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WO2002094904A1 - Resine photosensible, compositions de resine photosensible contenant cette resine, et articles durcis comprenant ces compositions - Google Patents

Resine photosensible, compositions de resine photosensible contenant cette resine, et articles durcis comprenant ces compositions Download PDF

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Publication number
WO2002094904A1
WO2002094904A1 PCT/JP2002/004700 JP0204700W WO02094904A1 WO 2002094904 A1 WO2002094904 A1 WO 2002094904A1 JP 0204700 W JP0204700 W JP 0204700W WO 02094904 A1 WO02094904 A1 WO 02094904A1
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WO
WIPO (PCT)
Prior art keywords
compound
epoxy
molecule
soluble
acid
Prior art date
Application number
PCT/JP2002/004700
Other languages
English (en)
Japanese (ja)
Inventor
Ryutaro Tanaka
Hiroo Koyanagi
Toru Ozaki
Minoru Yokoshima
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 JP2001147218A external-priority patent/JP2002338652A/ja
Priority claimed from JP2001348344A external-priority patent/JP3846856B2/ja
Priority claimed from JP2001355269A external-priority patent/JP2003155320A/ja
Priority claimed from JP2002068347A external-priority patent/JP2003268067A/ja
Application filed by Nippon Kayaku Kabushiki Kaisha filed Critical Nippon Kayaku Kabushiki Kaisha
Publication of WO2002094904A1 publication Critical patent/WO2002094904A1/fr

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Classifications

    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • 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

Definitions

  • Photosensitive resin photosensitive resin composition using the same, and cured product thereof
  • the present invention relates to an aqueous solution of an alkaline aqueous solution of a polyurethan compound (F), a photosensitive resin composition using the same, and a cured product thereof, and more particularly, to a flexible printed wiring board.
  • a polyurethan compound F
  • a photosensitive resin composition using the same, and a cured product thereof, and more particularly, to a flexible printed wiring board.
  • solder resist, plating resist, interlayer insulating film for multilayer printed wiring board, photosensitive optical waveguide, etc. developability, flexibility, flame retardancy, electrical insulation
  • the present invention relates to a resin composition that gives a cured product having excellent properties, adhesion, solder heat resistance, chemical resistance, and plating resistance, and a cured product thereof.
  • the solder resist of some commercial printed wiring boards and most industrial printed wiring boards includes a post-exposure and development process from a high-precision and high-density viewpoint.
  • Liquid development type solder resists are used to form images and to finish and cure by heat and light irradiation. I have.
  • liquid solder resists which are of a developer type using a dilute aqueous alkali solution as a developer, have become mainstream. Examples of such an alkaline development type solder resist using a dilute aqueous alkaline solution include, for example, Japanese Patent Application Laid-Open No. 61-243,695 discloses a novolak type epoxy.
  • a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a resin and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy resin is disclosed.
  • this composition is rigid and does not have flexibility. Therefore, in Patent Publication No. 2001-169398, after reacting an ethylenically unsaturated oligomer with a bisphenol A-type epoxy compound, the diisocyanate is reacted.
  • a method for producing a photo-toe-major composition containing a flexible oligomer, which is characterized by reacting with a compound, is proposed. Problems to be solved by the invention
  • Printed circuit boards are required to have high precision and high density in order to reduce the size and weight of mobile devices and improve communication speed.
  • requirements for solder resists have become increasingly sophisticated, and flame resistance, substrate adhesion, and high flexibility have been maintained while maintaining more flexibility than conventional requirements.
  • Performance that can withstand insulation and electroless gold plating is required, and the solder resists currently on the market cannot sufficiently meet these requirements.
  • the purpose of the present invention is to form fine images that can respond to the high performance of printed wiring boards today, have excellent photosensitivity to active energy, and be suitable for development with dilute aqueous solutions.
  • An object of the present invention is to provide a resin composition suitable for a solder resist ink having excellent electroless gold plating resistance and a cured product thereof. Disclosure of the invention
  • Compound (A) Epoxy having two epoxy groups in the molecule An epoxy carboxylate compound obtained by reacting the compound (a) with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule;
  • Compound (C) a carboxylic acid compound having two hydroxyl groups in the molecule
  • Compound (D) a diol compound other than compound (A) and compound (C);
  • Compound (E) an epoxy compound having an ethylenically unsaturated group in the molecule
  • Epoxy carboxylate obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule Compounds (A), diisocyanate compounds (B) and carboxylic acid compounds having two hydroxyl groups in the molecule
  • (C) is characterized by reacting (C) A process for producing a soluble aqueous solution of a polyurethan compound (F);
  • Epoxy carboxy obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule After reacting a silicate compound (A), a dissocyanate compound (B), and a carboxylic acid compound having two hydroxyl groups (C) in the molecule, an ethylenic compound is reacted in the molecule.
  • An epoxy compound (a) having two epoxy groups in the molecule is a phenyldiglycidyl ether compound, a bisphenol type epoxy compound, or a hydrogenated bisphenol type epoxy compound.
  • Monocarbonic oxide compound (b) having an ethylenically unsaturated group in the molecule contains (meth) acrylic acid, (meth) acrylic acid and ⁇ .
  • the diisocyanate-dye compound ( ⁇ ) can be used as a frenzy-isocyanate, a tri-renge-isocyanate, a xylylene-isocyanate, or a tetramethylsilyl- Range sociate, diphenylmethansiate, naphthalene sociate, tridiene sociate, hexamethylene sociate, dicyclohexylene mesyane To the sociate, iso-holiogenic societies, arylene sulfone sociate, allily cyane sociate, N-silicone sociate, trimethyl Kisamethylene diisocynate, 1,3—bis (isosocyanate methyl) cyclohexane, and norbornane diisocynate methyl
  • a soluble aqueous solution of an alkaline polyurethan compound (F) according to any one of (1) or (6) to (8), which is a compound;
  • a diol compound (D) other than compound (C) is a butadiene acrylonitrile copolymer having a terminal hydroxyl group, a spiroda alcohol having a terminal hydroxyl group, A diol compound selected from the group consisting of dioxandacolol having a hydroxyl group at the end, tricyclodecanedimethanol having a hydroxyl group at the end, and a macromolecule having a hydroxyl group at the end.
  • the soluble poly (urethane) compound (F) according to any one of (10);
  • (E) is an epoxy compound selected from the group consisting of glycidyl (meta) acrylate and glycidylcinnamic acid, (1) or (6) to (11) )
  • the soluble polyurethan compound (F) according to any one of the above,
  • a photosensitive resin composition comprising the aqueous alkali soluble soluble polyurethane compound (F) according to any one of (1) or (6) to (13);
  • the photosensitive resin composition according to (14) is combined with an aqueous solution of an alkali aqueous solution-soluble polyurethane compound (F), a photopolymerization initiator (G), a crosslinking agent (H), and optional components.
  • a photosensitive resin composition characterized by containing a curing component (I) by heating;
  • the alkaline aqueous solution soluble polyurethan compound (F) of the present invention comprises the above compound (A), iridani compound (B), iridani compound (C), and compound (D) as an optional component. ), which is obtained by reacting the compound (E).
  • the epoxy compound (a) having two epoxy groups in the molecule used for producing the alkali aqueous solution-soluble polyurethane compound (F) of the present invention has an epoxy equivalent of 100 to 100 in particular. It is desirable that the epoxy compound (a) be 900 g / equivalent. If the epoxy equivalent is less than 100, the molecular weight of the obtained aqueous alkali sol- ble polyurethan compound (F) will be small, and it may be difficult to form a film. If the epoxy equivalent is more than 900, the introduction ratio of monocarboxylic acid (b) having an ethylenically unsaturated group may be low, and the photosensitivity may be reduced. May decrease.
  • epoxy compound having two epoxy groups in the molecule include, for example, quinone diglycidyl ether of a lip opening, alcohol diglycidinol ether, and rosin regino glycidinol ether.
  • Etc. such as phenyl jigs
  • A-type epoxy resin bisphenol _ F-type epoxy resin, bisphenol-1 S-type epoxy resin, 2,2-bis (4-hydroxyphenyl) 1 1, 1, 1, 1, 3, 3, 3 — Bisphenolic epoxy compounds such as epoxy compounds of hexafluoropropane, etc.
  • Hydrogenated bisphenol A type epoxy resin Hydrogenated bisphenol F-type epoxy resin, Hydrogenated bisphenol F-type epoxy resin, hydrogenated bisphenol-S-epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) 1,1,1, 1,3,3,3_Hexafluoropropane epoxy conjugates, etc., hydrogenated bisphenol-type epoxy compounds, brominated bisphenol A type epoxy resin, bisbrominated bis Bisphenol-type epoxy compounds such as phenol F-type epoxy resins Kisa Njime data Roh Rujigu glycidyl ether compounds such as alicyclic jig glycidyl ether compounds in the mouth, 1, 6 - to Kisanjio Norejigu glycidyl ether, 1, 4 one pig Njiorujigu Li Siji Aliphatic diglycidyl ether compounds, such as polyether, diethyl glycol, diglycidyl ether, polysulfide-type diglycidyl ether compounds, etc.,
  • Epomic R — 140 Epomic R — 301
  • Epomic R — 30 4 all made by Mitsui Chemicals
  • DDR-331 DDR_332, DDR-324 (the gap is also made by Dow Chemical Co.)
  • Epicron 840 Bisphenols such as Picron 850 (both made by Dainippon Ink), UVR-640 (manufactured by Union Carbide), YD-81250 (manufactured by Toto Kasei) -A type epoxy resin, UVR-6490 (manufactured by Union Carbide), YDF-201, YDF-204, YDF-8170 (all of which are Tokyo Metropolitan Chemicals) Epiclon 830, Epicron 835 (any Bisphenol F-type epoxy resin such as Dainippon Ink), HBPA — DGD (Mar
  • the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule used for producing the aqueous alkali soluble compound (F) of the present invention is, for example, Examples include lylic acids, crotonic acid, ⁇ -cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monodalicidyl compound.
  • Acrylic acids include, for example, (meta) acrylic acid,] 3—styrylacrylic acid, 3_furfurylacrylic acid, Half-esters, which are equimolar reactants of saturated or unsaturated dibasic acid anhydrides and (meta) acrylate derivatives having one hydroxyl group in one molecule, saturated or unsaturated dibasic Examples include half-esters, which are equimolar reactants of an acid and a monoglycidyl (meth) acrylate derivative.
  • Particularly preferred are ta) acrylic acid, the reaction product of (meth) acrylic acid with ⁇ -force prolatatone or cinnamic acid.
  • the diisocyanate compound ( ⁇ ) used for producing the aqueous alkaline solution soluble polyurethan compound (F) of the present invention is one having two isocyanate groups in the molecule. All of them can be used, and a plurality of diisocynate compounds can be reacted at the same time.
  • diisocyanate compounds ( ⁇ ) which are particularly excellent in heat resistance or flexibility, such as phenylene succinate, tri-lensie succinate, and xylene multitudenate , Tetramethylsilicone zonate, diphenylmethanine zonate, naphthalene zonate, tridentene zonate, hexamethylene zonate, hexine Mouth Hexinolate Soynate, Isoholonite Isolate-Alienware Sociate, Alicia cyanide sineate, N-silyl thiocyanate, trimethyl hex methyl thiocyanate, 1, 3-bis (isocyanate methyl) Hexane or norbornane succinate methyl is preferred.
  • an alcohol in the molecule may be used. Any diol compound having a functional hydroxyl group or a phenolic hydroxyl group and a carboxyl group at the same time can be used, but an alcoholic hydroxyl group having an excellent aqueous solution aqueous solution is particularly preferred. Further examples include diol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid.
  • Examples of the diole compound (D) other than the compound (A) used for producing the aqueous alkali soluble compound (F) of the present invention (F) and the disulfide compound (C) include: Any aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms can be used, such as ethylene glycol, propylene glycol, and trimethyl.
  • the epoxy compound (E) having an ethylenically unsaturated group in the molecule used for producing the alkaline aqueous solution-soluble polyurethan compound (F) of the present invention includes an ethylenically unsaturated group. Any of the epoxy compounds used can be used, but glycidyl (meta) acrylate and glycidyl cinnamic acid are preferred.
  • the production of the aqueous alkali-soluble polyurethan compound (F) of the present invention comprises the aforementioned epoxy compound (a) and the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule.
  • the epoxycarboxylate compound (A) in which an alcoholic hydroxyl group has been formed by the reaction (hereinafter referred to as the first reaction) and the carboxylic acid compound (C) having two hydroxyl groups in the molecule are diisolated. It can be obtained by urethanation reaction (hereinafter referred to as the second reaction) with the cyanate compound (B).
  • the alkaline aqueous solution-soluble polyurethane compound (F) of the present invention is an epoxycarboxylate compound (A) in which an alcoholic hydroxyl group formed by the first reaction is formed, and two of the compounds are present in the molecule.
  • the carboxylic acid compound having a hydroxyl group (C), and the diol compound (D) other than the compound (A) and the compound (C) are urethanized with the diisocyanate compound (B) (hereinafter referred to as the third reaction). You can also get it.
  • the epoxy compound (E) having an ethylenically unsaturated group in the molecule can be obtained by dissolving the aqueous alkaline solution of an alkali aqueous solution (F) of the present invention. It can also be obtained by a reaction (hereinafter referred to as a fourth reaction).
  • the first reaction is carried out without a solvent or a solvent having no alcoholic hydroxyl group, specifically, ketones such as, for example, acetone, ethylmethylketone, and cyclohexanone.
  • Aromatic hydrocarbons such as benzene, benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol, ethylene glycol, ethyl alcohol, ethylene glycol, ethylene glycol, etc.
  • Glossy items such as Lengg Recon Retinole, Ginro Plein Glen Reco Reine Reinole, Trie Leng Re Gino Reno Reine Reinole Cole ethers, ethinole acetate, butyl acetate, methinocello sonolebut acetate, etinolaceo sonole acetate Esters such as petitnocellosolve acetate, carbitol acetate, propylene glycol monomethine oleate enorea acetate, dianolequinole gnoolenoate, dialkyl succinate, dialkyl succinate, y—petit In a cyclic ester such as ratatotone, a petroleum solvent such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, sorbent naphtha, and a single or mixed organic solvent such as a crosslinking agent (H) described later.
  • H crosslinking agent
  • the ratio of the raw materials charged in this reaction is determined by the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule.
  • the amount of the catalyst used is 0.1 to 10 weight based on the reactants. /. It is.
  • the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
  • the catalyst to be used include, for example, triethylamine, benzyldimethylaminoamine, triethynoleammonium chloride, and benzylol trimethylaminemonomer promoter.
  • Iodine benzoin trimethylene monadium iodide, trirefinolephosphine, triphenylenolistobin, methinolate triphenylene Norestibine, chrome octoate, zirconium octoate and the like can be mentioned.
  • thermal polymerization inhibitors hydroquinone monomethyl ether, 2-methylethyl hydroquinone, hydroquinone, diphenylpicryl hydrazine, diphthine It is preferable to use enoreamin, 3, 5-jitter-leptyl 4-hydroxytoluene.
  • the first reaction should be terminated when the oxidation of the sample is less than lmg 'KO HZ g, preferably less than 0.5 mg ⁇ KOH / g, while sampling as appropriate.
  • the above-mentioned carboxylic acid compound having two hydroxyl groups (C) is added to the reaction solution to form a dispersion or a solution.
  • This is a urethanization reaction in which the diisocyanate compound (B) is gradually added and reacted.
  • the reaction can be carried out without a catalyst, but a basic catalyst can be used to promote the reaction.
  • the amount of the catalyst used is 10% by weight or less based on the reactants. It is.
  • the reaction temperature is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours. In this case, a solvent or a thermal polymerization inhibitor as described above may be used.
  • the end point of the second reaction is a point in time when the absorption near 225 cm 1 in the infrared absorption spectrum of the sample disappears while sampling as appropriate.
  • a carboxylic acid compound (C) having two hydroxyl groups in the molecule and a diol compound other than the compound (A) and the compound (C) are added to the reaction solution.
  • the reaction can be carried out without a catalyst, but a basic catalyst can be used to promote the reaction.
  • the amount of the catalyst used is 10% by weight with respect to the reactants. / 0 or less.
  • the reaction temperature is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.
  • a solvent or a thermal polymerization inhibitor as described above may be used.
  • the end point is the time point at which the absorption around 225 cm- 1 in the infrared absorption spectrum of the sample disappears while sampling as appropriate.
  • an epoxy compound (E) having an ethylenically unsaturated group in a molecule is added to the reaction solution to form a dispersion or a solution.
  • This is an epoxyacrylate reaction with a carboxylic acid compound (C) having two hydroxyl groups in the molecule described above.
  • the reaction can be carried out without a catalyst, but a basic catalyst can be used to accelerate the reaction.
  • the amount of the catalyst used is 10% by weight with respect to the reactants. / 0 or less.
  • the reaction temperature at this time is 40 to 120 ° C, and the reaction time is preferably 5 to 120 ° C. 60 hours.
  • a solvent or a thermal polymerization inhibitor as described above may be used.
  • the carboxylic acid compound (C) having two hydroxyl groups in the molecule is the solid content acid value of the aqueous alkali-soluble polyurethan compound (F) of the present invention. Is calculated to be 50 to 150 ing ⁇ K ⁇ HZ g, and the diisocyanate compound (B) is converted into the compound (A) by the number of moles of the compound (A) in the second reaction.
  • the charge is performed so that the ratio of (moles) / (moles of compound (B)) is in the range of 1 to 5. If this value is less than 1, the isocyanate will remain at the end of the aqueous alkali soluble compound (F) of the aqueous alkali solution of the present invention, resulting in low heat stability and during storage. It is not preferred because it may gel.
  • the molecular weight of the soluble aqueous solution of the polyurethan compound (F) will be low, resulting in tackiness and low sensitivity. There is fear. If the solid acid value is less than 50 mgKOH / g, If the solubility is insufficient and the patterning is performed, it may remain as a residue, or in the worst case, the patterning may not be possible. On the other hand, when the solid acid value is more than 150 mg′KOHZ g, the solubility in an aqueous alkali solution becomes too high, and the photocured pattern may be undesirably peeled off.
  • the polyurethan compound (F) of the present invention thus obtained can be isolated by using a solvent and removing it by an appropriate method. However, when used as a photosensitive resin composition, it can often be used without removing the solvent.
  • the polyurethane compound (F) of the present invention is usually soluble in an aqueous alkali solution, but is also soluble in the above-mentioned solvents, and is used for a solder resist, a plating resist, and the like. In this case, development with a solvent is also possible.
  • the solubility in an aqueous solution of alkaline metal was insufficient, and patterning was performed. In such a case, there is a risk of remaining as a residue, and in the worst case, patterning may not be possible. If the solid acid value is more than 150 mgKOH / g, the solubility in alkaline aqueous solution is too high, and the photocured pattern is peeled off. It is not preferable because it may be separated.
  • the photosensitive resin composition of the present invention comprises, as an optional component, a curing component (I) which is an optional component of the above aqueous solution soluble polyurethane compound (F), a photopolymerization initiator (G), and a crosslinking agent (H). It is characterized by containing.
  • a curing component (I) which is an optional component of the above aqueous solution soluble polyurethane compound (F), a photopolymerization initiator (G), and a crosslinking agent (H). It is characterized by containing.
  • the content ratio of the above-mentioned water-soluble and water-soluble polyurethan compound (F) used in the photosensitive resin composition of the present invention is 100% by weight of the solid content of the photosensitive resin composition. / 0 , usually 15 to 70 weight. / 0 , preferably 20 to 60 weight. / 0 .
  • the photopolymerization initiator (G) used in the light-sensitive resin composition of the present invention include, for example, benzoin, benzoin methyl ether, benzene Benzoins, such as benzoin cinnole and benzoin lip, benzoin lip, benzoin, etc .; acetophenonone, 2,2—die Toxi 2-Ferro-acetophenone, 1, 1-Dichloroacetophenone, 2-Hydroxy 1-2-Methi-no-phenyl 1-on, 1-hydroxy-phenoxy, 1-hydroxycyclohexyl phenyl ketone, 2—methyl 1- [4- Phenylthio) phenyl]-2-morpholinopropane-1 1-on and other acetate phenones; 2- Rua down door La-board down, 2 - Turn-sheet catcher Li one-flops Cilaanthraquinone, 2—Cross mouth anthraquinone, 2—Amilanth
  • tertiary amines such as triethanolamine, methyljetanolamine, N, N-dimethylamine, and the like. It can be used in combination with accelerators such as benzoic acid derivatives such as aminobenzoyl ester, N, N—dimethylaminobenzoic acid isoamyl ester. it can.
  • the amount of these accelerators to be added is preferably 100% or less with respect to the photopolymerization initiator (G).
  • cross-linking agent (H) used in the photosensitive resin composition of the present invention include, for example, 2—hydroxyshetyl (meta) acrylate, 2—hydroxy Cipropill (meta) acrylate, 1,4-butanediol (meta) acrylate, canole bitonole (meta) acrylate, acrylate morpho Phosphorus, hydroxyl-containing (meta) acrylates (for example, 2—hydroxy shetyl (meta) acrylate, 2—hydroxypropyl (meta) acrylate, 1, 4 — butanediol mono (meta) acrylate, etc.
  • oleic acid compounds eg, succinic anhydride, maleic anhydride, phthalic anhydride, Trahydro phthalic anhydride, Hexahydroanhydride Talic acid, etc.
  • half-ester polyethylene glycol (meta) acrylate, tripropylene glycol (meta) acrylate, Trimethylo Repro No. II.
  • Trimetries (meta) acrylates, trimethylol propane acrylates (meta) acrylates, glycerine proxies Di (meta) acrylate, ⁇ -caprolactone adduct di (meta) acrylate of hydroxypentivalate neopentynoleglycol (For example, KAYARADHX-220, HX-620, etc., manufactured by S Hon Kayaku Co., Ltd.), pentaerythritol tetra (meta) acrylate, Poly (meta) acrylate, dipenta erythritol poly (meta) acrylate of the reaction product of pentae.
  • mono- or polyglycidyl compounds e.g., butyl daricidyl ether, phenylglycidyl ether, polyethylene glycol glycol diglycidyl ether, polypropylene
  • It is a reaction product of (meth) atalinoleic acid with sidyl ether, trimethylolpropane polyglycidyl ether, trimethylolone propane polyethoxypolyglycidyl ether, etc.
  • Epoxy (meta) acrylate, etc. may be, when the solid content of the photosensitive resin composition is 100% by weight, usually 2 to 4 0 weight ./., is rather than the preferred, Ru 5-3 0 weight 0/0 der.
  • the curing component (I) as an optional component used in the photosensitive resin composition of the present invention includes, for example, an epoxy compound, an oxazine compound and the like. Are mentioned.
  • the curable component (I) reacts with the carboxyl group remaining in the resin film after photocuring by heating to obtain a cured film having stronger chemical resistance. It is particularly preferably used.
  • epoxy compound used for the curing component (I) examples include phenolic novolak type epoxy resin, cresol'novolak type epoxy resin, and tris. Hydroxyphenyl methane epoxy resin, penta-gen phenol epoxy resin with epoxy resin, bisphenol A-type epoxy resin, bisphenol-F epoxy resin Resin, biphenol-type epoxy resin, bisphenol-one-block epoxy resin, naphthalene skeleton-containing epoxy resin, heterocyclic epoxy resin, etc. Can be
  • phenol novolak epoxy resins examples include Epiclon N-770 (manufactured by Dainippon Ink & Chemicals, Inc.) and D.D. N 438 (manufactured by Dow Chemical Co., Ltd.), Epiccoat 154 (manufactured by Yudani Sheraepoxi Co., Ltd.), RD-306 (Nippon Kayaku ( Co., Ltd.).
  • cresol novolac epoxy resins examples include Epiclon N—695 (manufactured by Dainippon Ink and Company Inc.) and DOCN—1 0 2 S, DOCN — 1 0 3 S, D OCN — l04S (manufactured by Nippon Kayaku Co., Ltd.), UVR — 660 (manufactured by Nyuon Carpide Co., Ltd.), DSCN —195 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.
  • Examples of the tris-hydroxy phenylmethane epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (Nippon Kayaku Co., Ltd.) ), TACTIX — 742 (manufactured by Dow Chemical Company), Epiccoat D1032H60 (manufactured by Yudani Chele Poxy Co., Ltd.), and the like.
  • Examples of the dicyclopentagen phenol type epoxy resin include Epiclon DXA_720 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and TACTIX—556 (Dow Chemical Co., Ltd.).
  • bisphenol-type epoxy resins include, for example, Epicoat 8288, Epicoat 101 (made of oil-based chenole epoxy), UVR — 640 (Union Car Bisphenol A-type epoxy resin such as B.D.), D.D.R-331 (Dow Chemical), YD-812.5 (Toto Kasei). And bisphenol-F type epoxy resin such as UVR-640 (manufactured by Union Carbide) and YDF-817 (manufactured by Toto Kasei).
  • biphenol type epoxy resin for example, NC — 30 Biphenol-type epoxy resin such as 00P, NC-30000S (produced by Nippon Kayaku Co., Ltd.), and vixylene resin of YX-400 (produced by Yuka Shell Epoxy Co., Ltd.) Epoxy resin, YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like.
  • the bisphenol A epoxy resin include epoxylone N-880 (manufactured by Dainippon Ink and Chemicals, Inc.) and epicoat D157S7. '5 (manufactured by Yuka Shell Epoxy Co., Ltd.).
  • Examples of the epoxy resin having a naphthalene skeleton include NC-700 (manufactured by Nippon Kayaku Co., Ltd.) and DXA-470 (manufactured by Nippon Ink Chemicals Co., Ltd.) And the like.
  • Examples of the alicyclic epoxy resin include DHPD_315 (manufactured by Daicel Chemical Industries, Ltd.).
  • Examples of the heterocyclic epoxy resin include TDPIC, TDPIC-L, TDPIC_H, and TDPIC-S (all manufactured by Nissan Chemical Industries, Ltd.).
  • oxazine compound used for the curing component (I) include, for example, B-m-type benzoxazine, P-a-type benzoxazine, B-a-type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.) ).
  • the addition ratio of the curing component (I) is as follows.
  • the amount is preferably 200% or less of the equivalent calculated from the solid content acid value of the liquid soluble polyurethane compound and the amount used. When the amount exceeds 200%, the developability of the photosensitive resin composition of the present invention may be remarkably reduced, which is not preferable.
  • additives such as talc, palladium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, Filling agents such as silica and clay, and thixotropic agents such as aerosil; coloring such as phthalocyanine ethanol, phthalocyanine green and acid chloride titanium Agents, silicones, fluorine-based leveling agents and defoamers; polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, etc. to enhance the performance of the composition. It can be added for the purpose.
  • the above-mentioned curing component (I) may be previously mixed with the resin composition, or may be used before being applied to the printed wiring board. That is, a two-component type of a main solution containing the component (F) as a main component and an epoxy curing accelerator and the like, and a curing agent solution mainly containing the curing component (I) are used. It is preferable to use a mixture of these.
  • the photosensitive resin composition of the present invention can also be used as a dry film resist having a structure in which the resin composition is sandwiched between a support film and a protective film. it can.
  • the photosensitive resin composition (liquid or film form) of the present invention can be used as an insulating material between layers of electronic components, an optical waveguide for connecting optical components, a solder resist for a printed circuit board, and a resist such as a coverlay. It can be used as a color filter, a color filter, a printing ink, a sealant, a coating, a coating, an adhesive, and the like.
  • the cured product of the present invention is obtained by curing the above-mentioned resin composition of the present invention by irradiation with energy rays such as ultraviolet rays.
  • Curing by irradiation with energy such as ultraviolet rays can be performed by a conventional method.
  • an ultraviolet ray generating device such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (such as an excimer laser) may be used.
  • the cured product of the resin composition of the present invention may be, for example, a resist film, an interlayer insulating material for a building-up method, or an electric or electronic device such as a print substrate, an optoelectronic substrate, or an optical substrate as an optical waveguide.
  • ⁇ Used for optical components. Specific examples of these include computers, home appliances, portable devices, and the like.
  • the thickness of this cured product layer is About 0 m, preferably about 1 to 100 / m.
  • 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 screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like is applied to a printed wiring board. According to the method, the composition of the present invention is applied in a film thickness of 5 to 160 im, and the coating film is usually heated to a temperature of 50 to 110 ° C, preferably 60 to 100 ° C. By drying with, a coating film can be formed.
  • the unexposed portion is developed by using a developing solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like. Then, if necessary, further irradiate with ultraviolet rays, and then perform heat treatment at the next temperature of usually 100 to 200 ° C, preferably 140 to 180 ° C.
  • a printed wiring board having a permanent protective film that is excellent in gold adhesion and satisfies various properties such as heat resistance, solvent resistance, acid resistance, adhesion, and flexibility can be obtained.
  • the aqueous alkaline solution used in the above development includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, and charcoal.
  • Aqueous solutions of inorganic alkalis such as sodium hydrogen oxyoxide, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, etc.
  • organic alcohol such as sodium hydroxide, tetrabutyl ammonium, sodium hydroxide, monoethanolamine, diethanolamine, triethanolamine, etc. is used. it can.
  • acrylic acid molecular weight: 72.06
  • hydroquinone monomethyl ether 1.02 g
  • Triphenylphosphine is used as a reaction catalyst. After charging 53 g, the reaction solution was reacted at a temperature of 98 ° C until the acid value of the reaction solution became 0.5 mg'KOH / g or less, and the epoxycarboxylate conjugate (A) (theoretical molecular weight: 50 9. 24) was obtained.
  • the epoxy compound ( a ) having two epoxy groups in the molecule was prepared as YX_80 manufactured by Japane Poxy Resin. 404 g (bifunctional hydrogenated bisphenol A type epoxy resin, epoxy equivalent: 220.06 mass), and a monocarboxylic acid having an ethylenically unsaturated group in the molecule.
  • acrylic acid molecular weight: 72.
  • the printed substrate was heated and cured for 60 minutes in a hot air dryer at 150 ° C to obtain a cured film.
  • photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold plating resistance was tested. Table 2 shows the results.
  • the test method and evaluation method are as follows.
  • a 5 O / m negative pattern is adhered to the dried coating film and the integrated light amount
  • the coating film after drying exposure by irradiation with 5 0 O mj ultraviolet Z cm 2.
  • 2.0 kg / c with 1% sodium carbonate aqueous solution for 60 seconds. developed at a spray pressure of m 2, to observe the cured film after drying.
  • the following criteria were used.
  • peeling was observed and evaluated according to the following criteria.
  • the evaluation was performed according to JISK 540.
  • the test substrate was immersed in a 30 ° C acidic degreasing solution (manufactured by Nippon Makadamit, a 20% aqueous solution of MDtDXL_5B in 20 V o 1%) for 3 minutes.
  • the test substrate was immersed in a 14.4 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes, washed with water, and further immersed in a 10 V o 1% sulfuric acid aqueous solution at room temperature for 1 minute, and then washed with water.
  • this substrate was immersed in a catalyst solution (30 V, 1% aqueous solution of 350 V of metal plate activator 350) at 30 ° C for 7 minutes.
  • Heat history was added to the test piece at 55 ° CZ for 30 minutes and 125 ° 530 minutes as one cycle.After 100 cycles, the test piece was observed under a microscope and the following criteria were applied. Was evaluated.
  • Example 7 54.44 g of the resin solution (F-4) obtained in Example 4 was used as a cross-linking agent (H), and HX-220 (trade name: Nippon Kayaku difunctional compound) 3.54 g of tallylate resin, and Irgacure 907 (trade name: Vantico photopolymerization initiator) was used as the photopolymerization initiator (G).
  • HX-220 trade name: Nippon Kayaku difunctional compound
  • Irgacure 907 trade name: Vantico photopolymerization initiator
  • the resulting composition was uniformly applied to a polyethylene terephthalate film serving as a support film by a roll coating method, and the temperature was adjusted to a predetermined value.
  • a polyethylene film as a protective film is placed on this resin layer.
  • Paste to obtain a dry film is placed on a polyimprint substrate (copper circuit thickness: 12 ⁇ ⁇ polyimid film thickness: 25 ⁇ ) at a temperature of 80 ° C.
  • the resin layer was stuck on the entire surface of the substrate while peeling off the protective film.
  • ultraviolet irradiation was performed using an ultraviolet reduction projection exposure apparatus equipped with a negative mask having an optical waveguide pattern (irradiation amount: 5 OO mj / square centimeter).
  • the support film was peeled off from the resin, and developed with a 0.25% aqueous solution of tetramethylammonium for 30 seconds to dissolve and remove the unirradiated portions. Washed and dried Thereafter, the printed substrate was heated and cured in a hot air dryer at 150 ° C. for 30 minutes to obtain a cured film.
  • the resulting cured product had good transparency and a pattern of 50 ⁇ m was resolved.
  • the aqueous solution of an aqueous solution of an acrylic acid of the present invention and the photosensitive resin composition using the same have no tackiness and high sensitivity.
  • the cured film is also excellent in solder heat resistance, chemical resistance, gold plating resistance, etc., does not generate cracks on the surface of the cured product, and is warped even when a thinned substrate is used. It is clear that this is a photosensitive resin composition for a print substrate having a low content. The invention's effect
  • the aqueous solution soluble polyurethane compound, the photosensitive resin composition using the same, and the cured product thereof have excellent photosensitivity in forming a coating film by being exposed and cured by ultraviolet light,
  • the obtained cured product fully satisfies the flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, etc., especially for printed wiring.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un composé (F) de polyuréthane soluble dans un alcali aqueux, qu'on prépare en faisant réagir (A) un composé de carboxylate d'époxy obtenue par la réaction de (a) un composé époxy dont la molécule comprend deux groupes époxydiques avec (b) un composé d'acide monocarboxylique comprenant une double liaison insaturée en éthylène dans sa molécule, (B) un composé diisocyanate, (C) un composé d'acide carboxylique dont la molécule comprend deux groupes hydroxy, et si nécessaire (D) un composé diol autre que les composés (A) et (C) et/ou (E) un composé époxy comprenant un groupe insaturé en éthylène dans sa molécule. Ces compositions de résine photosensible présentent une photosensibilité élevée et permettent de produire des articles durcis présentant une flexibilité élevée, une bonne adhérence, une dureté au crayon élevée, ainsi qu'une remarquable résistance aux solvants, aux acides, thermique, à la dorure etc.
PCT/JP2002/004700 2001-05-17 2002-05-15 Resine photosensible, compositions de resine photosensible contenant cette resine, et articles durcis comprenant ces compositions WO2002094904A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2001-147218 2001-05-17
JP2001147218A JP2002338652A (ja) 2001-05-17 2001-05-17 アルカリ水溶液可溶性ウレタン化エポキシカルボキシレート化合物及びそれを用いた感光性樹脂組成物並びにその硬化物
JP2001348344A JP3846856B2 (ja) 2001-11-14 2001-11-14 アルカリ水溶液可溶性ウレタン化エポキシカルボキシレート化合物及びそれを用いた感光性樹脂組成物並びにその硬化物
JP2001-348344 2001-11-14
JP2001-355269 2001-11-20
JP2001355269A JP2003155320A (ja) 2001-11-20 2001-11-20 感光性樹脂組成物及びその硬化物
JP2002068347A JP2003268067A (ja) 2002-03-13 2002-03-13 感光性樹脂、及びそれを用いた感光性樹脂組成物、並びにその硬化物
JP2002-68347 2002-03-13

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WO2005014682A1 (fr) * 2003-08-07 2005-02-17 Huntsman Advanced Materials (Switzerland) Gmbh Polyurethanes photoreticulables
WO2005076079A1 (fr) * 2004-02-09 2005-08-18 Nippon Kayaku Kabushiki Kaisha Composition de resine photosensible et produit durci
WO2006082776A1 (fr) * 2005-02-01 2006-08-10 Nippon Kayaku Kabushiki Kaisha Composé de polyuréthane réactif, procédé servant à produire celui-ci, composition de résine et produit durci de celle-ci
EP2096637A4 (fr) * 2006-12-19 2011-01-19 Mitsubishi Chem Corp Composition de durcissement par rayonnement pour un support d'enregistrement optique, et support d'enregistrement optique
CN101203915B (zh) * 2005-06-17 2012-11-14 日本化药株式会社 用于光盘的树脂组合物及其固化产物
WO2013146107A1 (fr) * 2012-03-28 2013-10-03 東レ株式会社 Pâte conductrice photosensible et procédé de production d'une impression conductrice
CN115044234A (zh) * 2022-06-21 2022-09-13 瑞通高分子科技(浙江)有限公司 一种可以紫外光固化(uv)h级绝缘涂料组合物及其制备方法

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JPH07102037A (ja) * 1993-10-05 1995-04-18 Dainippon Ink & Chem Inc 水溶性活性エネルギー線硬化型樹脂の製造方法
JP2001100410A (ja) * 1999-09-29 2001-04-13 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物
JP2001163948A (ja) * 1999-10-20 2001-06-19 Rohm & Haas Co 柔軟なオリゴマーを含むフォトイメージャブル組成物

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JPH07102037A (ja) * 1993-10-05 1995-04-18 Dainippon Ink & Chem Inc 水溶性活性エネルギー線硬化型樹脂の製造方法
JP2001100410A (ja) * 1999-09-29 2001-04-13 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物
JP2001163948A (ja) * 1999-10-20 2001-06-19 Rohm & Haas Co 柔軟なオリゴマーを含むフォトイメージャブル組成物

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7476484B2 (en) 2003-08-07 2009-01-13 Huntsman Advanced Materials Americas Inc. Photocrosslinkable polyurethanes
WO2005014682A1 (fr) * 2003-08-07 2005-02-17 Huntsman Advanced Materials (Switzerland) Gmbh Polyurethanes photoreticulables
JP4674902B2 (ja) * 2004-02-09 2011-04-20 日本化薬株式会社 感光性樹脂組成物並びにその硬化物
JPWO2005076079A1 (ja) * 2004-02-09 2007-10-18 日本化薬株式会社 感光性樹脂組成物並びにその硬化物
WO2005076079A1 (fr) * 2004-02-09 2005-08-18 Nippon Kayaku Kabushiki Kaisha Composition de resine photosensible et produit durci
WO2006082776A1 (fr) * 2005-02-01 2006-08-10 Nippon Kayaku Kabushiki Kaisha Composé de polyuréthane réactif, procédé servant à produire celui-ci, composition de résine et produit durci de celle-ci
CN101203915B (zh) * 2005-06-17 2012-11-14 日本化药株式会社 用于光盘的树脂组合物及其固化产物
EP2096637A4 (fr) * 2006-12-19 2011-01-19 Mitsubishi Chem Corp Composition de durcissement par rayonnement pour un support d'enregistrement optique, et support d'enregistrement optique
WO2013146107A1 (fr) * 2012-03-28 2013-10-03 東レ株式会社 Pâte conductrice photosensible et procédé de production d'une impression conductrice
US20150056560A1 (en) * 2012-03-28 2015-02-26 Toray Industries, Inc. Photosensitive conductive paste and method of producing conductive pattern
US9085705B2 (en) * 2012-03-28 2015-07-21 Toray Industries, Inc. Photosensitive conductive paste and method of producing conductive pattern
JPWO2013146107A1 (ja) * 2012-03-28 2015-12-10 東レ株式会社 感光性導電ペーストおよび導電パターンの製造方法
CN115044234A (zh) * 2022-06-21 2022-09-13 瑞通高分子科技(浙江)有限公司 一种可以紫外光固化(uv)h级绝缘涂料组合物及其制备方法

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