer, a polyester amide-based polymer, an acrylic polymer, a cellulose-based polymer, or a polylactic acid can be used.
  • These binder polymers may be used singly or in the form of a mixture of two or more.
  • the photocurable thermosetting resin composition of the present invention may use another elastomer in order to impart flexibility, improve the brittleness of the cured product, and the like.
  • a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer, or an olefin elastomer can be used.
  • an epoxy group-containing polybutadiene-based elastomer an acryl-containing polybutadiene-based elastomer, or the like may be used.
  • These elastomers may be used singly or in the form of a mixture of two or more.
  • the photocurable thermosetting resin composition of the present invention may be an organic solvent for the purpose of (A) synthesis of a carboxyl group-containing resin, preparation of a composition, or adjustment of viscosity to coat a substrate or a film.
  • Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methyl carbene.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene
  • cellosolve methyl cellosolve, butyl cellosolve, carbitol, and methyl carbene.
  • the photocurable thermosetting resin composition of the present invention can be added to prevent oxidation (1).
  • a radical scavenger (H-1) or/and (2) which can deactivate the generated radicals, which can decompose the generated peroxide into a harmless substance and a peroxide decomposition which does not generate new radicals.
  • Antioxidant (H) such as agent (H-2).
  • Examples of the specific antioxidant of the antioxidant (H-1) which functions as a radical scavenger include hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, hydroquinone monomethyl ether, and 2 ,6-di-tert-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-tert-butyl-4-hydroxybenzyl)benzene, 1, 3,5- Phenolic, p-methoxyphenol (methoquinone) such as tris(3',5'-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione
  • An anthraquinone compound such
  • the radical scavenger may also be a commercially available product, and examples thereof include ADEKASTAB AO-30, ADEKASTAB AO-330, ADEKASTAB AO-20, ADEKASTAB LA-77, ADEKASTAB LA-57, ADEKASTAB LA-67, ADEKASTAB LA-68, ADEKASTAB LA-87 (above, manufactured by Asahi Kasei Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111 FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals Inc. Manufacturing, trade name), etc.
  • the antioxidant (H-2) which functions as a peroxide decomposing agent may, for example, be a phosphorus compound such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate or dilauryl sulfur.
  • a sulfur-based compound such as a dipropionate or a distearyl 3,3'-thiodipropionate.
  • the peroxide decomposing agent may be a commercially available product, and examples thereof include ADEKASTAB TPP (manufactured by Asahi Kasei Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), and Sumilizer TPS. (manufactured by Sumitomo Chemical Co., Ltd., trade name).
  • antioxidants (H) may be used alone or in combination of two or more.
  • the photocurable thermosetting resin composition of the present invention can be used in addition to the above-mentioned antioxidant in order to carry out decomposition and deterioration.
  • UV absorber (I) UV absorber
  • Examples of the ultraviolet absorber (I) include a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, and an ortho An aminobenzoate derivative, a dibenzoylmethane derivative or the like.
  • Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-di. Hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone.
  • benzoate derivatives examples thereof include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, and 2,4-di-tert-butylphenyl-3,5-di. Tert-butyl-4-hydroxybenzoate and cetyl-3,5-di-tert-butyl-4-hydroxybenzoate.
  • benzotriazole derivative include 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methyl group.
  • Phenyl)benzotriazole 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' , 5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole and the like.
  • Specific examples of the triazine derivative include hydroxyphenyltriazine and bis-ethylhexyloxyphenol methoxyphenyltriazine.
  • the ultraviolet absorber (I) may be a commercially available product, and examples thereof include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, and TINUVIN 405.
  • TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals Inc., trade name) and the like.
  • the ultraviolet ray absorbing agent (I) can be used singly or in combination of two or more kinds, and the molded article obtained by the photocurable thermosetting resin composition of the present invention can be stabilized by being used in combination with the above-mentioned antioxidant (H). Chemical.
  • thermosetting resin composition of the present invention in order to improve the sensitivity, a well-known conventional N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid or mercaptothiazole can be used as the chain transfer agent. Wait.
  • chain transfer agent examples include chain transfer agents having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, a chain transfer agent having a hydroxyl group such as mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxythiophenol, and derivatives thereof; 1-butyl mercaptan, butyl 3-mercaptopropionate, 3- Methyl mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylthiophenol, dodecyl mercaptan, propanethiol, butyl mercaptan, pentane Mercaptan, 1-octyl mercaptan, cyclopent
  • a polyfunctional thiol compound can be used without particular limitation, and for example, it can be used.
  • Aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercapto diethyl ether, dimercapto diethyl sulfide, phthalic thiol, 4, 4 Aromatic thiols such as '-dimercaptodiphenyl sulfide and 1,4-benzenedithiol; ethylene glycol bis(mercaptoacetate), polyethylene glycol bis(mercaptoacetate), propylene glycol double (mercaptoacetate), glycerol tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate) Poly(mercaptoacetate) of polyhydric alcohol
  • Examples of the commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, ⁇ Chemical Industries, Ltd.), KARENZ MT-PE1, KARENZ MT- BD1 and KARENZ-NR1 (above, manufactured by Showa Denko KK).
  • heterocyclic compound having a mercapto group which functions as a chain transfer agent examples include mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-mercapto-4-methyl group 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-thiobutyrolactone, 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-indenyl- 4-butyrolactam, N-(2-methoxy)ethyl-2-indolyl-4-butyrolactam, N-(2-ethoxy)ethyl-2-indolyl-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-vale
  • the heterocyclic compound having a mercapto group as a chain transfer agent which does not impair the developability of the photocurable thermosetting resin composition is preferably mercaptobenzothiazole or 3-mercapto-4-methyl-4H-1. 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole.
  • chain transfer agents may be used alone or in combination of two or more.
  • an adhesion promoter may be used in order to improve the adhesion between the layers or the adhesion between the resin layer and the substrate.
  • an adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Industry) Accelerator M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2- Mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, aminobenzotriazole-containing, silane coupling agent, and the like.
  • the photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as fine powder silica, organic bentonite, montmorillonite or hydrotalcite as needed. From the viewpoint of stability over time as a thixotropic agent, organic bentonite and hydrotalcite are preferred, and hydrotalcite is particularly excellent in electrical properties.
  • a thixotropic agent such as fine powder silica, organic bentonite, montmorillonite or hydrotalcite as needed.
  • organic bentonite and hydrotalcite are preferred, and hydrotalcite is particularly excellent in electrical properties.
  • an antifoaming agent such as a thermal polymerization inhibitor, a silicone-based, a fluorine-based or a polymer-based polymer, and/or a leveling agent, a silane coupling agent such as an imidazole-based, a thiazole-based or a triazole-based compound, or a rust preventive agent may be blended.
  • the aforementioned thermal polymerization inhibitor can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound.
  • the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol, pyrogallol, 2-hydroxybenzophenone, and 4 -Methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2 a reaction product of '-methylenebis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and an organic chelating agent, Methyl salicylate, and phenothiazine, sub a nitro compound
  • the printed wiring board of the present invention has a cured product obtained from the photocurable thermosetting resin composition of the present invention on a substrate.
  • the photocurable thermosetting resin composition is adjusted to a viscosity suitable for the coating method using the organic solvent, and the photocurable thermosetting resin composition is dip coated.
  • Method, flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc. are applied to a substrate, and the organic solvent contained in the composition is volatilized at a temperature of about 60 to 100 ° C. Dry (temporary drying) to form a non-stick coating film.
  • the active energy ray is selectively exposed by contact (or non-contact) through the patterned photomask, or direct pattern exposure is performed by a laser direct exposure machine, and the unexposed portion is treated with an aqueous alkali solution (for example, 0.3).
  • aqueous alkali solution for example, 0.3
  • aqueous sodium carbonate solution for example, 0.3
  • it is heated to a temperature of, for example, about 140 to 180 ° C to be thermally cured, thereby reacting the (A) carboxyl group-containing resin with the (D) thermosetting component to obtain heat resistance, chemical resistance, and moisture absorption resistance.
  • a printed circuit board of a cured coating film having excellent properties such as properties, adhesion, and electrical properties.
  • a copper clad laminate As the substrate, in addition to a printed circuit board or a flexible printed circuit board on which a circuit is formed in advance, a copper clad laminate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer can be used. Board and so on.
  • the copper clad laminate is made of paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/non-woven fabric, epoxy resin, glass cloth/paper-ring
  • the volatilization drying which is carried out after applying the photocurable thermosetting resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a device having a heat source using an air heating method using steam).
  • the hot air convection contact method in the dryer and the method of blowing the nozzle to the support are performed.
  • a direct drawing device for example, a laser direct imaging device that directly draws an image by laser based on CAD data from a computer
  • an exposure machine equipped with a metal halide lamp can be used
  • a dipping method, a shower method, a spray method, a brushing method, or the like can be used.
  • potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, or ammonia can be used.
  • An aqueous alkali solution such as an amine.
  • the photocurable thermosetting resin composition of the present invention may be used in the form of a dry film in addition to a method of directly applying a liquid to a substrate, the dry film having a polyethylene terephthalate in advance.
  • the dry film has a structure in which a film, a resin layer, and a peelable cover film used as needed are laminated in this order.
  • the resin layer is a layer obtained by applying and drying a photocurable thermosetting resin composition on a carrier film or a cover film. After the resin layer is formed on the carrier film, a cover film is laminated thereon, or a resin layer is formed on the cover film, and the 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 can be used.
  • the photocurable thermosetting resin composition is uniformly coated on the carrier film or the cover film with a thickness of 10 to 150 ⁇ m by a knife coater, a lip coater, a comma coater, a film coater or the like. It is formed by coating and drying.
  • cover film a polyethylene film, a polypropylene film, or the like can be used, and a cover film having a lower adhesive force to the resin layer than the carrier film and the resin layer can be used.
  • a cured coating film is formed on a printed circuit board using a dry film, the cover film is peeled off, and the resin layer is superposed on the substrate on which the circuit is formed, and bonded by a laminator or the like to form a substrate on which the circuit is formed.
  • a resin layer When the formed resin layer is exposed, developed, and cured in the same manner as described above, a cured coating film can be formed.
  • the carrier film may be peeled off before or after exposure.
  • the photocurable thermosetting resin composition of the present invention is suitably used for forming a cured coating film on a printed circuit board.
  • the cured coating film is preferably a permanent insulating coating film, and particularly preferably a solder resist layer or a coating layer.
  • the photocurable thermosetting resin composition of the present invention can also be used as an interlayer insulating material, a buried via filler, and a solder dam forming material.
  • An o-cresol novolac type epoxy resin [EPICLON N-695, manufactured by DIC Corporation, softening point 95 ° C, epoxy equivalent 214, average functionality 7.6] 1070 g was added to 600 g of diethylene glycol monoethyl ether acetate. (Glycidyl group number (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone, and the mixture was heated and stirred to 100 ° C to be uniformly dissolved. Next, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110 ° C for 2 hours, and then heated to 120 ° C for further 12 hours.
  • a novolac type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4) 119.4 g was placed in an autoclave equipped with a thermometer, a nitrogen gas introducing device, an alkylene oxide introducing device, and a stirring device. 1.19 g of potassium hydroxide and 119.4 g of toluene were subjected to nitrogen substitution in the system while stirring, and the temperature was raised by heating. Subsequently, 63.8 g of propylene oxide was slowly added dropwise, and the mixture was reacted at 125 to 132 ° C for 0 to 4.8 kg/cm 2 for 16 hours.
  • polycaprolactone diol (PLACCEL 208 manufactured by Daicel Chemical Co., Ltd., molecular weight 830) as a polymer polyol was introduced as 201 g of dihydroxymethylpropionic acid as a dihydroxy compound of a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, and 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and then sequentially put into a pair of 0.5 g of oxyphenol and di-tert-butyl-hydroxytoluene.
  • PLACCEL 208 manufactured by Daicel Chemical Co., Ltd., molecular weight 830
  • thermosetting resin composition According to the various components shown in Tables 1 and 2 below and the ratios (parts by mass) shown in Tables 1 and 2, compounded by a mixer, and then kneaded by a three-roll mill to prepare photocuring. A thermosetting resin composition.
  • the compounding ratio (parts by mass) of the carboxyl group-containing resin is expressed in terms of solid content.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10
  • Example 11 (A-1) Carboxyl group-containing resin*1 40.0 40.0 40.0 20.0 60.0 20.0 40.0 20.0 20.0 (A-1) Carboxyl group-containing resin*2 40.0 20.0 (A-2) Carboxyl group-containing resin*3 60.0 80.0 40.0 60.0 60.0 30.0 30.0 20.0 (A-2) Carboxyl group-containing resin *4 60.0 30.0 (A-2) Carboxyl group-containing resin*5 60.0 (A-3) Carboxyl group-containing resin *6 50.0 60.0 (A-3) Carboxyl group-containing resin*7 50.0 Photopolymerization initiator*8 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Photopolymerization initiator*9 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Photosensitive monomer *10 10.0 10.0 10.0
  • Antioxidant IRGANOX1010 manufactured by BASF, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]
  • the photocurable thermosetting resin composition of the above examples and comparative examples was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried at 80 ° C for 30 minutes, and naturally cooled to room temperature.
  • the substrate was exposed to light using an exposure apparatus equipped with a high-pressure mercury lamp and a negative film, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C for 90 seconds under a pressure of 0.2 MPa to obtain a resist pattern.
  • the substrate was heated at 150 ° C for 60 minutes to be cured to prepare a substrate for evaluation.
  • the evaluation substrate coated with the rosin-based flux was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with a modified alcohol, and then the swelling and peeling of the cured coating film was visually evaluated.
  • the judgment criteria are as follows.
  • the cured coating film was cross-cut in a checkerboard pattern, and the presence or absence of cracks in the cured coating film was observed with an optical microscope.
  • the cured coating film has a large number of cracks
  • the photocurable thermosetting resin composition of the above examples and comparative examples was applied to a glass plate of 150 mm ⁇ 75 mm by screen printing so as to have a film thickness of 20 ⁇ m. Then, it was dried to form a coating film, and the reflectance of the coating film at 420 nm was measured using an integrating sphere apparatus (V-670 ILN-725 type manufactured by JASCO Co., Ltd.).
  • the reflectance is 90% or more
  • the reflectance is 80% or more and less than 90%
  • the reflectance is 70% or more and less than 80%
  • ⁇ : reflectance is lower than 70%
  • the photocurable thermosetting resin composition of the present invention can be suitably used as an excellent resistance to cracking resistance even when the content of titanium oxide is large, and the resistance to soldering heat resistance is not lowered.
  • a resin composition for flux it is understood that a white coating film having a high reflectance can be obtained by using the photocurable thermosetting resin composition of the present invention.

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Abstract

Cette invention concerne une composition de résine thermodurcissable durcie à la lumière, un film sec, un matériau durci et une carte de circuit imprimé. La composition de résine thermodurcissable durcie à la lumière comprend : (A) une résine contenant un carboxyle, (B) un initiateur de photopolymérisation, (C) un monomère photosensible, (D) un constituant thermodurcissable et (E) de l'oxyde de titane. La (A) résine contenant un carboxyle comprend (A-1) une résine du type bisphénol contenant un carboxyle et (A-2) une résine du type novolaque contenant un carboxyle, le rapport massique de la (A-1) résine du type bisphénol contenant un carboxyle à la (A-2) résine du type novolaque contenant un carboxyle (la (A-1) résine du type bisphénol contenant un carboxyle : le (A-2) résine du type novolaque contenant un carboxyle) est dans la plage de 20 : 80 à 60 : 40.
PCT/CN2014/090861 2014-07-31 2014-11-12 Composition de résine thermodurcissable durcie à la lumière, film sec, produit durci et carte de circuit imprimé WO2016015398A1 (fr)

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WO2023190456A1 (fr) * 2022-03-31 2023-10-05 太陽ホールディングス株式会社 Produit durci, composition de résine photosensible, film sec et carte de circuit imprimé

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