WO2001051991A1 - Composition a base de resine, produit polymerise obtenu a partir de cette composition et article realise avec cette composition - Google Patents

Composition a base de resine, produit polymerise obtenu a partir de cette composition et article realise avec cette composition Download PDF

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Publication number
WO2001051991A1
WO2001051991A1 PCT/JP2001/000024 JP0100024W WO0151991A1 WO 2001051991 A1 WO2001051991 A1 WO 2001051991A1 JP 0100024 W JP0100024 W JP 0100024W WO 0151991 A1 WO0151991 A1 WO 0151991A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
acid
compound
molecule
oligomer
Prior art date
Application number
PCT/JP2001/000024
Other languages
English (en)
Japanese (ja)
Inventor
Yuichiro Matsuo
Satoshi Mori
Hiroo Koyanagi
Minoru Yokoshima
Toru Ozaki
Original Assignee
Nippon Kayaku Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2000003681A external-priority patent/JP2001192431A/ja
Priority claimed from JP2000264783A external-priority patent/JP2002072470A/ja
Application filed by Nippon Kayaku Kabushiki Kaisha filed Critical Nippon Kayaku Kabushiki Kaisha
Publication of WO2001051991A1 publication Critical patent/WO2001051991A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a resin composition, particularly a photosensitive resin composition suitable for forming an etching resist or a protective film (cover layer) which can be used for producing a flexible printed wiring board and the like, and a photosensitive film using the same.
  • a resin composition particularly a photosensitive resin composition suitable for forming an etching resist or a protective film (cover layer) which can be used for producing a flexible printed wiring board and the like, and a photosensitive film using the same.
  • a printed wiring board on which wiring is formed is used for limiting soldering positions, protecting wiring, and the like.
  • Some printed wiring boards are in the form of films that can be folded and incorporated into small devices such as cameras, and these are called flexible printed circuit boards (FPCs).
  • FPCs flexible printed circuit boards
  • This FPC also requires a register to limit the soldering position and protect the wiring, and it is called a cover or cover coat.
  • the coverlay is formed by punching a polyimide / polyester with an adhesive layer into a predetermined mold and then thermocompression bonding on the FPC.
  • the cover coat is printed with thermosetting or photocurable ink. It is formed by curing.
  • a photosensitive resin composition for forming a solder mask For this purpose, attempts have been made to use a photosensitive resin composition for forming a solder mask.
  • a photosensitive resin composition containing an acrylic polymer and a photopolymerizable monomer as main components JP-B-53-56018, JP-A-54-10818, etc.
  • Good heat resistance JP-A-54-82073 and JP-A-58-62636 disclose a photosensitive resin composition which is mainly composed of a photosensitive epoxy resin having a chalcone group in a main chain and an epoxy resin curing material.
  • Etc. a composition mainly composed of a novolak type epoxy acrylate containing an epoxy group and a photopolymerization initiator (JP-A-61-27)
  • a photosensitive resin composition for forming a solder mask which is excellent in safety and economy and can be developed with an alkaline aqueous solution, includes a carboxyl group-containing polymer, a monomer, a photopolymerization initiator and a thermosetting resin.
  • the present invention solves the above-mentioned drawbacks of the conventional technology, and provides a photosensitive resin composition excellent in workability, flexibility, solder heat resistance and the like, and a photosensitive film using the same. is there. Disclosure of the invention
  • the present invention is a.
  • a monocarboxylic acid (b) having one unsaturated double bond and one carboxyl group in one molecule Contains an oligomer (A) obtained by reacting an unsaturated boryl compound (c), a diamine compound (d), and a polybasic acid anhydride (e) having at least two acid anhydride groups in one molecule.
  • a diamine compound (d) is reacted with a polybasic anhydride (e) having two acid anhydride groups in one molecule to synthesize a terminal acid anhydride polyamide prepolymer (h).
  • the resin composition according to the above item 1 or 2 comprising an oligomer (A) obtained by reacting the unsaturated polyol compound (c),
  • Epoxy resin (f) having two or more epoxy groups in one molecule, monocarboxylic acid (E-b) having one unsaturated double bond and one carboxyl group in one molecule, and polybasic anhydride The resin composition according to any one of the above items 1 to 3, which contains an unsaturated group-containing polycarboxylic acid resin (E) which is a reaction product with the product (g),
  • a resin composition comprising the oligomer (A), the diluent (B), and the photopolymerization initiator (C) according to any one of the above items 1 to 3,
  • thermosetting component (D) a thermosetting component
  • a photosensitive film obtained by laminating a layer of the resin composition according to any one of the above items 1 to 7 on a support film,
  • Two phenyl groups having a carboxyl group are bonded directly or via a crosslinking group having a molecular weight in the range of 14 to 144.
  • the oligomer (A) used in the present invention is composed of an epoxy resin (a) having two epoxy groups in one molecule and a monocarboxylic acid having one unsaturated double bond and one carboxyl group in one molecule (hereinafter, referred to as “a”).
  • a polyunsaturated polyol compound (c) obtained by reacting (b) with an ethylenically unsaturated group-containing monocarboxylic acid, a diamine compound (d), and two acid anhydride groups in one molecule. To obtain a polybasic acid anhydride (e).
  • a hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the monocarboxylic acid containing an ethylenically unsaturated group (b), and the polyunsaturation is carried out.
  • a polyol compound (c) is obtained.
  • the hydroxyl group of (c) and the amino group of (d) undergo an esterification reaction and an amidation reaction with the polybasic acid anhydride (e) having two acid anhydride groups in one molecule.
  • Examples of the epoxy resin (a) having two epoxy groups in one molecule include a diglycidyl ether compound, a diglycidyl ester compound, a diglycidylamine compound, and the like. These diglycidyl compounds are not particularly limited, but usually those having a molecular weight of about 170 to 542 are preferred.
  • the diglycidyl ether compound can be obtained by a known method in which a polyol compound and epichlorohydrin are added to one equivalent of the former hydroxyl group and at least one equivalent of the latter is reacted.
  • the polyol compound include a polyphenol having 2 to 3 hydroxy groups, a bisphenol compound in which two phenyl groups having a hydroxy group are bonded with or without a crosslinking group, and a bisphenol compound of the bisphenol compound.
  • Examples include hydrogenated compounds and aliphatic diols having 1 to 10 carbon atoms.
  • polyol compound examples include bisphenol A, bisphenol F, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, Tetraalkylbiphenol such as resorcinol, biphenol, tetramethylbiphenol, hydrogenated bisphenol A, hydrogenated bisphenol F, tetrabromobisphenol A, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene Glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl 1,5-pentanonediol, 1,9-nonanediol, 1,4-hexanediol, dimer acid diol And the like.
  • the diglycidyl ester compound can be obtained by a known method in which a polycarboxyl compound and epichlorohydrin are added to one equivalent of the former carboxyl group and reacted in an amount of one or more equivalents of the latter.
  • Examples of the polycarboxyl compound for the diglycidyl ester compound include a 6-membered ring compound having 2 or more carboxyl groups as a substituent or an aliphatic hydrocarbon compound having 1 to 3 carbon atoms having 2 or more carboxyl groups.
  • the 6-membered ring compound may be an aromatic ring or a saturated or unsaturated aliphatic ring, and may have a substituent such as a lower alkyl group on the ring.
  • examples of the polycarboxyl compound include fluoric acid, tetrahydrophthalic acid, hexahydrofluoric acid, endomethylenetetrahydrophthalic acid, methyl endmethylenetetrahydrofluoric acid, succinic acid, and maleic acid.
  • the diglycidylamine compound is obtained by adding and reacting an amino compound with epichlorohydrin in an amount of at least one equivalent of the former with respect to one equivalent of the amino group.
  • examples of the amino compound include aniline and o-toluidine. Is mentioned.
  • the ethylenically unsaturated group-containing monocarboxylic acid (b) includes, for example, an ethylenically unsaturated aliphatic carboxylic acid having 3 to 5 carbon atoms, or a saturated or unsaturated dibasic acid and an ethylenically unsaturated group-containing monocarboxylic acid.
  • a reaction product with a monoglycidyl compound or an ethylenically unsaturated group-containing hydroxy compound is exemplified.
  • the ethylenically unsaturated aliphatic carboxylic acid having 3 to 5 carbon atoms may be substituted with a substituent such as a phenyl group or a furyl group.
  • Examples of the ethylenically unsaturated group-containing monoglycidyl compound or the ethylenically unsaturated group-containing hydroxy compound include monodaricidyl. (Meth) acrylate derivatives or (meth) acrylate derivatives having one hydroxyl group in the molecule.
  • the monocarboxylic acid (b) include, for example, acrylic acid, acrylic acid dimer, acrylic acid such as methacrylic acid, 3-styrylacrylic acid, and 3-furfurylacrylic acid; crotonic acid; Examples include monocyanocinnamic acid, cinnamic acid, or half-esters that are equimolar reactants of a saturated or unsaturated dibasic acid with monoglycidyl (meth) acrylate or hydroxyalkyl (meth) acrylate. Of these, preferred are ethylenically unsaturated aliphatic carboxylic acids having 3 to 5 carbon atoms, and particularly preferred is (meth) acrylic acid. These ethylenically unsaturated group-containing monocarboxylic acids (b) can be used alone or as a mixture.
  • (meth) acrylic acid means acrylic acid or methacrylic acid.
  • saturated or unsaturated dibasic acid anhydride used in the production of half esters include, for example, an acid anhydride of a 6-membered ring compound having two carboxyl groups at adjacent positions as a substituent or a fatty acid having 2 to 5 carbon atoms. And acid anhydrides of aromatic dicarboxylic acids.
  • 6-membered ring include a benzene ring and a saturated or unsaturated alicyclic 6-membered ring.
  • a saturated or unsaturated dibasic anhydride suitable for producing a half ester with an ethylenically unsaturated group-containing hydroxy compound for example, succinic anhydride, maleic anhydride, fumaric anhydride, tetrahydroanhydride
  • succinic anhydride maleic anhydride, fumaric anhydride, tetrahydroanhydride
  • examples thereof include phthalic acid, hexahydrophthalic anhydride, methylhexahydrofluoric anhydride, methyltetrahydrofluoric anhydride, itaconic anhydride, and methylendmethylenetetrahydrophthalic anhydride.
  • (meth) acrylate derivatives having one hydroxyl group in one molecule are preferable, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • Examples of the saturated or unsaturated dibasic acid used for the production of half esters with an ethylenically unsaturated group-containing monodaricidyl compound include, for example, succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrofuran. Examples thereof include phosphoric acid, itaconic acid, and fumaric acid, and examples of the monoglycidyl (meth) acrylate derivatives include glycidyl (meth) acrylate.
  • the above-mentioned ethylenically unsaturated group-containing monocarboxylic acid (b) is added to one equivalent of the epoxy group of the epoxy resin (a). Is preferably reacted at a ratio of about 0.8 to 1.3 mol, and particularly preferably at a ratio of about 0.9 to 1.1 mol. Preferably, a diluent is used during the reaction.
  • diluent examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, dipropylene glycol dimethyl ether, and dipropylene daritol dimethyl ether.
  • Glycol ethers such as ethyl acetate, butyl acetate, butyl acetate solv acetate, carbitol acetate, and other esters, arptyrolactone, valerolactone, lactones such as 7 "-proprolactone, octane, Aliphatic hydrocarbons such as decane, alicyclic hydrocarbons such as cyclohexane and cyclohexanone, and organic solvents such as petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Or carbitol (meth) acrylate, pheno Kishetil (meta) acrylate, pen erythritol tritetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, dipentyl erythritol
  • a catalyst to promote the reaction for example, triethylamine, benzyldimethylamine, methyltriethylamine.
  • the amount of the catalyst to be used is preferably 0.1 to 10% by weight based on the reaction raw material mixture.
  • a polymerization inhibitor In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor.
  • Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
  • the amount used is preferably 0.01 to 1% by weight based on the reaction raw material mixture.
  • the reaction temperature is preferably from 60 to 150 ° C.
  • the reaction time is preferably 5 to 60 hours.
  • the diamine compound (d) is not particularly limited, and preferably has a molecular weight in the range of 60 to 563.
  • diamine compound (d) for example, an aliphatic or aromatic hydrocarbon compound having 1 to 13 carbon atoms having two amino groups directly or via a bridging group, or one amino group directly or via a bridging group Diphenyl compounds in which two phenyl groups having a group are bonded directly or via a cross-linking group; and polysiloxanes having two amino substituents.
  • the crosslinking group for the amino group is not particularly limited, and those exemplified below for the crosslinking group for the phenyl group can be used.
  • —C 6 H 4 — ⁇ _ (wherein 1 C— represents a phenylene group) Is preferred.
  • cross-linking group connecting two phenyl groups examples include an alkylene group having 1 to 6 carbon atoms, one O—, —S—, one SO 2 —, —SO—, one CO—, and one C 6 H 4 — CO- C 6 H 4 - one C 6 H 4 - CONH- C 6 H 4 -, - NH- , and the like.
  • the above aminodiamine compound (d) may have a substituent other than an amino group or a crosslinking group having an amino group, for example, a halogen atom or the like as a substituent.
  • Preferred examples of the diamine compound (d) include a diamine compound (d-1) containing a sulfur atom and a compound having a crosslinking group usually containing a sulfur atom.
  • Preferred diamine compounds other than the above-mentioned diamine compound containing a sulfur atom (d-1), that is, diamine compounds not containing a sulfur atom (d-2) include, for example, 2,2-bis [4- (4-1 Aminophenoxy) phenyl] propane, 2,2-bis [4-1 (3-aminophenoxy) phenyl] hexafluoropropane, bis [4-1 (4-aminophenoxy) phenyl] biphenyl, bis [4— ( 4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (3-aminophenoxy) phenyl] benzophenone, Bis [4- (4-aminophenoxy) phenyl] benzanilide, S [4
  • the above diamine compounds (d) can be used alone or in combination of two or more.
  • a tetracarboxylic anhydride is preferable, and a dianhydride of an aromatic tetracarbonic acid having 6 to 10 carbon atoms, Aliphatic tetracarboxylic dianhydride of number 4 to 10, next to W
  • Examples thereof include dicarboxylic anhydrides of tetracarboxylic acids in which two phenyl groups having two carboxyl groups in contact with 1 are bonded directly or via a crosslinking group having a molecular weight in the range of 14 to 144.
  • the crosslinking group here may be the diamine compound
  • cross-linking group described in the section (d) can be used, but preferred are one O—, one S ⁇ 2 —, — C ⁇ —, —CO— ⁇ — (alkylene group having 1 to 4 carbon atoms) O—CO— and the like.
  • pyromellitic dianhydride benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, 3, 3 ′, 4, 4′—
  • Diphenylsulfonetetracarboxylic dianhydride such as diphenylsulfonetetracarboxylic dianhydride; butanetetracarboxylic dianhydride; ethylene glycol bis (anhydrotrimellitate); and the like, alone or in combination of two or more. These can be used in combination.
  • the polyunsaturated polyol compound (c) and the diamine compound (d) obtained above are reacted with the compound (e) having at least two acid anhydride groups in one molecule to form the oligomer (A).
  • the compound (e) having at least two acid anhydride groups in one molecule to form the oligomer (A).
  • a compound having two acid anhydride groups in one molecule may be used. It is preferred to react (e) with 0.1 to 0.9 equivalents (as acid anhydride equivalents).
  • the reaction temperature is preferably 0 to 150 ° C, and the reaction time is preferably 1 to 10 hours.
  • a catalyst such as triethylamine may be added in an amount of 0.1 to 10%.
  • the method of reacting the polyunsaturated polyol compound (c) after synthesizing the terminal acid anhydride polyamide prepolymer (h) includes, first, a diamine compound (d) and a polyamine having at least two acid anhydride groups in the molecule.
  • the acid anhydride (e) is reacted to prepare terminal anhydride polyamide prepolymer (h), and then the polyunsaturated polyol compound (c) is reacted.
  • the terminal acid anhydride polyamide prepolymer (h) is a polybasic acid anhydride (e) having at least two acid anhydride groups in the molecule per one equivalent of the amino group of the diamine compound (d).
  • the reaction is preferably performed in a range of 1.05 to 2.05 equivalents (as acid anhydride equivalents).
  • the reaction temperature of this amidation reaction is preferably 0 to 80 ° C., and the reaction time is preferably 1 to 10 hours.
  • a polyunsaturated polyol compound (c) is reacted with the terminal acid anhydride polyamide prepolymer (h) to obtain an oligomer (A).
  • the terminal acid anhydride polyamide prepolymer was used for one equivalent of the hydroxyl group of the polyunsaturated polyol compound (c).
  • the reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 90 ° C.
  • a polymerization inhibitor such as 50 to 200 ppm of hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, or p-benzoquinone is added. Is preferred.
  • the reaction between the hydroxyl group and the acid anhydride group proceeds without a catalyst, but a basic compound such as triethylamine or triphenylphosphine may be added as a catalyst.
  • a diluent may be added during this reaction.
  • the diluent include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; glycol ethers such as dipropylene dalicol dimethyl ether and dipropylene dalicol getyl ether.
  • Esters such as ters, ethyl acetate, butyl acetate, sorbet acetate, carbitol-lu-acetate, lactones such as a-butyrolactone, a-valerolactone, and a-proprolactone; and aliphatic carbonization such as octane and decane
  • Alicyclic hydrocarbons such as hydrogen, cyclohexane and cyclohexanone
  • organic solvents such as petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha
  • Acrylate Hue Kishechiru (main evening) Akurireto, pen evening erythritol tall tetra (meth) Akurireto, trimethylolpropane tri (meth) Akurireto, tris (hydroxymethyl E chill) iso Xia isocyanurate tri (meth) Akurireto, to Jipen evening erythr
  • the amount of the oligomer (A) contained in the resin composition of the present invention is preferably from 10 to 100% by weight, particularly preferably from 15 to 100% by weight, and usually from 35 to 80% by weight in the composition. % By weight.
  • a diluent and other additives may be contained as components other than the oligomer (A).
  • the additives include a polymerization inhibitor and a catalyst. Their content is 90 to 0% by weight of diluent, preferably 85 to 0% by weight, usually 60 to 15% by weight, and other additives at about 0 to 11% by weight, usually 0.1 to 0.1%. 5% by weight.
  • the photosensitive resin composition of the present invention can be generally prepared by adding a photopolymerization initiator.
  • the photosensitive resin composition of the present invention (hereinafter simply referred to as photosensitive resin composition) generally contains an oligomer (A), a diluent (B) and a photopolymerization initiator (C), and further comprises a thermosetting component. (D) may be contained.
  • the diluent (B) the diluent (the diluent used in the synthesis of the oligomer (A)) contained in the resin composition containing the oligomer (A) can be used as it is, but it may be further added as necessary.
  • Component (B) is a diluent usually used for the synthesis of oligomer (A).
  • ( ⁇ -1), abutyrolactone, avalerolactone, aprolactolactone, and aprolactolactone Lactones such as heptane lactone, ⁇ -acetyl-butyrolactone, ⁇ -caprolactone; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol getyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene diol alcohol dimethyl ether, tetraethylene daricol dimethyl ether, Ethers; carbonates such as ethylene carbonate and propylene carbonate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; phenols such as phenol, cresol and xylenol; Esters such
  • Hydrocarbons such as getylbenzene and cyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochrome benzene; organic solvents such as petroleum solvents and petroleum solvents such as petroleum naphtha ( B-2).
  • the diluents may be used alone or as a mixture of two or more.
  • a photopolymerization initiator (C) is used in the photosensitive resin composition of the present invention.
  • the photopolymerization initiator is not particularly limited as long as it can be used as a photopolymerization initiator.
  • Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc .; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy_2-phenylacetophenone , 1,1-Dichloroacetophenone, 2-Hydroxy-2-methyl-1-phenylpropane-1-one, Diethoxyacetophenone, 1-Hydroxychlorohexylphenyl ketone, 2-Methyl-1- [4— ( Methylthio) phenyl] —2-acetophenones such as morpholinopropane-oneone; 2-ethylanthraquinone, 2—shallybutylanthraquinone, anthraquinones such as 2-chloroanthraquinone and 2-amylanthraquinone; 4—Je
  • an unsaturated group-containing polycarboxylic acid resin (E) may be used.
  • the unsaturated group-containing polycarboxylic acid resin (E) is composed of an epoxy resin (f) having two or more epoxy groups in one molecule, an ethylenically unsaturated group-containing monocarboxylic acid compound (E-b), and a polybasic acid. It is a reaction product with the anhydride (g).
  • An epoxy resin (f) having two or more epoxy groups in one molecule used in the production of an unsaturated group-containing polycarboxylic acid resin (E), an ethylenically unsaturated group-containing monocarboxylic acid compound (Eb Basically, the epoxy resin (a) having two epoxy groups in one molecule in the production of oligomer (A), having one unsaturated double bond and one carboxyl group in one molecule
  • the one described as the monocarboxylic acid (b) is used, but independently of the oligomer (A), it may be the same or different.
  • epoxy resin ( ⁇ ) having two or more epoxy groups in one molecule include, for example, bisphenol type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, Daricidyl ethers such as luminoplac type epoxy resin, trisphenol methane type epoxy resin, brominated epoxy resin, biquilenol type epoxy resin, biphenol type epoxy resin; 3,4-epoxy-16-methylcyclohexylmethyl-3,4-epoxy Alicyclic epoxy resins such as 1-6-methylcyclohexanecarboxylate, 3,4-epoxycyclyl hexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-1-epoxyethyl-3,4-epoxycyclohexane ; Didalicidyl phthalate, Tetrahi Glycidyl esters such as didalidicyl lophthalate and daricidyl dimer; glycidylamines such as tetragly
  • the reaction between the alcoholic hydroxyl group of the epoxy resin and the ephalohydrin is preferably performed in the presence of dimethyl sulfoxide.
  • Epihalohydrin may be used in an amount of 1 equivalent or more based on 1 equivalent of alcoholic hydroxyl group in the raw material epoxy compound. Although there is no particular upper limit, it is usually preferable to use up to about 15 equivalents per equivalent of the alcoholic hydroxyl group.
  • an alkali metal hydroxide is used.
  • the alkali metal hydroxide for example, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferable. It is sufficient to use about 1 equivalent of the alkali metal hydroxide and 1 equivalent of the alcoholic hydroxyl group to be epoxidized in the starting epoxy compound. When the total amount of the alcoholic hydroxyl groups of the starting epoxy compound is epoxidized, it may be used in excess, but if it exceeds 2 equivalents to 1 equivalent of the alcoholic hydroxyl group, the polymer tends to be slightly polymerized. Usually, 2 equivalents or less is preferable.
  • the reaction temperature is preferably 30 to 100 ° C. If the reaction temperature is lower than 30 ° C, the reaction becomes slow and a long-time reaction is required. If the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable.
  • the excess ephalohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resulting resin is dissolved in an organic solvent, and the dehydrohalogenation reaction can be carried out with an alkali metal hydroxide.
  • the epoxy resin (f) is reacted with the ethylenically unsaturated group-containing monocarboxylic acid (E-Ib) to obtain an epoxy carboxylate (polyunsaturated polyol compound), for example, an epoxy (meth) acrylate compound. It is preferable to react 0.3 to 1.2 equivalents of the carboxyl group of the total amount of the component (Eb) with one equivalent of the ethoxy group of the epoxy resin, and more preferably 0.9 to 1.05. Equivalents are preferred. During or after the reaction, use one or more of the above diluents (B). Can be
  • a catalyst can be used to promote the reaction.
  • the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, triphenylstilbin, triphenylphosphine and the like.
  • the amount used is preferably from 0.1 to 10% by weight, more preferably from 0.3 to 5% by weight, based on the reaction raw material mixture.
  • a polymerization inhibitor is preferably used to prevent polymerization of the ethylenically unsaturated group.
  • the polymerization inhibitor include methoquinone, hydroquinone, methylhydroquinone, and phenothiazine.
  • the amount used is preferably from 0.01 to 1% by weight, more preferably from 0.05 to 0.5% by weight, based on the reaction raw material mixture.
  • the reaction temperature is preferably from 60 to 150 ° C, more preferably from 80 to 120 ° C.
  • the reaction time is preferably 5 to 60 hours.
  • polybasic acid anhydride (g) is reacted.
  • polybasic acid anhydrides (g) examples include succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrohydrofluoric anhydride, hexahydrofluoric anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrofluoric anhydride; and the like, preferably a dibasic acid anhydride. It is preferable that the amount of the polybasic anhydride (g) is reacted with the hydroxyl group in the epoxy (meth) acrylate in an amount of 0.05 to 1.00 equivalent per equivalent of the hydroxyl group.
  • the reaction temperature is preferably from 60 to 150 ° C, more preferably from 80 to 100 ° C.
  • thermosetting component (D) a thermosetting component used in the present invention
  • (D) includes an oligomer (A) and an unsaturated group-containing polycarboxylic acid resin.
  • a functional group capable of thermally curing (E) in the molecule it is not particularly limited, and examples thereof include an epoxy resin, a melamine compound, a urea compound, an oxazoline compound, a phenol compound, and a dihydrobenzoxazine. Ring-containing compounds Things and the like.
  • epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenol methane type epoxy resin, and bromine.
  • Glycidyl ethers such as epoxidized epoxy resins, biquilenol-type epoxy resins, and biphenol-type epoxy resins; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-16-methylcyclohexanecarboxylate; Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl_3,4-epoxycyclohexancarboxylate, 1-epoxyethyl_3,4-epoxycyclohexane; diglycidyl phthalate, tetrahydrofuran Acid diglycidyl ester, dimer Darishi Jill esters such as acid Dali glycidyl ester; glycidyl Ruamin such as tetraglycidy
  • heterocyclic epoxy resins such as tri Dali triglycidyl iso Xia cyanurate.
  • an epoxy resin having a melting point of 50 ° C. or more is preferable since a tack-free photopolymerizable film can be formed after drying.
  • Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin.
  • Examples of the urea compound include urea and urea resin which is a polycondensate of urea and formalin.
  • oxazoline compound examples include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline, 2, 4-diphenyloxazoline and the like.
  • phenol compound examples include phenol, cresol, chilenol, catechol, resorcinol, hydroquinone, pyrogallol, resole and the like.
  • dihydrobenzoxazine ring-containing compound examples include, for example, a mixture of 1 equivalent of a hydroxyl group of a compound having a phenolic hydroxyl group and about 1 equivalent of an amino group of a primary amine in 1 to 5 mol of formaldehyde heated to 70 ° C or more. And reacted at 70 to 110 ° C., preferably at 90 to 100 ° C. for 20 to 120 minutes, and thereafter, It can be synthesized by drying under reduced pressure at a temperature of not more than ° C.
  • the compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include compounds such as bisphenol 8, bisphenol F, biphenol, trisphenol, and tetraphenol, and phenol resins.
  • the phenolic resin include monovalent phenolic compounds such as phenolic or xylenol, alkylphenols such as t-butylphenol and octylphenol, and polyvalent phenolic compounds such as resorcinol and bisphenol A.
  • novolak resins or resole resins obtained by reacting a phenol compound with formaldehyde, phenol-modified xylene resins, melamine phenol resins, and polyphenol-modified phenol resins.
  • the primary amine is not particularly limited, and includes methylamine, cyclohexylamine, aniline, substituted aniline and the like.
  • Formaldehyde may be used in the form of formalin or polyformaldehyde.
  • the dihydrobenzozoxazine ring-containing compound can be prepared by a known method (for example, German Patent Publication No. 22 17099, H. Ishida, J. Polym. Sci., Part A 32, 1121 (1994) ) Etc.).
  • thermosetting components (D) an epoxy resin is particularly preferred because it has excellent reactivity with the carboxyl group in the component (A) and the component (E) and has good adhesion to copper.
  • thermosetting component (D) When an epoxy resin is used as the thermosetting component (D), it is preferable to use a curing accelerator for the epoxy resin in order to accelerate the reaction with the carboxyl group in the component (A).
  • epoxy resin curing accelerators include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-didecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2.
  • Imidazole compounds such as ethylimidazole, 1-cyanoethyl—2- decylimidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-diaminotriazine, 2,4- Triazine derivatives such as diamino-6-tolyltriazine and 2,4-diamino-6-xylyltriazine; tertiary derivatives such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine and m-aminophenol Amines; polyphenols and the like.
  • curing accelerators can be used alone or in combination.
  • various additives and the like can be further added as needed.
  • various additives include fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, etc., thixotropic agents such as aerosil, and phthalocyanine.
  • Colorants such as blue, phthalocyanine green, and titanium oxide, silicones, fluorine-based leveling agents and defoamers, dyes, polymerization inhibitors such as hydroquinone, p-methoxyphenol, and hydroquinone monomethyl ether.
  • the use ratio of each component is 20 to 96% by weight of the component (A), 3 to 50% by weight of the component (B), 1 to 30% by weight of the component (C), and (A) 30 to 80% by weight of component, (B) 5 to 50% by weight of component, and (C) 2 to 20% by weight of component.
  • the component (E) it is preferable to replace 0 to 80% by weight, more preferably 10 to 50% by weight, of the component use ratio of the component (A) with the component (E).
  • the functional group of the thermosetting component (D) should be 0.2 to 3 per carboxyl group in the component (A) or the components (A) and (E).
  • the photosensitive resin composition of the present invention is prepared by dissolving, mixing and kneading the components (A), (B), (C), (D), (E) and various additives. Can be manufactured.
  • the photosensitive film of the present invention is obtained by molding the photosensitive resin composition into a film.
  • the photosensitive film of the present invention can be produced by laminating a layer of the photosensitive resin composition of the present invention on a support film.
  • the support include a polymer film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene and the like, and among them, a polyethylene terephthalate film is preferable. Since these polymer films must be removed from the photosensitive layer later, they must not be surface-treated or made of a material that cannot be removed. Further, the thickness of these polymer films is preferably 5 to 100 m, more preferably 10 to 30 / xm. These polymer films can be laminated on both sides of the photosensitive layer as a support film for one photosensitive layer and another as a protective film for the photosensitive layer.
  • the prepared photosensitive resin composition is uniformly applied on the polymer film of the support film, and then the solvent is removed by heating and spraying with Z or hot air to form a dry film.
  • the thickness of the dry film is not particularly limited, and is preferably from 10 to 100 / m, more preferably from 20 to 60 tm.
  • the photosensitive film of the present invention comprising two layers, a photosensitive layer and a polymer film, obtained as described above, is wound up in a roll form as it is or by further laminating a protective film on the other surface of the photosensitive layer. Can be stored.
  • the photosensitive resin composition and the photosensitive film of the present invention are particularly useful as etching resists for flexible printed wiring boards and resists such as solder resists, and can also be used as paints, coating agents, adhesives, and the like.
  • the printed wiring board of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, a film thickness of 5 to 160 m is applied to a printed wiring board by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like.
  • a tack-free coating film By applying the resin composition of the present invention at a temperature of 60 to 110 ° C., preferably at a temperature of 60 to 100 ° C., a tack-free coating film can be formed. After that, a photo with an exposure pattern such as a negative film The mask is brought into direct contact with the coating (or placed on top of the coating in a state where it does not come into contact with the coating) and irradiated with ultraviolet light at an intensity of about 10 to 200 mJ / cm. The unexposed portion is developed using a developing solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like.
  • a printed wiring board having a permanent protective film that satisfies various characteristics such as heat resistance, solvent resistance, acid resistance, adhesion, and electrical characteristics of the film can be obtained.
  • organic solvent used in the development examples include octogens such as trichloroethane, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; 1,4-dioxane; Ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone; lactones such as carb tyrolactone; butyl acetate sorb acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate Alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; petroleum solvents such as petroleum ether and petroleum naphtha; water and alkaline aqueous solutions such as potassium hydroxide and sodium hydroxide; , Sodium carbonate , Potassium carbonate, sodium phosphate, Gay acid sodium, ammoni
  • the protective film is removed, and then the photosensitive film is pressure-bonded to the substrate while heating. By doing so, they can be laminated. At this time, it is preferable to laminate under reduced pressure.
  • the surface to be laminated is not particularly limited, and is preferably an FPC on which wiring is formed by etching or the like.
  • the heating temperature of the light-sensitive layer is not particularly limited, and is preferably 90 to 130 ° C.
  • the pressing pressure is not particularly limited, and the pressing is preferably performed under reduced pressure.
  • the photosensitive layer thus laminated is brought into direct contact with a photomask having an exposure pattern such as a negative film or the like (or placed on the coating film in a state where the photomask is not in contact with the photomask). Irradiate at an intensity of about 0 mJ / cm.
  • the polymer film present on the photosensitive layer is transparent, it can be exposed as it is, but if it is opaque, it must be removed.
  • the polymer film is preferably transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining.
  • Suitable light sources for photocuring include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps.
  • a laser beam or the like can also be used as active light for exposure.
  • the polymer film is removed and then removed by a known method such as spraying, rocking immersion, and brushing using the developing solution. The exposed portion can be removed for development.
  • a printed wiring board having a permanent protective film that satisfies various properties such as heat resistance, solvent resistance, acid resistance, adhesion, and electrical properties of the resist film can be obtained.
  • a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (product name: ZX-1059, manufactured by Toto Kasei Co., Ltd.) is placed in a round bottom flask equipped with a stirring device and a condenser tube. g, 72.06 g of acrylic acid, 1.2 g of triphenylphosphine and 0.24 g of methoxyphenol, heated to 60 ° C and dissolved, reacted at 98 ° C for 24 hours, and reacted with an acid value of 0. A polyunsaturated polyol (c 2) having a concentration of 3 mgK ⁇ HZg was obtained.
  • compositions were blended according to the blending composition shown in Table 1 (the numerical values are parts by weight) and kneaded with a three-roll mill. This is printed on a copper-clad polyimide film substrate (copper thickness / 12 m ⁇ polyimide) by using a 100 mesh polyester screen to form a pattern with a thickness of 20 to 30 m by screen printing. The whole thickness was applied to a film thickness of Z25 // m), and the coating film was dried with a hot air dryer at 80 ° C for 30 minutes.
  • Table 1 the numerical values are parts by weight
  • a negative film having a resist pattern was brought into close contact with the coating film, and irradiated with ultraviolet rays (exposure amount: 500 mJZcm 2 ) using an ultraviolet exposure apparatus (Oak Works, Model HMW—680 GW).
  • the film was developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kgZcm 2 to dissolve and remove unexposed portions.
  • the obtained product was evaluated for developability and light sensitivity as described below.
  • test method and evaluation method are as follows.
  • the dried coating film was stuck to Step 1 Bullet 21 (manufactured by Stoffer Co., Ltd.) and exposed to ultraviolet light having an integrated light amount of 500 mJZcm 2 . Then 60 seconds with a 1% carbonate aqueous sodium, 2. development at a spray pressure of 0 k gZc m z, to confirm the number of the remaining coating film without being developed.
  • test piece was immersed in isopropyl alcohol at room temperature for 30 minutes. After confirming that there were no abnormalities in the appearance, a peeling test was performed using cellophane tape and evaluated according to the following criteria.
  • test piece was immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there were no abnormalities in the appearance, a peeling test was performed using cellophane tape and evaluated according to the following criteria.
  • a rosin-based flux was applied to the test piece and immersed in a solder bath at 260 ° C for 5 seconds. This was taken as one cycle and repeated three cycles. After allowing to cool to room temperature, a peeling test was performed using a cellophane and evaluated according to the following criteria.
  • the measurement was performed according to JISK5016.
  • the radius of curvature of the bent surface was 0.38 mm, and the number of bendings before cracking was measured.
  • KAYARAD Z BR— (trade name): Bisphenol A-type epoxy acrylate (trade name, manufactured by Nippon Kayaku Co., Ltd.) Acid) and succinic anhydride, containing 24.5% by weight of carbitol acetate and 10.5% by weight of solvent naphtha, and the acid value of the solid is 10 OmgKOHZg .
  • KAYARAD DPHA (trade name): Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pen pen and hexaacrylate
  • Irgacure-1 907 (trade name): Ciba-Geigy-1 Co., Ltd., photopolymerization initiator, 2-methyl- [4- (methylthio) phenyl] _2-morpholinol-1-propanone
  • KAYACURE DETX—S (trade name): Nippon Kayaku Co., Ltd., photopolymerization initiator, 2,4-getylthioxanthone
  • KAYACURE BMS (trade name): Nippon Kayaku Co., Ltd., photopolymerization initiator, 4-benzoyl-4'-methylphenyl sulfide
  • EXA-4800 (trade name): Bisphenol S-type epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.
  • the photosensitive resin composition containing the materials shown in Table 2 was applied to a printed circuit board (a copper foil laminated on an imide film) by screen printing and dried at 80 ° C for 20 minutes. Then, a negative film is applied to this substrate, and irradiated with ultraviolet light at an integrated exposure amount of 500 mJ / cm 2 using an exposure machine according to a predetermined pattern, and an organic solvent or a 1 wt% Na 2 CO 3 aqueous solution is applied.
  • the test substrate was prepared by heat hardening at 150 ° C for 50 minutes. With respect to the obtained test substrate, properties of alkali developability, solder heat resistance, flexibility, heat deterioration resistance, and electroless plating resistance were evaluated. Table 2
  • the coating film was dried at 80 ° C for 60 minutes, and the developability by spray development with a 1% aqueous sodium carbonate solution at 30 ° C was evaluated.
  • a rosin-based flux was applied to the test substrate, immersed in molten solder at 260 ° C for 10 seconds, and evaluated by the state of the cured film when peeled off with a cellophane adhesive tape.
  • test substrate was plated as described below, it was judged by the state when it was peeled off with a cellophane adhesive tape.
  • Electroless gold plating method Dip the test substrate in a 30 ° C acidic degreasing solution (20 vol% aqueous solution of Metex L-5B, manufactured by Nippon MacDermid Co., Ltd.) for 3 minutes to degrease, and then run in running water For 3 minutes and washed with water. Next, the test substrate was immersed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes, soft-etched, and then immersed in running water for 3 minutes and washed with water.
  • the test substrate was immersed in a 10 V o 1% sulfuric acid aqueous solution at room temperature for 1 minute, immersed in running water for 30 seconds to 1 minute, and washed with water.
  • the test substrate was immersed in a 30 ° C catalyst solution (Meltex Co., Ltd., Metal Plate Activator, 350 lO vol% aqueous solution) for 7 minutes, and the catalyst was applied. It was immersed in a 3 vol% aqueous solution, pH 4.6) for 20 minutes to perform electroless nickel plating.
  • a 10 V o 1% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water.
  • the test substrate is immersed in a 95 ° C gold plating solution (meltex, Co., Ltd., no ore hole opening UP 15 Vo 1% and potassium cyanide 3 Vo 1% aqueous solution, pH 6) for 10 minutes.
  • a 95 ° C gold plating solution (meltex, Co., Ltd., no ore hole opening UP 15 Vo 1% and potassium cyanide 3 Vo 1% aqueous solution, pH 6) for 10 minutes.
  • electroless gold plating it was immersed in running water for 3 minutes and washed with water, and immersed in warm water of 60 ° C for 3 minutes and washed with hot water. After thorough washing with water, the water was thoroughly removed, dried, and a test board with electroless gold plating was obtained.
  • the photosensitive resin composition of the present invention exhibits good alkali developability, and is excellent in heat resistance, flexibility, heat deterioration and electroless gold plating resistance. Give the membrane.
  • the photosensitive resin composition of the present invention has good workability, is excellent in flexibility and solder heat resistance, and is suitable for a photosensitive film for an etching resist for FPC and a coverlay.

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Abstract

Cette invention concerne une composition à base de résine convenant comme résist à l'attaque acide et comme couche de couverture pour plaquettes de circuit imprimé ; une composition de résine photosensible renfermant cette composition ; un film comprenant un support sur lequel est superposé un film de la composition de résine photosensible ; un produit polymérisé obtenu par traitement de la composition à base de résine ; et un article, tel qu'une plaquette de circuit imprimé, comportant une couche du produit polymérisé. Cette composition à base de résine comprend (A) un oligomère que l'on obtient en faisant réagir (a) une résine époxy comptant deux groupes époxy par molécule avec (b) un acide monocarboxylique comptant une double liaison insaturée unique et un groupe carboxyle par molécule pour obtenir (c) un composé polyol insaturé, et en faisant réagir le composé (c) avec (d) un composé diamine et (e) un anhydride acide polybasique comptant au moins deux groupes anhydride acide par molécule. Le film qui comporte une couche de la composition de résine photosensible, peut être développé au moyen d'une solution d'alcali dilué, présente une aptitude au façonnage satisfaisante et permet d'obtenir une pellicule polymérisée excellente en termes de souplesse et de résistance à la soudure chaude.
PCT/JP2001/000024 2000-01-12 2001-01-05 Composition a base de resine, produit polymerise obtenu a partir de cette composition et article realise avec cette composition WO2001051991A1 (fr)

Applications Claiming Priority (4)

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JP2000/3681 2000-01-12
JP2000003681A JP2001192431A (ja) 2000-01-12 2000-01-12 樹脂組成物、その硬化物及び物品
JP2000264783A JP2002072470A (ja) 2000-09-01 2000-09-01 感光性樹脂組成物、及びこれを用いた感光性フイルム
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005061586A1 (fr) * 2003-12-22 2005-07-07 Nippon Kayaku Kabushiki Kaisha Resine d'acide polyamide contenant un groupe insature, composition de resine photosensible l'utilisant et produit durci obtenu avec ces resines
JP2017122912A (ja) * 2016-01-06 2017-07-13 Jnc株式会社 感光性組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134390A (ja) * 1994-09-13 1996-05-28 Nippon Kayaku Co Ltd フレキシブルプリント配線板用レジストインキ組成物及びその硬化物
JPH10330481A (ja) * 1997-03-31 1998-12-15 Hitachi Chem Co Ltd 親水性ポリアミド系樹脂の製造法
JPH11288087A (ja) * 1998-04-03 1999-10-19 Hitachi Chem Co Ltd 感光性樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134390A (ja) * 1994-09-13 1996-05-28 Nippon Kayaku Co Ltd フレキシブルプリント配線板用レジストインキ組成物及びその硬化物
JPH10330481A (ja) * 1997-03-31 1998-12-15 Hitachi Chem Co Ltd 親水性ポリアミド系樹脂の製造法
JPH11288087A (ja) * 1998-04-03 1999-10-19 Hitachi Chem Co Ltd 感光性樹脂組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005061586A1 (fr) * 2003-12-22 2005-07-07 Nippon Kayaku Kabushiki Kaisha Resine d'acide polyamide contenant un groupe insature, composition de resine photosensible l'utilisant et produit durci obtenu avec ces resines
JPWO2005061586A1 (ja) * 2003-12-22 2008-04-17 日本化薬株式会社 不飽和基含有ポリアミド酸樹脂及びそれを用いた感光性樹脂組成物並びにその硬化物
JP4686364B2 (ja) * 2003-12-22 2011-05-25 日本化薬株式会社 不飽和基含有ポリアミド酸樹脂及びそれを用いた感光性樹脂組成物並びにその硬化物
KR101041958B1 (ko) * 2003-12-22 2011-06-16 니폰 가야꾸 가부시끼가이샤 불포화기 함유 폴리아미드산 수지 및 그것을 이용한 감광성수지 조성물 및 그 경화물
JP2017122912A (ja) * 2016-01-06 2017-07-13 Jnc株式会社 感光性組成物

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