WO2008053985A1 - Composition de résine photosensible, produit durci de celle-ci et procédé de production de résine photosensible - Google Patents

Composition de résine photosensible, produit durci de celle-ci et procédé de production de résine photosensible Download PDF

Info

Publication number
WO2008053985A1
WO2008053985A1 PCT/JP2007/071373 JP2007071373W WO2008053985A1 WO 2008053985 A1 WO2008053985 A1 WO 2008053985A1 JP 2007071373 W JP2007071373 W JP 2007071373W WO 2008053985 A1 WO2008053985 A1 WO 2008053985A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
photosensitive
meth
carboxyl group
Prior art date
Application number
PCT/JP2007/071373
Other languages
English (en)
Japanese (ja)
Inventor
Nozomu Hatano
Itaru Shimizu
Hiroko Azuma
Takashi Ishikawa
Takahiro Matsuzawa
Hidenobu Kobayashi
Original Assignee
Toyo Ink Manufacturing Co., Ltd.
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
Application filed by Toyo Ink Manufacturing Co., Ltd. filed Critical Toyo Ink Manufacturing Co., Ltd.
Priority to KR1020097011224A priority Critical patent/KR101536366B1/ko
Priority to CN2007800409539A priority patent/CN101535896B/zh
Priority to JP2008542192A priority patent/JP5298855B2/ja
Publication of WO2008053985A1 publication Critical patent/WO2008053985A1/fr

Links

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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/674—Unsaturated compounds containing the unsaturation at least partially in a cyclic ring having at least one oxygen atom in the ring
    • 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
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
    • 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
    • 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 photosensitive resin composition containing a carboxyl group-containing photosensitive urethane resin useful for printed wiring boards and the like, a cured product thereof, and a method for producing the photosensitive resin. More specifically, it is useful as a solder resist for flexible printed wiring boards, a plating resist, an interlayer electrical insulation material for multilayer printed wiring boards, a photosensitive optical waveguide, etc., and has excellent developability.
  • the present invention relates to a method for producing the photosensitive resin. Furthermore, the present invention relates to a highly flame-retardant photosensitive solder resist ink and a dry film type photosensitive solder resist containing the photosensitive resin composition.
  • solder In a soldering process that is performed when a wiring (circuit) pattern formed on a substrate is protected from external environmental forces or when an electronic component is surface-mounted on a printed wiring board, solder is applied to unnecessary portions.
  • a protective layer called a coverlay or solder mask is coated on the printed wiring board.
  • a protective layer used for a wiring pattern formed on a polyimide film, called a flexible printed wiring board is required to have adhesion with polyimide, flexibility, and folding resistance.
  • a protective layer for a flexible printed wiring board a type in which a polyimide film called a cover lay film is formed by punching a mold in accordance with a pattern and then pasted using an adhesive, or by screen printing.
  • thermosetting inks to be applied, etc. but due to the recent progress in electronics, high-density and high-definition, UV-curable photoresist-type solder resist inks that can be patterned with higher accuracy, or Dry film type solder resist is being studied.
  • a resist ink composition that includes a resin obtained by reacting succinic anhydride with an addition product of an epoxy resin having a bisphenol A skeleton in the main chain and an unsaturated group-containing monocarboxylic acid (Patent Documents). 1). Although this is excellent in developability, photosensitivity, adhesion, heat resistance, etc., there is a problem that flexibility and folding resistance are still insufficient.
  • thermosetting composition a reaction between a secondary hydroxyl group formed by an esterification reaction of a cresol nopolac type epoxy compound and an unsaturated monocarboxylic acid and a saturated or unsaturated polybasic acid anhydride.
  • Patent Document 2 A product, a reaction product of the secondary hydroxyl group and an unsaturated group-containing isocyanate compound has been proposed (Patent Document 2). Although these are extremely excellent in adhesion, solder heat resistance, and coating film resistance, they have a problem in terms of flexibility and folding resistance! It was.
  • Patent Document 3 a photosensitive element containing a polymer obtained by copolymerizing a monomer containing (meth) acrylic acid and (meth) acrylic acid ester as a binder component has been proposed. These are excellent in developability and resolution, but when used in flexible printed wiring board applications, sufficient adhesion / flexibility and folding resistance cannot be obtained.
  • a carboxyl group containing an ester bond derived from half esterification in the main chain by reacting a polyol compound with a polybasic acid anhydride having two acid anhydride groups in the molecule A polyester polyol is prepared, and a polyisocyanate compound is reacted with this to obtain a carboxyl group-containing urethane prepolymer. Further, one in the molecule with respect to a part of the carboxyl groups in the urethane prepolymer.
  • a photosensitive resin composition containing a carboxyl group-containing urethane oligomer obtained by reacting a (meth) acrylate having an epoxy group Patent Document 4).
  • Patent Document 5 a photosensitive resin composition containing a phosphorus-based flame retardant is disclosed.
  • a printed wiring board is required to have high accuracy and high density in order to reduce the size and weight as a portable device and improve the communication speed, and is mainly used around the bent portion and connection portion of the device. The same is true for flexible printed wiring boards.
  • demands for protective layers for flexible printed wiring boards are becoming more and more sophisticated, and developability that can achieve high definition of resist patterns and higher flexibility than conventional requirements.
  • the performance that satisfies solder heat resistance, substrate adhesion, high insulation, coating film resistance, flame resistance, etc. while maintaining folding resistance is required! Photo solder resists that are currently available on the market do not fully meet these requirements.
  • Patent Document 1 Japanese Patent No. 3281473
  • Patent Document 2 Japanese Patent No. 2707495
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-279479
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-159815
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2006-251715
  • the present invention is excellent in photosensitivity to active energy rays, and presently uses dilute alkaline aqueous solutions. A fine pattern can be formed by the image, and the cured coating film obtained through the post-curing process has excellent flexibility, insulation, adhesion, solder heat resistance, coating resistance, flame resistance, etc. It is an object of the present invention to provide a photosensitive resin composition suitably used for a photo solder resist, a cured product thereof, and a method for producing a photosensitive resin.
  • the first invention is a photosensitive resin containing a carboxyl group-containing photosensitive urethane resin (A), a photopolymerization initiator (B), and a photosensitive ethylenically unsaturated group-containing compound (C).
  • a composition comprising:
  • a carboxyl group-containing urethane prepolymer obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components A noreboxinole group;
  • a hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) obtained by reacting an epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group;
  • the present invention relates to a photosensitive resin composition, which is a resin obtained by reacting an acid anhydride group in an acid anhydride group-containing compound (d).
  • the second invention further relates to the photosensitive resin composition of the first invention, further comprising a thermosetting compound (D).
  • the third invention further relates to the photosensitive resin composition of the second invention, further comprising a thermosetting aid (E).
  • the fourth invention relates to the photosensitive resin composition of any one of the first to third inventions, wherein the acid value of the carboxyl group-containing photosensitive urethane resin (A) is 10 to 200 mgKOH / g.
  • the fifth invention is the photosensitive resin group of any one of the first to fourth inventions, wherein the ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin (A) is 200 to 3000 g / eq. Concerning the composition.
  • the sixth invention relates to the photosensitive resin composition according to any one of the first to fifth inventions, wherein the weight-average molecular weight force of the carboxyl group-containing photosensitive urethane resin (A) is 1000 to 100,000.
  • the seventh invention is the photosensitive resin composition according to any one of the second to sixth inventions, wherein the thermosetting compound (D) is a compound (k) having two or more epoxy groups or oxetane groups.
  • the eighth invention relates to a cured product obtained by curing the photosensitive resin composition of any one of the first to seventh inventions.
  • the ninth invention relates to a photosensitive solder resist ink comprising the photosensitive resin composition of any one of the first to seventh inventions and a flame retardant.
  • the tenth invention relates to a dry film type photosensitive solder resist comprising the photosensitive resin composition of any one of the first to seventh inventions and a flame retardant.
  • the eleventh invention comprises reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components.
  • a polymer polyol (e) a polymer polyol having two hydroxyl groups in the molecule
  • a diisocyanate compound (g) as essential components.
  • a method for producing a carboxyl group-containing photosensitive urethane resin comprising a third step of reacting the hydroxyl group-containing urethane prepolymer (c) with the acid anhydride group-containing compound (d). .
  • the photosensitive film has excellent photosensitivity to active energy rays, and a fine pattern can be formed by development with a dilute aqueous alkali solution.
  • the cured coating film obtained through a post-curing (post-cure) process has flexibility and insulating properties.
  • a photosensitive resin composition that is excellent in adhesion, solder heat resistance, coating film resistance, flame retardancy, etc., and is suitable for use as a photo solder resist, and its cured product, as well as a method for producing a photosensitive resin. I was able to do that.
  • the photosensitive resin composition of the present invention comprises a solder resist for flexible printed wiring boards, a light-sensitive cover lay film, a mask resist, an interlayer electrical insulating material for wire boards, a photosensitive optical waveguide, and a polyethylene terephthalate film. It can be suitably used as a coverlay resist for a flexible printed circuit board formed with a circuit by printing a conductive ink such as silver paste or carbon paste.
  • the carboxyl group-containing urethane oligomer described in Patent Document 4 includes an ester bond derived from half esterification with a polybasic acid anhydride in the main chain.
  • the photosensitive resin composition has no ester bond derived from such half-esterification in the main chain, and the main chain is chemically stable. It exhibits excellent heat resistance even when exposed to high-temperature conditions such as a solder bath, and at the same time, it exhibits the adhesiveness and flexibility unique to urethane resins.
  • the carboxyl group-containing photosensitive urethane resin (A) of the present invention has a photosensitive group and a carboxyl group in the 1S side chain, so that it exhibits excellent developability even when the amount of carboxyl group contained is small. Since the side chain functional group is more reactive than when it is directly bonded to the main chain, it can exhibit excellent photocurability, resolution, and coating film resistance.
  • the photosensitive resin composition of the present invention will be described in detail.
  • the carboxyl group-containing photosensitive urethane resin (A) of the present invention comprises a compound having an epoxy group or oxetane group and an ethylenically unsaturated group (b) with respect to 1 mol of the carboxyl group in the carboxyl group-containing urethane prepolymer (a).
  • Epoxy group or oxetane group is preferably reacted with 0.1 monole to 1.0 monole harm ij, more preferably 0.30 monole to 0.95 monole harm ij.
  • the acid anhydride group in the acid anhydride group-containing compound (d) is preferably 0.1 monolayer to 1 mole per 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c). Harm of monole, ij, more preferably 0.330 monole to 0.95, harm of monole IJ.
  • the molar ratio is a reaction molar ratio, and each starting material is used in an amount that enables the reaction at the molar ratio. Therefore, for example, the above-mentioned “carboxyl group-containing urethane pre-
  • the “polymer (a)” and the “compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group” are combined with the carboxyl group 1 in the “carboxyl group-containing urethane prepolymer (a)”.
  • the reaction is performed in such an amount that the epoxy group or oxetane group in the “compound having an epoxy group or oxetane group and an ethylenically unsaturated group (b)” is 0.1 mol to 1.2 mol with respect to mol. There is power S. Moreover, the description regarding the reaction molar ratio in this specification is the same meaning as the above.
  • the carboxyl group in the carboxyl group-containing urethane prepolymer (a) is reacted with the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group.
  • the ratio is less than 0.1 mol, the amount of unsaturated groups in the finally obtained carboxyl group-containing photosensitive urethane resin (A) decreases, and the photosensitive resin composition has a! /, Therefore, it is difficult to obtain desired photosensitivity.
  • the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group to 1.
  • mol of carboxyl group in the carboxyl group-containing urethane prepolymer (a) is 1. It cannot be reacted in an amount greater than 0 mole.
  • the acid anhydride group in the acid anhydride group-containing compound (d) cannot be reacted in an amount greater than 1.0 mol with respect to 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c).
  • the carboxyl group-containing urethane prepolymer (a) is obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components. It is manufactured by letting. Further, as a desired component, a hydroxyl group-containing compound (h) [excluding the “polymer polyol (e)” and the “carboxylic acid compound (f) having two hydroxyl groups in the molecule”) and an isocyanate in the molecule An isocyanate compound (i) having one or more groups and an amine compound (j) can be appropriately used.
  • the carboxyl group-containing urethane prepolymer (a) when synthesized, the reaction ratio of the starting materials of polymer polyol (e), carboxylic acid compound (f) having two hydroxyl groups in the molecule, and optionally added hydroxyl group-containing compound (h), and amine compound (j) When the total of the hydroxyl group and the amino group contained therein is 1 mole, the diisocyanate compound (g) and the isocyanate group (i) having one or more isocyanate groups in the molecule are included. It is preferable to react at a ratio of 0.50 mol to 1.00 mol, and more preferably at a ratio of 0.70 mol to 0.95 mol.
  • the isocyanate group When the isocyanate group is less than 0.50 mol, the molecular weight of the carboxyl group-containing urethane prepolymer (a) decreases, making it difficult to obtain desired coating film resistance and film-forming properties. Also, if the isocyanate group is more than 1.00 mol, excess isocyanate groups will remain in the system, resulting in by-products in the subsequent reaction process or gelation during the reaction. It is easy to produce!
  • the polymer polyol (e), the carboxylic acid compound (f) having two hydroxyl groups in the molecule, the optionally added hydroxyl group-containing compound (h), and the amine compound (j) it is preferable to add the carboxylic acid compound (f) having two hydroxyl groups in the molecule at a rate of an acid value of 5 to 200 mgKOH / g of the carboxyl group-containing urethane prepolymer (a) finally obtained. Preferably 10 to 180 mg KOH / g).
  • the polymer polyol (e) used in the present invention is a compound containing two or more hydroxyl groups, and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter also referred to as "GPC").
  • GPC gel permeation chromatography
  • the weight average molecular weight means the weight average molecular weight in terms of polystyrene by GPC measurement.
  • polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block copolymer or random copolymer polytetramethylene glycol, tetramethylene glycol and neopentyl glycol are used.
  • Polyether polyols such as block copolymers or random copolymers;
  • Polyester polyols that are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
  • Polycarbonate polyols obtained by reaction of glycol or bisphenol with carbonate, or reaction of phosgene with glycol or bisphenol in the presence of alkali;
  • Examples thereof include force prolatatone-modified polyols such as force prolatatone-modified polytetramethylene polyol, polybutadiene-type polyols such as polyolefin polyol and hydrogenated polybutadiene polyol, and polyols such as silicone-type polyol.
  • these polymer polyols (e) may be used alone or in combination.
  • polyether polyols such as polytetramethylene glycol, a block copolymer of tetramethylene glycol and neopentyl glycol or a random copolymer have a skeletal flexibility, hydrolysis resistance, and hydrophilicity. Therefore, when used in the present invention, the flexibility, chemical resistance, developability and the like of the coating film are particularly preferable.
  • Carboxylic acid compound (f) having two hydroxyl groups in molecule used in the present invention comprises two hydroxyl groups and one or more (preferably 1 to 3) carboxyl groups in the molecule.
  • dimethylolbutanoic acid and dimethylolpropionic acid are preferred in the present invention in that the concentration of carboxyl groups in the resin can be increased.
  • force prolatatone adducts, ethylene oxide adducts, propylene oxide adducts, etc. can reduce the amount of urethane bonds in the carboxyl group-containing urethane prepolymer (a), thus improving the flexibility of the coating film.
  • aromatic compounds such as hydroxysalicylic acid can be used for the purpose of improving the heat resistance of the coating film.
  • these carboxylic acid compounds (f) can be appropriately selected and used according to the purpose and application, and only one kind may be used alone or a plurality may be used in combination. May be.
  • Examples of the diisocyanate compound (g) used in the present invention include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.
  • aromatic salts include 1,3-phenyl diisocyanate, 4,4 phenyl diisocyanate, 1,4 phenyl diisocyanate, 4,4 eight, 2 , 4 Tolylene diisocyanate, 2, 6-Tote, 4, 4 'Toluoresin diisocyanate, 2, 4, 6 Triisocyanate deoxygenate, 1, 3, 5, 5-Triisocyanate benzene, Di C.
  • aliphatic diisocyanate for example,
  • Examples of the araliphatic diisocyanate include ⁇ , ⁇ '-diisocyanate—1,3-dimethylbenzene, ⁇ , ⁇ , monodiisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ , monodiisocyanate 1,4, Examples thereof include tilbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
  • Examples of the alicyclic diisocyanate include, for example, 3-isocyanate methyl 1,3,5,5 trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl 2,4 cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 4, 4 Examples include '-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, and the like.
  • the hydroxyl group-containing compound (h) used in the present invention is a compound having one or more hydroxyl groups.
  • the compound belonging to the "polymer polyol (e)” and the “carboxyl having two hydroxyl groups in the molecule” The compound excluding the compound belonging to “acid compound (f)”, and typical examples thereof include, for example, a monoalcohol compound (hi) having one hydroxyl group in the molecule, and two hydroxyl groups in the molecule.
  • Examples of monoalcohol compounds (hi) having one hydroxyl group in the molecule include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, laurinore.
  • Aliphatic monoalcohols such as anoleconole and stearyl alcohol;
  • Alicyclic monoalcohols such as cyclohexanol
  • Aromatic monoalcohols such as benzyl alcohol, fluorenol, phenol, and methoquinone;
  • monoalcohol compounds having functional groups other than hydroxyl groups include hydroxyl group-containing carboxylic acid compounds such as 12-hydroxystearic acid, 2-hydroxyethyl (meth) acrylate (“2
  • Hydroxyl group-containing (meth) acrylate compounds such as 4-hydroxybutynole (meth) acrylate, hydroxyl group-containing epoxy compounds such as glycidol, and hydroxyl group-containing oxetane compounds such as oxetane alcohol.
  • Hydroxyl group-containing (meth) acrylate compounds such as 4-hydroxybutynole (meth) acrylate
  • hydroxyl group-containing epoxy compounds such as glycidol
  • hydroxyl group-containing oxetane compounds such as oxetane alcohol.
  • Other examples include oligomer type monoalcohols such as one-end methoxylated polyethylene glycol, one-end methoxylated polypropylene glycol, and force prolatatone addition polymer using monoalcohol as an initiator.
  • the polymerization end of the resulting carboxyl group-containing urethane prepolymer ⁇ can be blocked, so that the low molecular weight carboxyl group-containing urethane prepolymer ⁇ is intentionally formed. It can be used suitably when it is necessary to adjust the molecular weight, such as when synthesizing. Further, when a hydroxyl group-containing compound having a functional group other than a hydroxyl group is used, a functional group other than a hydroxyl group can be introduced into the terminal of the carboxyl group-containing urethane prepolymer (a). It can be suitably used when terminal modification of ⁇ is required.
  • lauryl alcohol in consideration of hydroxyl reactivity and polymerization control, lauryl alcohol, stearylene alcohol, cyclohexanol, 12-hydroxystearic acid, glycidol, 2 hydroxyethyl (meth) atalylate, 4 hydroxybutyl ( It is preferable to use (meth) acrylate.
  • Examples of the diol compound (h2) having two hydroxyl groups in the molecule and not having a carboxyl group and having a weight average molecular weight of 50 to 499 include ethylene glycol, polyethylene glycol, triethylene glycol and the like. , Tetraethyleneglycol, propyleneglycol
  • Dipropylene glycol butylene glycol, 1,3-butanediol, 1,4-butanediole, 3-methinoleol 1,5-pentanediole, 1,6-hexanedioleol, neopentyldarlicol, 1,9 -Nonanediol, hydrogenated bisphenolanol A, 1,4-cyclohexanedimethanol, spiroglycol and other aliphatic diols;
  • Aromatic diols such as hydroquinone, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, bisphenolanol, bisphenoxyethanolanolenolene, bisphenolenolenolene, biscrezonolefluorene;
  • these diol compounds (h2) may be used alone or in combination.
  • the use of a diol compound containing a tertiary amino group such as N, N-bis (2-hydroxypropyl) aniline increases the cohesive strength of the coating film, and maintains more flexibility while maintaining flexibility. It is preferable because it can form a strong tough coating film.
  • Examples of the polyhydric alcohol compound (h3) having three or more hydroxyl groups in the molecule and having a weight average molecular weight of 50 to 499 include trimethylolethane, polytrimethylolethane, Examples include limethylonorepronone, polytrimethylonolepronone, pentaerythritol, polypentaerythritol, sonorebitonore, mannitol, arabitol, xylitolore, galactitonor, glycerin and the like.
  • these polyhydric alcohol compounds (h3) when used, it is possible to branch a part of the resulting carboxyl group-containing urethane prepolymer (a).
  • the resistance of the coating film can be improved. Therefore, in the present invention, it may be used as necessary for the purpose of further improving the resistance of the cured coating film.
  • these polyhydric alcohol compounds (h3) it is preferable to use trimethylolpropane or pentaerythritol in terms of reaction control.
  • Isocyanates include (meth) ataloyloxetyl isocyanate, 1, 1-bis [(sochanate, (meth) atalyloyl isocyanate, isopropenyl-a, a-dimethylbenzyl isocyanate, etc.
  • 1,6-Diisocyanatohexane 1,6-Diisocyanatohexane, Isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, Toluene polymeric diphenyl methacrylate, Toluene 2,4-diisocyanate, Hexamethylene diisocyanate , Diisocyanate 4-methylenole m-phenylene, naphthylene diisocyanate, nora fure Sodium, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, trizine diisocyanate, 2, 2, 4-trimethylhexamethylene diisocyanate, 2, 4, 4-to
  • the polyfunctional isocyanate having three or more isocyanate groups in one molecule includes, for example, aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, and aromatic aliphatic polyisocyanates. And trimethylolpropane adduct of diisocyanate (g) described above, a buret body reacted with water, and a trimer having an isocyanurate ring.
  • a single group having one isocyanate group in one molecule is used for the purpose of sealing the terminal. It is preferable to use a functional isocyanate, and for the purpose of improving the resistance of a coating film obtained by photocuring from the photosensitive resin composition according to the present invention, or a coating film obtained by photocuring and heat curing, etc.
  • a polyfunctional isocyanate having three or more isocyanate groups in one molecule is preferable to use.
  • these isocyanate compounds can be appropriately selected and used according to the purpose and application, or only one kind may be used alone, or a plurality may be used in combination.
  • an amine compound (j) when the carboxyl group-containing urethane prepolymer (a) is synthesized, an amine compound (j) can be reacted as a desired component.
  • the amine compound (j) as used in the present invention refers to a compound having at least one primary or secondary amino group in the molecule.
  • Examples of the amine compound (j) of the present invention include propylamine, hexylamine, cyclohexanamine, benzylamine, 2-ethylhexylamine, octylamine, and dodecyl.
  • Monoamine compounds such as luamine and aniline, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2 , 2, 4 Aliphatic polyamines such as trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, cycloaliphatic polyamines such as isophoronediamine, dicyclohexylmethane 4, 4'-diamine, and phenol Aromatic polyamines such as direndiamine and xylylenediamine are listed.
  • diamine compounds such as both-end amino group-modified polyethylene oxide, both-end amino group-modified polypropylene oxide, polysilicone diamine, polybutadiene diamine, one-end amino group-modified polyethylene oxide, one-end amino group
  • examples thereof include monoamine compounds such as modified polypropylene oxide, polysilicone monoamine and polybutadiene monoamine, and polymer type polyamine compounds such as polyethylenimine and polyallylamine.
  • the primary amino group in the compound having a primary amino group is subjected to a Michael addition reaction with the (meth) acrylate group of the (meth) acrylate group-containing compound.
  • the amine compound obtained by modification to a primary amino group can be introduced into the carboxyl group-containing urethane prepolymer ( a ) by devising a (meth) acrylate group-containing compound.
  • a diamine having a secondary amino group is synthesized by Michael addition of the acrylate group of 4-hydroxybutyl acrylate to the primary amino group of isophorone diamine, and used as a raw material for the urethane resin of the present invention. By using it, a hydroxyl group can be introduced into the resin.
  • an amin compound having a functional group other than an amino group can be used.
  • these amine compounds (j) may be used alone or in combination.
  • a plurality of monoamines, diamines and polyamines can be appropriately selected or used in combination depending on the purpose and application.
  • the amount of residual isocyanate groups can be reduced and the ends can be blocked, so that the molecular weight can be easily controlled.
  • a diamine compound it becomes possible to extend the polymer chain, and a high molecular weight polymer can be obtained.
  • the polymer chain can be branched to ultimately improve the cohesive strength / resistance of the coating film.
  • the reaction with the diisocyanate compound (g) [and optionally further with the isocyanate compound (i)] is carried out simultaneously with other raw materials such as the polymer polyol (e). Or by synthesizing an isocyanate-terminated urethane chain in advance and adding or dropping the amine compound (j) to extend the chain, thereby the carboxyl group-containing urethane prepolymer (a) containing a urea bond is obtained. The method of obtaining is mentioned.
  • the amine compound (j) when the amine compound (j) is reacted in this manner, the cohesive force of the resulting carboxyl group-containing photosensitive urethane resin (A) is improved, and a coating film with more excellent heat resistance and durability is formed. You can use the amine compound (j) if necessary! /.
  • the synthesis conditions of the carboxyl group-containing urethane prepolymer (a) are not particularly limited and can be carried out under known conditions.
  • a polymer polyol (e), a carboxylic acid compound (f), and a solvent [and optionally a hydroxyl group-containing compound (h)] are charged in a flask, and heated and stirred at 20 to 120 ° C. under a nitrogen stream. Then, the diisocyanate compound (g) [and optionally the isocyanate compound (i)] is added and heated at 50 to 150 ° C with stirring to obtain a carboxyl group-containing urethane prepolymer (a ) Can be obtained.
  • a urethanization catalyst such as an organotin compound or a tertiary amino group-containing compound may be used as necessary.
  • the diisocyanate compound (g) the polymer polyol (e), the carboxylic acid compound (f), and the solvent previously charged in the flask were heated and stirred at 100 ° C or higher to obtain a part of the solvent. May be removed. This operation is usually performed to remove water (dehydration treatment) in the system, and when the diisocyanate compound (g) is reacted by this operation, The deactivation of the isocyanate group due to is suppressed, and finally, the carboxyl group-containing urethane prepolymer (a) having physical properties closer to the theoretical values is obtained.
  • the present invention comprises reacting a carboxyl group-containing urethane prepolymer (a) with a compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group, to thereby produce a hydroxyl group-containing urethane prepolymer.
  • a polymer (c) is synthesized.
  • the proportion of the carboxyl group-containing urethane prepolymer (a) and the compound (b) having an epoxy group or an oxetane group and an ethylenically unsaturated group is as described above.
  • the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group is preferably from 0.1 mol to 1 mol of the carboxyl group in the containing urethane prepolymer (a).
  • the reaction is preferably carried out at a ratio of 1.0 mole, more preferably at a ratio of 0.3 mole to 0.95 mole.
  • the carboxy group in the carboxyl group-containing urethane prepolymer (a) is reacted with the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group.
  • the proportion to be added is less than 0.1 mol, the amount of unsaturated groups in the finally obtained carboxyl group-containing photosensitive urethane resin (A) decreases, so that the photosensitive resin composition has a reduced amount. It is difficult to obtain desired photosensitivity.
  • the "compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group” used in the present invention is preferably a compound having 6 to 50 carbon atoms, such as glycidyl (meth) acrylate.
  • Glycidyl cinnamic acid 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl aryl ether, 2, 3 epoxy 2 methyl propyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) attaly Hydroxyl groups of hydroxyl-containing polyfunctional acrylic monomers such as 4-butyl-1-cyclohexene 1,2 epoxide, 1,3 butadiene monoepoxide, oxetaninole (meth) acrylate, oxetanyl cinnamic acid, and pentaerythritol tritalylate And a monofunctional ester containing a polyfunctional acrylate group reacted with epichlorohydrin.
  • hydroxyl-containing polyfunctional acrylic monomers such as 4-butyl-1-cyclohexene 1,2 epoxide, 1,3 butadiene monoepoxide,
  • Poxide obtained by modifying most of the epoxy groups of phenol nopolac type epoxy resin to acrylate groups with acrylic acid, etc., containing polyfunctional acrylate groups leaving one epoxy group per molecule on average Monoepoxide, carboxyl group of carboxyl group-containing polyfunctional acrylic monomer, 2 or more in the molecule
  • Examples include polyfunctional attalylate group-containing monoepoxides obtained by reacting a part of the epoxy group of a compound having an epoxy group, and reacting these epoxy group or oxetane group with a carboxyl group in urethane prepolymer ⁇ .
  • a hydroxyl group-containing urethane prepolymer (C) is obtained.
  • the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group may be used alone or in combination.
  • glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether are rich in reactivity with the carboxyl group in the carboxyl group-containing urethane prepolymer (a) in the present invention.
  • the photosensitive resin composition obtained is particularly preferable because of extremely excellent photosensitivity.
  • the "compound (o) having no ethylenically unsaturated group and having an epoxy group or oxetane group” is referred to as "epoxy group or oxetane group and ethylenically unsaturated group.” It can also be used in combination with the “compound (b) having a group”.
  • the “compound (o) having no ethylenically unsaturated group and having an epoxy group or oxetane group” which can be optionally used in the present invention is preferably a compound having 6 to 50 carbon atoms, such as styrene oxide, Phenyl glycidyl ether, o-phenol phenol glycidyl ether, p-feyulfeno monoreglycidinoreatenore, glycidinoresin namate, methinoreglycidinoatenore, butinore glycidinoreatenore, 2-ethinorehexenoleguri Shizino reetenore, decinore glycidino ether, stearyl glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl daricidyl
  • these “compounds having no ethylenically unsaturated groups and having an epoxy group or oxetane group (o)” are referred to as “compounds having an epoxy group or oxetane group and an ethylenically unsaturated group (b) ”In combination, it is possible to control the photosensitivity of the carboxyl group-containing photosensitive urethane resin (A) of the present invention more widely, so that it is preferable to use it appropriately depending on the purpose and application. ,.
  • the reaction conditions for reacting with the xetane group are not particularly limited and can be carried out under known conditions.
  • a carboxyl group-containing urethane prepolymer (a), an epoxy group or a compound having an oxetane group and an ethylenically unsaturated group (b) [and optionally “having no ethylenically unsaturated group, epoxy group or The compound having an oxetane group (o) ”] and a solvent are charged and heated at 50 to 150 ° C. with stirring in an oxygen stream to obtain a hydroxyl group-containing urethane prepolymer (c).
  • a tertiary amino group-containing compound such as triethylamine or dimethylbenzylamine
  • a polymerization inhibitor of an ethylenically unsaturated group such as hydroquinone methoquinone.
  • the amount of catalyst added is in the range of 0.;! To 10 wt% with respect to the sum of (a) and (b), and the amount of inhibitor added is in the range of 0.05 to 10 wt%. It is preferable to do.
  • the carboxyl group-containing photosensitive urethane resin (A) when the carboxyl group-containing photosensitive urethane resin (A) is produced, the hydroxyl group-containing urethane prepolymer (c) and the acid anhydride group-containing compound (d) are reacted. It is characterized by.
  • the acid anhydride group-containing compound (d) used in the present invention is a compound having an acid anhydride group, and by reacting the acid anhydride group with a hydroxyl group in the hydroxyl group-containing urethane prepolymer (c), The carboxyl group-containing photosensitive urethane resin (A) is obtained.
  • the ratio of reacting the hydroxyl group-containing urethane prepolymer (c) with the acid anhydride group-containing compound (d) is based on 1 mol of hydroxyl group in the hydroxyl group-containing urethane prepolymer (c).
  • the acid anhydride group in the acid anhydride group-containing compound (d) is reacted at a ratio of 0.1 mol to 1.0 mol.
  • the ratio of reacting the acid anhydride group in the acid anhydride group-containing compound (d) with respect to 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) is less than 0.1 mol, the curability and The ratio of introducing carboxyl groups having excellent developability decreases, and the desired developability is difficult to obtain.
  • the acid anhydride group-containing compound (d) used in the present invention is preferably a compound having one or two carboxylic acid anhydride groups in the molecule and having 4 to 50 carbon atoms.
  • Phthalic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, methyl hymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride Contains an acid anhydride group having an alicyclic structure or aromatic ring structure such as titrihydrohydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, anhydrous heptic acid, tetrabromophthalic anhydride, etc.
  • acid anhydride group-containing compounds (d) include succinic anhydride, maleic anhydride, dartaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecino succinic anhydride, butyl Maleic anhydride, pentylmaleic anhydride, hexinole maleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecinole maleic anhydride, butylglutamic anhydride, hexylglutamic anhydride, heptylglutamic anhydride Products, octyl glutamic anhydride, decyl glutamic anhydride, dodecyl glutamic anhydride, and the like.
  • the acid anhydride group-containing compound (d) may be used alone or in combination.
  • succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable because the photosensitive resin composition obtained in the present invention has very excellent developability, pattern formability, and coating film resistance.
  • the reaction conditions for reacting the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) with the acid anhydride group in the acid anhydride group-containing compound (d) are not particularly limited. Can be done. For example, a hydroxyl group-containing urethane prepolymer (c), an acid anhydride group-containing compound (d), and a solvent are placed in a flask and heated at 50 to 150 ° C with stirring in an oxygen stream to contain a carboxyl group. A photosensitive urethane resin (A) is obtained. In this case, it is preferable to add a tertiary amino group-containing compound such as triethylamine or dimethylbenzylamine as a catalyst. In this case, the hydroxyl group-containing urethane prepolymer (c) and the acid anhydride group-containing compound (d) It is preferable to add in the range of 0.;! To 10% by weight.
  • the acid value of the carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably 10 to 200 mg KOH / g, more preferably 30 to 150 mg KOH / g.
  • the acid value is less than 10 mgKOH / g, sufficient developability may be difficult to obtain. For example, a film may remain as a residue in a portion where it is desired to dissolve and remove the film during development.
  • the acid value exceeds 200 mgKOH / g, the solubility of the coating film in the developer increases. Photocured and left as a pattern! /, Even the part dissolves and the shape of the pattern may deteriorate.
  • the ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably 200 to 3000 g / eq ⁇ , more preferably ⁇ is 300 to 2000 g / eq. is there. If the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity may be too high, and even the part to be removed by dissolving the film during development will be cured by light, resulting in a good pattern. It may not be possible.
  • the “ethylenically unsaturated group equivalent” as used in the present invention is a theoretical value calculated from the weight of the raw material used during the synthesis of the resin, and the weight of the resin is the ethylene present in the resin.
  • the weight-average molecular weight of the carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably from 100 to 100,000; more preferably from 3000 to 60000. If the weight average molecular weight is less than 1000, sufficient solder heat resistance and flexibility may not be obtained. On the other hand, if the weight average molecular weight exceeds 100,000, the soldering heat resistance is excellent, but the developability may be deteriorated, and the viscosity and handling during coating may be problems.
  • the method for producing a carboxyl group-containing photosensitive urethane resin (A) according to the present invention comprises a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, a diisocyanate compound (g ) As an essential component to obtain a carboxyl group-containing urethane prepolymer (a);
  • the hydroxyl group-containing urethane prepolymer (a) obtained in the first step is reacted with the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group to react with the hydroxyl group-containing urethane prepolymer.
  • a third step of reacting the hydroxyl group-containing urethane prepolymer (c) obtained in the second step with the acid anhydride group-containing compound (d) is included.
  • the reaction conditions of the first step it is preferable to carry out the reaction by heating and stirring at a temperature of room temperature to 180 ° C, and a reaction catalyst can be used if necessary.
  • reaction conditions for the second step it is preferable to react by heating and stirring at a temperature of 50 to 150 ° C in the presence of oxygen. Polymerization of reaction catalyst and ethylenically unsaturated groups is prohibited if necessary. An agent can also be used.
  • reaction conditions for the third step are the same as for the second step, in the presence of oxygen, 50 to 50 °; after completion of the second step, the reaction is preferably performed by heating and stirring at 150 ° C. If necessary, a suitable reaction catalyst and a polymerization inhibitor for ethylenically unsaturated groups can be newly added.
  • the carboxyl group-containing urethane prepolymer (a) is produced in the first step, the polymer polyol (e), the carboxylated compound (f) having two hydroxyl groups in the molecule, The diisocyanate compound (g) is reacted as an essential component. Further, the hydroxyl group-containing compound (h) as an optional component, the isocyanate compound (i) as an optional component, and the amine compound (j) as an optional component , Can also be reacted.
  • the solvent used for the synthesis of the carboxyl group-containing photosensitive urethane resin (A) can be appropriately selected according to the end use and the solubility of the reaction product.
  • a solvent having a low boiling point because it is necessary to quickly dry the solvent in the dry film preparation process.
  • the low boiling point solvent in this case include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene and isopropyl alcohol.
  • liquid solder resist ink when liquid solder resist ink is used as the final application, it is necessary to suppress the volatilization of the solvent as much as possible in consideration of the process of mixing fillers and pigments with rolls in the ink preparation process and the storage stability of the ink. Therefore, it is preferable to use a high boiling point solvent.
  • the high boiling point solvent in this case include carbitol acetate, methoxypropyl acetate, cyclohexanone, diisoptyl ketone and the like.
  • these solvents may be used alone or in combination, if necessary, or may be used in combination, or after solvent removal or after solvent removal, You can add a new solvent.
  • the photosensitive resin composition of the present invention includes the carboxyl group-containing photosensitive urethane resin (A). And a photopolymerization initiator (B) and a photosensitive ethylenically unsaturated compound (C).
  • the photopolymerization initiator (B) is added for the purpose of curing the photosensitive compound with active energy rays (for example, ultraviolet rays).
  • the photopolymerization initiator is not particularly limited as long as it has a function capable of initiating butyl polymerization by photoexcitation, for example, a monocarbonyl compound, a dicarbonyl compound, a acetophenone compound, a benzoin ether compound, an acyl phosphine oxide compound, A minocarbonyl compound or the like can be used.
  • Specific monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2, 4, 6 trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- ( 4-Methylphenylthio) pheneluenetanone, 3, 3'-dimethylenole 4-methoxybenzophenone, 4-one (1,3 attalyloinole 1,4,7,10,13-pentaxotridecyl) benzophenone, 3, 3 '4, 4'—tetra (t butylperoxy force noreboninole) benzophenone, 4-benzoyl N, N, N trimethylbenzenemethammonium chloride, 2 hydroxy 1 3— (4 benzoyl monophenoxy) 1 N, N, N trimethyl 1 Propanamine hydrochloride, 4-benzoyl N, N dimethyl-n— [2— (loxo-2propenyloxetyl)] methammonium odorate
  • Dicarbonyl compounds include 1,7,7 trimethylbicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10 phenanthrenequinone, methyl- ⁇ Examples include xobenzene acetate and 4-phenylbenzyl.
  • Examples of the acetophenone compound include 2-hydroxy-1, 2-methyl-1-phenylpropane.
  • benzoin ether compound examples include benzoin, benzoin methyl ether, benzoin ethinoreatenore, benin isopropinoreatenore, benzoin iso: / tinole ether, benzoin normal butyl ether and the like.
  • acylphosphine oxide compound examples include 2,4,6 trimethylbenzoyldiphenylphosphine oxide, 4-n propylphenolium (2,6 dichlorobenzoinole) phosphinoxide, and the like.
  • aminocarbonyl compound examples include methyl-4- (dimethylamino) benzoate, ethinole-4 (dimethylenoreamino) benzoate, 2-nbutoxy chinenole 4 (dimethylenoreamino) benzoate, isoaminole-4 (dimethylamino) benzoate, 2 (dimethylamino)
  • examples thereof include ethyl benzoate, 4,4 ′ bis-4-dimethylaminobenzobenzophenone, 4,4′bis-4-jetylaminobenzophenone, 2,5,1bis (4-jetylaminobenzanol) cyclopentanone, and the like.
  • Compound (C) is a general photosensitive compound that is usually blended in photosensitive solder resist inks. Compound having an ethylenically unsaturated double bond in the structure. In the present invention, among these general photosensitive compounds, they are not included in the definition of the above-mentioned “carboxyl group-containing urethane resin (A)”!
  • the photosensitive compound is a photosensitive ethylenically unsaturated group-containing compound Can be used as (C) S
  • Examples of the photosensitive ethylenically unsaturated group-containing compound (C) that can be used in the present invention include those having an ethylenically unsaturated double bond in the structure and the above-mentioned “carboxyl group-containing urethane”. It is not particularly limited as long as it is not included in the definition of “resin (A)”.
  • alkyl (meth) acrylate, alkylene glycol (meth) acrylate, carboxyl group and ethylenic unsaturated A compound having a group (excluding a compound included in the definition of the carboxyl group-containing urethane resin (A)), a (meth) acrylate compound having a hydroxyl group, a nitrogen-containing (meth) acrylate compound, and the like. .
  • a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.
  • alkyl-based (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl ( (Meth) Atarylate, 2-Ethylhexyl (Meth) Atylate, Heptyl (Meth) Atylate, Hexyl (Meth) Atylate, Octyl (Meth) Atylate, Nonyl (Meth) Atylate, Decyl (Meth) Atari Rate, undecyl (meth) atarylate, dodecyl (meth) a
  • Alkyl having 1 to 22 carbon atoms such as (meth) atarylate, hexadecyl (meth) atarylate, heptadecyl (meth) attalylate, tote, hencosyl (meth) atalylate, docosyl (meth) atalylate
  • an alkyl (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms is preferred.
  • alkylene glycol (meth) acrylate examples include, for example, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene.
  • Examples of the compound having a carboxyl group and an ethylenically unsaturated group other than the carboxyl group-containing urethane resin (A) include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalates.
  • Acid / 3— (Meth) Atari Mouth Rephthalic Acid ⁇ -(Meth) Atalyloxetyl Monoester, Succinic Acid 13-(Meth) Atalyloxy Exemplify cetyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc.
  • examples of the compound having a hydroxyl group and an ethylenically unsaturated group include 2 hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono ( (Meta) Atalylate, 4-HydroxyBuylbenzene and so on.
  • compounds having a nitrogen atom and an ethylenically unsaturated group include (meth) acrylamide, N methylol (meth) acrylamide, N methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meta ) Acrylamide, N Propoxymethyl- (meth) acrylamide, N Butoxymethyl- (meth) acrylamide, N Pentoxymethyl- (meth) acrylamide, etc.
  • a quaternary ammonium salt of a dialkylamino group-containing unsaturated compound having (Q: an alkyl group having 1 to 12 carbon atoms) can be exemplified.
  • other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, norfluoroethyl methyl (meth) acrylate, 2-perfluorobutinoleethyl (meth) attaly Rate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctyl cetyl (meth) acrylate, 2-perfluoroisononyl cetyl (meth) atelier 2-perfluorononinoleethyl (meth) acrylate, 2-perfluorodecyl echenore (meth) acrylate, novoleo mouth propinorepropinore (meth) acrylate, novoleo mouth Perfluoro having an alkyl group having 1 to 20 carbon atoms such as octylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluoro
  • Peralkyloalkyl (meth) acrylates perfluoroalkyl, alkylene such as neoprenol butinoleethylene, neopreno hexenoleethylene, neoprenoethylene ethylene, perfluorodecylethylene
  • perfluoroalkyl group-containing butyl monomers such as
  • Alkoxysilyl group-containing vinyl compounds such as butyltrichlorosilane, butyltris (/ 3methoxyethoxy) silane, butyltriethoxysilane, and ⁇ (meth) ataryloxypropyltrimethoxysilane and their derivatives;
  • Examples include glycidyl group-containing (meth) acrylate, such as glycidyl (meth) acrylate, 3, 4 epoxycyclohexyl (meth) acrylate, and one or more types selected from these groups are used as appropriate. be able to.
  • fatty acid bur compound butyl acetate butyl, butyrate butyl, propionate butyl, hexane butyl, strong prill butyl, laurate butyl, palmitate butyl, stearate butyl, etc .;
  • alkyl butyl ether compounds include butyl butyl ether and ethyl butyl ether;
  • a-olephine compounds such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, etc .;
  • bur compounds include allylic compounds such as allylic acetate, arnanol alcohol, allylic benzene, and cyano cyanide, cyano cyanide, biscyclohexane, butyl methyl ketone, styrene, ⁇ -methyl styrene, 2-methyl styrene, chlorostyrene, and the like. ;
  • ethul compounds include acetylene, ethulbenzene, ethultoluene, 1-ethyl bis-l, 1-cyclohexanol, etc .;
  • a polyfunctional compound having two or more ethylenically unsaturated groups is specifically exemplified.
  • an aliphatic compound is illustrated among the compounds which have an ethylenically unsaturated group.
  • aromatic compounds are exemplified.
  • eth (propi) len oxide ethylene oxide or “propylene oxide”. The same applies below.
  • compounds of polyfunctional (meth) acrylates such as urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate are compounds.
  • (C) can be preferably used.
  • Epoxy (meth) acrylate is an esterification of the epoxy group of epoxy resin with (meth) acrylic acid to convert the functional group to (meth) acrylate.
  • Urethane (meta) atelate is
  • a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under a hydroxyl group-excess condition can be obtained by reacting with a (meth) acrylate having an isocyanate group.
  • NK Oligo MA 6, NK Oligo U— 4HA, NK Oligo U— 6HA, NK Oligo U-324A;
  • Arakawa Chemical Industries, Ltd . beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
  • KAYARAD DPHA KAYARAD DPHA2C
  • KAYARAD DPHA-40H KAYARAD D-310
  • KAYARAD D-330 KAYARAD D-330
  • SR-35 etc.
  • the photosensitive ethylenically unsaturated group-containing compound (C) is usually blended in a photosensitive solder resist ink or the like.
  • the carboxyl group-containing compound is a developability or thermosetting of the composition. It is known to improve the property, and the hydroxyl group-containing compound is known to improve the adhesion of the composition to the substrate and the developability.
  • a carboxynole group-containing compound is a composition.
  • the hydroxyl group-containing compound is preferably used to improve the adhesion of the composition to the substrate and the developability.
  • polyfunctional compounds having two or more ethylenically unsaturated groups can be used to improve the photosensitivity and resolution of the composition, and aromatic unsaturated compounds are used for the heat resistance of the coating film. It is preferably used for improving the refractive index and controlling the refractive index.
  • an oligomer type (meth) acrylate such as urethane (meth) acrylate and epoxy (meth) acrylate, for the purpose of improving the strength and scratch resistance of the coating film.
  • the use of these compounds in the present invention is particularly preferable because it can produce a photosensitive resin composition having very good developability and resolution.
  • the photosensitive ethylenically unsaturated group-containing compound (C) is preferably used in an amount of 0.;! To 300 parts by weight with respect to 100 parts by weight of the carboxyl group-containing photosensitive urethane resin (A).
  • the photosensitive ethylenically unsaturated group-containing compound (C) is used for the purpose of adjusting the photosensitivity and resolution of the photosensitive resin composition. If the amount is less than 1 part by weight, the photosensitive resin composition may be insufficient in photosensitivity, and if it exceeds 300 parts by weight, there may be a problem in flexibility.
  • thermosetting compound (D) a thermosetting aid (E), which preferably contain the thermosetting compound (D).
  • thermosetting compound (D) will be described below.
  • the thermosetting compound (D) is not particularly limited as long as it has two or more functional groups capable of reacting with the functional group contained in the carboxyl group-containing photosensitive urethane resin (A).
  • the functional group that reacts with the thermosetting compound (D) is preferably a hydroxyl group in the carboxyl group-containing photosensitive urethane resin (A) or a force oxyl group!
  • thermosetting compound (D) having at least two functional groups capable of reacting with a hydroxyl group examples include polyisocyanate compounds, amino resins, phenol resins, and polyfunctional polycarboxylic acid anhydrides. It is done.
  • the polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule.
  • examples of polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate naphthalene.
  • Polyisocyanate compounds such as isocyanate, triphenylmethane triisocyanate, polymethylenepolyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, and these polyisocyanates Burettes and isocyanurates of cyanate compounds, and these polyisocyanates Examples include adducts of compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like.
  • amino resin and phenol resin examples include an addition compound of a compound such as urea, melamine, benzoguanamine, phenol, talesols, and bisphenol and formaldehyde, or a partial condensate thereof.
  • the polyfunctional polycarboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but includes tetracarboxylic dianhydride, hexacarboxylic acid dianhydride, hexacarboxylic acid. Examples thereof include polyhydric carboxylic acid anhydrides such as acid dianhydride and maleic anhydride copolymer resin.
  • polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that become an anhydride via a dehydration reaction during the reaction have “two or more carboxylic acid anhydride groups” in the present invention. Included in “compound”.
  • examples of tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, and diphenyl.
  • maleic anhydride copolymer resins examples include SMA resin series manufactured by Sartoma Co., Ltd., and styrene maleic anhydride copolymer resins such as GSM series manufactured by Gifu Shellac Co., Ltd., p-phenylstyrene maleic anhydride copolymer resins.
  • maleic anhydride copolymer resins such as polyethylene maleic anhydride, ⁇ ] (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride-modified polyolefin (“aurolene”) Series ": manufactured by Nippon Paper Chemical Co., Ltd.) and maleic anhydride copolymer acrylic resin.
  • the thermosetting component (D) having at least two functional groups capable of reacting with a carboxyl group includes a compound (k) having two or more epoxy groups or oxetane groups, a polyfunctional vinyl Examples include ruether compounds, high molecular weight polycarpositimides, and aziridine compounds. Among these, the compound (k) having two or more epoxy groups or oxetane groups is very preferable from the viewpoint of curing speed and durability of the cured product.
  • the compound (k) having two or more epoxy groups or oxetane groups is not particularly limited as long as it is a compound having two or more epoxy groups or oxetane groups in the molecule.
  • Specific examples of the compound having an epoxy group as the compound (k) include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol epoxichlorohydride.
  • Phosphorous epoxy resin bisphenol F. Epoxychlorohydrin type epoxy resin, biphenol 'epoxyhydrin type epoxy resin, glycerin.
  • Epoxychlorohydrin adduct polyglycidyl ether polyglycidyl ether, phenol nopolac epoxy resin, cresol nopolac Type epoxy resin, dicyclopentagen type epoxy resin, naphthalene type epoxy resin, polyglycidyl ether of ethylene glycol'-epoxychlorohydrin adduct disclosed in JP-A-2001-240654, pentaerythritol Polyglycidyl ether, resorcinol diglycidinoreatenore, polybutadiene diglycidinoreatenore, hydroquinone diglycidinore ethereole, dibromoneopentinoglycoresinglycidinoreatenore, neopentinoreglycol diglycidyl ether, trimethylol Propane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A diglycidyl ether,
  • the compound (k) specifically, as a compound having an oxetane group, for example, 4, 4, 1-bis [(3 ethyl-3 oxetaninole) methoxymethinole] biphenyl, (2 ethyl 2-oxetanyl) ethanol and Examples include esterified products with terephthalic acid, etherified products of (2-ethyl-2-oxetanyl) ethanol and phenol nopolac resin, and esterified products of (2-ethynole 2-oxetanyl) ethanol and polyvalent carboxylic acid compounds.
  • an oxetane group for example, 4, 4, 1-bis [(3 ethyl-3 oxetaninole) methoxymethinole] biphenyl, (2 ethyl 2-oxetanyl) ethanol and Examples include esterified products with terephthalic acid, etherified products of (2-ethyl-2-oxet
  • Examples of the compound (k) include aliphatic epoxy compounds and epoxy compounds described in JP-A-2004-156024, JP-A-2004-315595, and JP-A-2004-323777. Since it is excellent in the softness
  • dicyclopentagen type epoxy compounds described in JP-A-2001-240654 phenol nopolac type epoxy resins, cresol nopolac type epoxy resins, biphenol 'epchlorohydrin type epoxy resins, 4, 4 '' Bis [(3-Ethyl-3-oxetanyl) methoxymethyl] biphenyl, (2-Ethyl-2-oxetanyl) ethanol esterified with terephthalic acid
  • the present invention is preferable because it is excellent in the durability of cured coatings including thermosetting, hygroscopicity and heat resistance.
  • polyfunctional butyl ether compound examples include ethylene glycol dibutene tenole, diethylene glyconoresinino enoate, triethylene glyconoresinino enoenoate, tetraethylene glyconoresinino enoenoate.
  • Pentaerythritino Resininore Tenoré Propylene Glycono Resininore Tenore, Dipropylene Glycono Resininore Tenore, Tripropylene Glycono Resinino Tenor, Neopentino Resinino Resininore Etherenole, 1,4 butanezinoresininoreatenore, 1,6--hexanezinoresinini noreatenore, glycerin divininoreatenore, trimethylonorepronon divininoreatenore, 1,4-dihydroxylcyclo Hexadiview Ether, 1,4-dihydroxymethylcyclohexane divinino elenotere, nodular quinone divinino eletenole, ethylene oxide modified hydride quinone dibule ether, ethylene oxide modified resorcin dibule ether, ethylene oxide modified bis Phenolic A dibule ether, E
  • Examples of the high molecular weight polycalposimides include the Nisshinbo Co., Ltd. Calposlite series. Of these, carpolite V-01, 03, 05, 07, and 09 are preferred because of their excellent compatibility with organic solvents.
  • aziridine compound examples include 2,2′-bishydroxymethylbutanol tris [3 1 (1 aziridinyl) propionate], 4, 4, 1 bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.
  • thermosetting compounds (D)
  • benzoxazine compounds, benzocyclobutene compounds, maleimide compounds, nadiimide compounds, allylnadiimide compounds, melamine compounds, guanamine compounds, block isocyanate compounds, etc. are cured by heating. Conversion Any compound can be used effectively.
  • These photopolymerizable groups, functional groups capable of reacting with carboxyl groups, and compounds having functional groups capable of reacting with hydroxyl groups can improve the heat resistance of the coating film after curing, and are therefore used more effectively. can do.
  • thermosetting compounds (D) may be used alone or in combination of two or more.
  • the amount of the thermosetting compound (D) used is not particularly limited as long as it is determined in consideration of the use of the photosensitive resin composition, but the carboxyl group-containing photosensitive urethane resin (A) 100 More preferably within the range of 0.1 to 100 parts by weight relative to parts by weight, still more preferably within the range of 0.5 to 80 parts by weight.
  • the crosslinking density of the photosensitive resin composition can be adjusted to an appropriate value, various physical properties of the photosensitive resin composition can be further improved.
  • the amount of the thermosetting compound (D) used is less than 0.1 part by weight, the cross-linking density of the coating after heat curing becomes too low, and the cohesive strength and durability may be insufficient. Further, when the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, and as a result, the flexibility and flexibility of the coating film are lowered, and the warpage of the substrate is remarkably deteriorated. There is.
  • thermosetting aid (E) refers to a compound that contributes directly or catalytically to the curing reaction during thermosetting.
  • thermosetting aid (E) is appropriately selected depending on the thermosetting compound (D) to be used. Moreover, the curing conditions for the carboxyl group-containing photosensitive urethane resin (A) and the thermosetting compound (D) can be appropriately selected depending on the thermosetting compound (D) and the thermosetting aid (E) used.
  • thermosetting aid (E) examples include tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethinole) phenol, N-methylbiperazine, and the like. Its salts;
  • carboxylic acid hydrazide examples include succinic acid hydrazide and adipic acid hydrazide.
  • thermosetting aid (E) when an epoxy compound is used as the thermosetting compound (D), the thermosetting aid (E) includes dicyandiamide, carboxylic acid hydrazide, imidazoles, and diazabicyclo compounds.
  • the use of a kind is preferable because the thermosetting reaction proceeds more efficiently and the resistance of the coating film is excellent.
  • the thermosetting aid (E) is used in an amount of 0.;! To 10 parts by weight based on 100 parts by weight of the carboxyl group-containing photosensitive urethane resin (A). It is preferable to use within the range of 0.5 to 8 parts by weight. If the amount used is less than 0.1 parts by weight, sufficient effects as a thermosetting aid cannot be exhibited, and eventually the cohesive strength and durability of the coating film may be insufficient. In addition, if the amount used is more than 10 parts by weight, excess thermosetting aid may remain in the system, which may deteriorate various physical properties of the coating film such as bleeding and deterioration of insulation properties.
  • the photosensitive resin composition of the present invention contains a resin other than the carboxyl group-containing photosensitive urethane resin (A) and the photosensitive ethylenically unsaturated group-containing compound (C) as necessary.
  • Resins other than carboxyl group-containing photosensitive urethane resin (A) and photosensitive ethylenically unsaturated group-containing compound (C) include acrylic resin, polyester resin, urethane resin, urea resin, urethane urea resin, epoxy resin, polyamide resin. And polyimide resin.
  • those containing a carboxyl group are preferred from the viewpoint of developability, and are also compatible with a carboxyl group-containing photosensitive urethane resin (A) and a photosensitive ethylenically unsaturated group-containing compound (C).
  • a resin other than the carboxyl group-containing photosensitive urethane resin (A) or the photosensitive ethylenically unsaturated group-containing compound (C) it can be used alone or in combination.
  • the photosensitive resin composition of the present invention includes, as an optional component, a solvent, a dye, a pigment, a flame retardant, an antioxidant, a polymerization inhibitor, a leveling agent, a moisturizing agent as long as the purpose is not impaired.
  • a viscosity modifier an antiseptic, an antibacterial agent, an antistatic agent, an antiblocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic shielding agent, a filler and the like can be added.
  • insulating materials such as circuit protection films, coverlay layers, interlayer insulating materials
  • materials that can become hot around the circuit such as printed wiring board adhesives and support substrates
  • a flame retardant it is preferable to use a flame retardant together.
  • Examples of the flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium phosphate, amido ammonium phosphate, amido ammonium phosphate, phosphorus phosphate Phosphate compounds such as acid strength rubamate and polyphosphate strength rubamate, polyphosphate compounds, red phosphorus, organophosphate compounds, phosphazene compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoranes Phosphorus flame retardants such as compounds, phosphoramide compounds, triazine compounds such as melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea Which nitrogen system Flame retardants, silicone flame retardants such as silane compounds, halogenated
  • non- and rogen-based flame retardants such as phosphorus-based flame retardants and nitrogen-based flame retardants.
  • photosensitive resin composition It is preferable to use a phosphazene compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, etc. that are more effective in flame retardancy depending on the combined use.
  • these flame retardants can be used alone or in combination.
  • the photosensitive resin composition of the present invention and the cured product thereof are characterized by excellent alkali developability, they are suitable for applications in which a coating film forming process including photocuring, alkali development, and post-cure is used. Can be used. In addition, it has excellent solder heat resistance and coating film resistance, as well as excellent flexibility and flexibility, so it is particularly suitable for use in solder-resist inks and photosensitive cover lay film applications for flexible printed wiring boards. Can do.
  • the photosensitive resin composition of the present invention can be applied to a metal, ceramics, glass, plastic, wood, slate, etc. as a substrate, and is not particularly limited.
  • plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, and melamine resin.
  • the shape of the substrate is not particularly limited, and includes a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber-like material.
  • the photosensitive resin composition of the present invention can be hardened by a known radiation curing method to form a cured product, and as an active energy ray, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm is used. Can do.
  • a thermionic emission gun, a field emission gun, or the like can be used as the electron beam source.
  • a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as an ultraviolet ray or a visible light source (light source) of 400 to 500 nm. .
  • an ultra-high pressure mercury lamp, a xenon mercury lamp, a methanol lamp, and a ride lamp are often used because of the point light source and the stability of luminance.
  • the active energy dose to be irradiated is preferably a force S that can be set in a timely range from 5 to 200 Omj / cm 2 , 50 to easily manageable in the process, and a range from 1000 mj / cm 2 .
  • these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.
  • the photosensitive resin composition of the present invention is used as a photo solder resist, a liquid resist ink dissolved in a solvent, a dry film resist obtained by previously drying a solvent, Can be used.
  • the photosensitive resin composition of the present invention may be subjected to radiation curing after coating the substrate and volatilizing the solvent by natural or forced drying.
  • the coating may be naturally or forcibly dried after the coating is cured by radiation, but it is preferred that the coating is cured by natural or forced drying.
  • the solvent does not evaporate during handling until the application to the substrate, such as the storage process and coating process, is completed.
  • a high boiling point solvent is preferable.
  • carbitol acetate methoxypropyl acetate, cyclohexanone, diisoptyl ketone, or the like.
  • liquid resist inks in consideration of storage stability and handling, store in advance separately from the curing agent, and mix and use the curing agent as needed before coating. There is also.
  • the photopolymerization initiator (B), the thermosetting compound (D), and the thermosetting auxiliary agent (E) are stored separately from the others, if necessary. It can also be used as a night type.
  • a solvent having a low boiling point is preferred as the solvent to be used because it is necessary to dry the solvent completely in a short time unlike the above-described liquid resist ink.
  • the dry film created on the separate film is laminated to a copper circuit or the like formed on polyimide, bubbles and the like are removed and adhered to the circuit by lamination or vacuum lamination.
  • this laminating step there may be a case where the radiation curing is performed through a separate film, or a case where the development pattern is brought into contact after the separation film is peeled to perform the radiation curing.
  • the development pattern may be contaminated. Therefore, a dry film resist with a low dry film tack is required. .
  • the photosensitive resin composition of the present invention can be used as needed. Since tack can be reduced, it can be usefully used as a dry film resist.
  • the photosensitive resin composition of the present invention forms a pattern by developing after radiation curing, and forms a film having excellent resistance by thermosetting as post-cure.
  • Post cure is preferably 100 ° C to 200 ° C for 30 minutes to 2 hours.
  • active energy rays after post-curing it is possible to irradiate active energy rays after post-curing as necessary. Irradiation with active energy rays after post-cure can further improve solder heat resistance.
  • GPC gel permeation chromatography
  • HPC-8020 manufactured by Tosoh Corporation was used.
  • GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in their molecular sizes.
  • THF tetrahydrofuran
  • LF-604 manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mmlD XI 50 mm size
  • the column temperature was 40 ° C
  • Mw weight average molecular weight
  • the ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 863 g / eq
  • the weight-average molecular weight in terms of polystyrene is 15400
  • the acid value of the resin solid content by actual measurement was 73 mgK OH / g.
  • the ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 931 g / eq
  • the weight-average molecular weight in terms of polystyrene is 18800
  • the acid value of the resin solid content measured is Was 65 mgK OH / g.
  • the ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 920 g / eq
  • the polystyrene equivalent weight average molecular weight is 16500
  • the actually measured acid value of the resin solid content is 62 mg KOH / g.
  • the ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared according to this production example is 840 g / eq, the weight average molecular weight in terms of polystyrene is 17100, and the acid content of the resin solid content is measured.
  • the price was 7211 3 ⁇ 4 1 ⁇ 0 ⁇ 1 / ⁇ .
  • dimethylolbutanoic acid manufactured by Nippon Kasei Co., Ltd.
  • Carboxyl group-containing photosensitive prepared by this production example
  • the equivalent weight of the ethylenically unsaturated group in the resin solid content of the curable urethane resin was 870 g / eq
  • the weight average molecular weight in terms of polystyrene was 25500
  • the acid value of the resin solid content measured was 70 mgK OH / g.
  • the ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 851 g / eq
  • the weight average molecular weight in terms of polystyrene is 22600
  • the acid value of the resin solid content by actual measurement was 74 mgK OH / g.
  • Table 1 shows the physical properties of the carboxyl group-containing photosensitive urethane resin obtained in Production Examples 1 to 13;
  • a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, and cresol nopolac epoxy resin with epoxy equivalent of 218g / eq manufactured by Toto Kasei Co., Ltd .: YDCN-702 330 parts were charged, heated and melted at 90 to 100 ° C., and stirred. Next, 120 parts of attalinoleic acid, 0.6 part of hydroquinone and 5 parts of dimethylbenzylamine were added, and the mixture was heated to 115 ° C. with stirring in the presence of oxygen and reacted for 12 hours.
  • the ethylenically unsaturated group equivalent of the resin solid content of the acid anhydride-modified cresol nopolac resin prepared by this production example is 319 g Zeq, the weight average molecular weight in terms of polystyrene is 11000, and the acid value of the resin solid content measured is It was 85 mgKOH / g.
  • the monomer solution was charged into a dropping funnel installed in the flask, and the monomer solution in the dropping funnel was dropped into the flask over 2 hours while stirring the flask at 90 ° C. in a nitrogen atmosphere. Dripping Stirring was continued at 90 ° C. even after the completion, and 0.5 part of azobisisoptyronitrile was charged into the flask after 2 hours from the end of the dropwise addition. After 1 hour, 0.5 part of azobisisobutyronitrile was again added to the flask, and stirring was continued for another 2 hours. Thereafter, the flask was cooled to stop the reaction. A small amount of sampling was performed to obtain a carboxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 18700 and an acid value of 98 mgKOH / g for the resin solid.
  • the ethylenically unsaturated group equivalent of the resin solid content of the acrylic resin prepared according to this production example is 863 g / eq
  • the weight average molecular weight in terms of polystyrene is 2200
  • the acid value of the resin solid content measured is 70 mg KOH / g. Met.
  • a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, polyethylene tetramethylene dallicol (PTG850: Hodogaya Chemical Co., Ltd .: hydroxyl value 129 mgK OH / g), 212 parts, ethylene Glycol 75 parts, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, and stirred for 10 hours at 100 ° C under nitrogen flow The mixture was stirred to carry out a half esterification reaction.
  • 212 parts ethylene Glycol 75 parts
  • pyromellitic anhydride manufactured by Daicel Chemical Industries, Ltd.
  • dimethylbenzylamine 2 parts dimethylbenzylamine
  • the ethylenically unsaturated group equivalent of the resin solid content of the acid anhydride-modified urethane resin prepared by this production example is 896 g / eq
  • the weight average molecular weight in terms of polystyrene is 18800
  • the acid value of the resin solid content actually measured is 72 mg KOH. / g.
  • Acid anhydride-modified urethane tree prepared according to this production example The ethylenically unsaturated group equivalent of the resin solids of the fat was 765 g / eq, the weight average molecular weight in terms of polystyrene was 21400, and the acid value of the resin solids measured was 67 mgKOH / g.
  • Table 2 shows the summary of physical properties of the resins obtained in Production Examples 14 to 18;
  • Resin varnish obtained in Production Example 1 (Carboxyl group-containing urethane prepolymer solution) 100.0 parts, Irgacure as a photopolymerization initiator 907 (manufactured by Chinoku 'Specialty' Chemicals Co., Ltd .: 2 Methyl 1 [4 ( Methylthio) phenyl] 2 monoreforino 1 propane) 2.
  • Production Examples 2 to 13 The resin varnishes obtained in Example 13 were blended in the same proportions as in Example 1 to prepare photosensitive resin compositions containing the respective resins.
  • Production Example The resin varnish obtained in L4 to 18 was blended in the same ratio as in Example 1 to prepare a photosensitive resin composition containing each resin.
  • the obtained photosensitive resin composition was evaluated as follows. [Create sample A]
  • the obtained photosensitive resin composition was applied onto a polyimide film (Kapton 100H: manufactured by Toray DuPont Co., Ltd .: 25 ⁇ m thick) so that the dry film thickness was 20 ⁇ m, and hot air at 80 ° C. After drying for 30 minutes in a drier, it was cooled to room temperature. This is sample A.
  • sample A After irradiating sample A with ultraviolet light of 300mJ / cm 2 using an ultraviolet exposure device (Usio Electric Co., Ltd .: “UVC-2534 / 1MN LC3—AA08”, 120W / cm metal halide lamp, 1 lamp), It was heat-cured (post-cured) for 1 hour in a hot air dryer at 150 ° C. The obtained cured film was cooled to room temperature. This is sample B.
  • an ultraviolet exposure device Usio Electric Co., Ltd .: “UVC-2534 / 1MN LC3—AA08”, 120W / cm metal halide lamp, 1 lamp
  • Step Tablet manufactured by Kodak Co., Ltd. 21 steps of Step Tablet (manufactured by Kodak Co., Ltd.) were brought into close contact with Sample A, and the same UV exposure apparatus used when Sample B was prepared was exposed to UV light with an integrated light amount of 150 mj / cm 2 . This is sample C.
  • a step tablet is a film that is shielded from light so that its optical density increases sequentially in 21 steps. When this is in close contact with the test coating, it is irradiated with light from the top of the film, and then developed. Depending on the resolution of the test coating film, the number of steps at which the coating film peels changes. This serves as an index for evaluating the resolution of the test coating film.
  • Sample B was cut into 100 pieces of lmm x lmm grids on the cured coating film and subjected to a peeling test using cello tape (registered trademark). (2) The peeled state of the checkered cut pieces was observed and evaluated according to the following criteria.
  • Sample B was bent 180 degrees with the cured coating surface facing outward, and the coating state at that time was evaluated according to the following criteria.
  • Sample C was developed with a 1% aqueous sodium carbonate solution at a spray pressure of 2 kg / cm 2 for 60 seconds.
  • the number of steps in which the coating film was swollen by the developer was defined as the number of swelling steps, and the number of steps in which the coating film was thoroughly washed away by the developer was defined as the number of stripping steps. It can be said that the lower the number of peeling steps, the higher the developing speed and the better the developability. Using this number of stripping steps, developability was judged according to the following criteria.
  • resolution step the sharper the pattern can be formed in the actual pattern forming process and the better the resolution.
  • resolution step resolution was judged according to the following criteria.
  • Resin varnish obtained in Production Example 1 (solution of carboxyl group-containing urethane prepolymer) 100.0 parts, 2 methyl-1 [4 (methylthio) phenyl] 2-morpholino 1 propane (Irgacure 1 907 as a photopolymerization initiator) Chino 'Specialty' Chemicals Co., Ltd.) 2.
  • Production Examples 2 to 13 The resin varnish obtained in Example 13 was blended in the same ratio as in Example 14 to prepare a photosensitive resin composition containing each resin.
  • Production Examples 14 to 18 The resin varnish obtained in 18 was blended in the same ratio as in Example 14 to prepare a photosensitive resin composition containing each resin.
  • the obtained photosensitive resin composition was evaluated as follows.
  • Sample D was used in place of Sample A, and the cured film was obtained by processing in the same manner as in the preparation of Sample 1 in Evaluation 1. This is sample E.
  • Sample D was used in place of Sample A, and the cured film was obtained by processing in the same manner as in the preparation of Sample 1 in Evaluation 1. This is sample F.
  • the obtained photosensitive resin composition was applied to a 38 m thick polyethylene terephthalate (hereinafter also referred to as “PET”) separator film so that the dry film thickness was 20 m, and hot air at 80 ° C. After drying for 30 minutes in a dryer, the mixture was cooled to room temperature. Next, after irradiating UV light with an integrated light intensity of 300 mj / cm 2 using the same UV exposure equipment used when creating Sample B in Evaluation 1, heat cure (post-cure) with a hot air dryer at 150 ° C. ) The obtained cured film was cooled to room temperature, and the cured coating film was peeled off from the separator film. This is sample G. [0215] [Evaluation of finger touch]
  • Sample E was used in place of sample B, and the flexibility test was performed and evaluated in the same manner as in evaluation 1.
  • Sample F was used instead of Sample C, and a developability test was conducted in the same manner as in Evaluation 1, and the evaluation was performed according to the following criteria.
  • Sample E was cut into a square of 5 cm ⁇ 5 cm, left on a flat table at 25 ° C. and a humidity of 50% with the cured coating surface facing upward for 12 hours.
  • the height at which the four corners of the square were lifted from the platform was measured, the average value was calculated, and evaluated according to the following criteria. The smaller the value, the better the sample warp.
  • Sample G was folded 180 degrees and the same part was folded 180 degrees on the opposite side.
  • the state of the coating film at that time was judged according to the following criteria.
  • the resin compositions of the present invention are excellent in adhesion, flexibility and developability as well as Evaluation 1, and have a dry coating with less tack. It was found that it was excellent in workability. Furthermore, it has been found that it has performance that could not be achieved by the conventional technology (Comparative Examples 6 to 10), which has both the resistance of the coating film and flexible performance such as substrate warpage and flexibility.
  • Production Examples 2 to 13 The resin varnishes obtained in 13 were blended in the same proportions as in Example 27 to prepare solder resist inks containing the respective resins.
  • Examples 40 to 52 Production Examples 2 to 13: The resin varnishes obtained in 13 were blended in the same proportions as in Example 40 to prepare photosensitive solder resist inks containing the respective resins.
  • Production Examples 14 to 18 The resin varnishes obtained in 18 were blended in the same proportions as in Example 40 to prepare photosensitive solder resist inks containing the respective resins.
  • the obtained photosensitive solder resist ink was evaluated as follows.
  • Example 21 to 40 comparative example so that the film thickness after drying is 20 m on the peeled surface of a 38 Hm-thickness separator PET film with one side peelable!
  • the photosensitive solder resist ink obtained from !! ⁇ 20 was applied and dried by hot air drying at 80 ° C for 20 minutes.
  • the surface of the photosensitive resin composition on this film and a 25 ⁇ m thick PET film are bonded together, so that both sides of the photosensitive resin composition are sandwiched between PET films.
  • a solder resist was created.
  • sample H was prepared by heat-curing for 1 hour in a hot air dryer at 150 ° C.
  • Sample H was used instead of Sample E, and a solvent resistance test was conducted and evaluated in the same manner as in Evaluation 2.
  • Sample H was used instead of Sample C, and the developability test was conducted in the same manner as in Evaluation 1, and the judgment was made according to the following criteria.
  • the coating film is partially swollen or peeled off.
  • the film has swelling or peeling.
  • Examples 27-52 comparative examples; Apply the photosensitive solder resist ink obtained from !! to 20 onto a 38-inch separator PET film so that the dry film thickness is 20 m.
  • Sample J was evaluated for flame retardancy according to the UL Subject94V method, and the results were judged according to the following criteria.
  • Comparative Examples 11 and 12 are excellent in coating film resistance, developability and heat resistance, but as a flexible insulating protective film used for flexible printed wiring boards and the like. The most important physical property, flexibility, could not be satisfied.
  • Comparative Examples 13 to 15 the coating film resistance and developability were inferior instead of excellent flexibility.
  • the photosensitive resin composition of the present invention Examples 27 to 39 was able to satisfy all of these physical properties essential as a flexible insulating protective layer at a high level.
  • the carboxyl group-containing photosensitive urethane resin of the present invention that does not have an ester skeleton derived from half esterification with an acid anhydride in the main chain has the same urethane main chain because the main chain is chemically stable. Compared with Comparative Examples 14 and 15 which are skeletons, especially excellent coating film resistance. Features that can exhibit adhesion and flexibility unique to urethane resin while maintaining heat resistance.
  • the carboxyl group-containing photosensitive urethane resin of the present invention has a photosensitive group and a carboxyl group in the side chain, so that the amount of the carboxyl group is small! Since these side chain functional groups are more reactive than when directly connected to the main chain, they can exhibit excellent resolution and coating film resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition de résine photosensible contenant une résine d'uréthane photosensible contenant un groupe carboxyle (A), un initiateur de photopolymérisation (B) et un composé contenant un groupe insaturé éthyléniquement photosensible (C). Cette composition de résine photosensible est caractérisée en ce que la résine d'uréthane photosensible contenant un groupe carboxyle (A) est une résine obtenue en faisant réagir un groupe hydroxy dans un prépolymère d'uréthane contenant un groupe hydroxy (c) avec un groupe anhydride acide dans un composé contenant un groupe anhydride acide (d). Le prépolymère d'uréthane contenant un groupe hydroxy (c) est obtenu en faisant réagir un groupe carboxyle dans un prépolymère d'uréthane contenant un groupe carboxyle (a), qui est obtenu en faisant réagir un polyol polymère (e), un composé d'acide carboxylique (f) ayant deux groupes hydroxy dans une molécule et un groupe diisocyanate (g) en tant qu'ingrédients essentiels, avec un groupe époxy ou un groupe oxéthane dans un composé (b) ayant un groupe époxy ou un groupe oxéthane et un groupe insaturé éthyléniquement. Cette composition de résine photosensible a une sensibilité excellente à un rayon d'énergie actif et permet de former un motif fin. Un film de revêtement durci de la composition de résine photosensible a une souplesse, propriété isolante, adhérence, résistance à la chaleur de soudure, résistance du film de revêtement et capacité ignifuge excellentes et est ainsi utilisé de façon appropriée pour une résine de photosoudure.
PCT/JP2007/071373 2006-11-02 2007-11-02 Composition de résine photosensible, produit durci de celle-ci et procédé de production de résine photosensible WO2008053985A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020097011224A KR101536366B1 (ko) 2006-11-02 2007-11-02 감광성 수지 조성물과 그의 경화물, 및 감광성 수지의 제조방법
CN2007800409539A CN101535896B (zh) 2006-11-02 2007-11-02 感光性树脂组合物及其固化物、以及感光性树脂的制备方法
JP2008542192A JP5298855B2 (ja) 2006-11-02 2007-11-02 感光性樹脂組成物とその硬化物、及び感光性樹脂の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-298361 2006-11-02
JP2006298361 2006-11-02
JP2007252808 2007-09-28
JP2007-252808 2007-09-28

Publications (1)

Publication Number Publication Date
WO2008053985A1 true WO2008053985A1 (fr) 2008-05-08

Family

ID=39344324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/071373 WO2008053985A1 (fr) 2006-11-02 2007-11-02 Composition de résine photosensible, produit durci de celle-ci et procédé de production de résine photosensible

Country Status (5)

Country Link
JP (1) JP5298855B2 (fr)
KR (1) KR101536366B1 (fr)
CN (1) CN101535896B (fr)
TW (1) TWI432897B (fr)
WO (1) WO2008053985A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173848A (ja) * 2008-01-22 2009-08-06 Shinrikibi Kagi Kofun Yugenkoshi 放射により硬化・現像可能なポリウレタンとそれを含有する放射線により硬化・現像可能なフォトレジスト組成物
JP2009230076A (ja) * 2008-03-25 2009-10-08 Kaneka Corp 新規な感光性樹脂組成物、それから得られる感光性樹脂組成物溶液、感光性フィルム、絶縁膜及び絶縁膜付きプリント配線板
JP2010053231A (ja) * 2008-08-27 2010-03-11 Aica Kogyo Co Ltd 樹脂組成物および成型物
JP2010523756A (ja) * 2007-10-11 2010-07-15 エルジー・ケム・リミテッド ウレタン基を含むフルオレン系樹脂重合体、その製造方法、およびこれを含むネガ型感光性樹脂組成物
WO2010110338A1 (fr) * 2009-03-27 2010-09-30 東洋インキ製造株式会社 Composition colorante photosensible et filtre coloré
JP2011227246A (ja) * 2010-04-19 2011-11-10 Tokyo Ohka Kogyo Co Ltd ネガ型感光性樹脂組成物、感光性ドライフィルム、及び受光装置
JP2012042601A (ja) * 2010-08-17 2012-03-01 Jsr Corp 感光性接着剤組成物、前記組成物を用いる積層体または固体撮像素子の製造方法、および固体撮像素子
CN102414617A (zh) * 2009-04-27 2012-04-11 太阳控股株式会社 光固化性热固化性树脂组合物
JP2013522687A (ja) * 2010-03-22 2013-06-13 エルジー・ケム・リミテッド 光硬化性及び熱硬化性を有する樹脂組成物、並びにドライフィルムソルダレジスト
JP2014209260A (ja) * 2014-06-25 2014-11-06 日立化成株式会社 感光性樹脂組成物、感光性フィルム、レジストパターンの形成方法及び永久レジスト
JP2018203820A (ja) * 2017-05-31 2018-12-27 凸版印刷株式会社 水性ウレタン樹脂分散体及びそれを用いたフィルム及びシート
JP2019211540A (ja) * 2018-05-31 2019-12-12 太陽インキ製造株式会社 光導波路形成用光硬化性熱硬化性樹脂組成物、その硬化物および光導波路、並びに、光導波路を備えた光電気混載基板、導波路型光スプリッタ、および光モジュール
JP2020079359A (ja) * 2018-11-13 2020-05-28 株式会社Adeka 硬化性樹脂組成物
WO2020148237A1 (fr) * 2019-01-14 2020-07-23 Voestalpine Stahl Gmbh Revêtement de vernis à base de phosphate ayant une bonne résistance aux agents d'estampage alcalins
JP2020537706A (ja) * 2017-10-20 2020-12-24 エルジー・ケム・リミテッド インク組成物

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6028360B2 (ja) * 2011-06-29 2016-11-16 東洋インキＳｃホールディングス株式会社 感光性樹脂組成物とその硬化物、及び感光性樹脂の製造方法
JP6343449B2 (ja) * 2011-07-20 2018-06-13 株式会社カネカ 新規な導電層一体型ｆｐｃ
CN103926791B (zh) * 2013-01-15 2016-11-16 太阳油墨制造株式会社 固化性树脂组合物、其干膜和固化物以及使用它们的印刷电路板
CN103969951A (zh) * 2013-01-30 2014-08-06 太阳油墨制造株式会社 导电性树脂组合物及导电电路
CN103616800B (zh) * 2013-10-21 2016-08-10 溧阳市东大技术转移中心有限公司 感光固化树脂组合物
WO2016068254A1 (fr) * 2014-10-30 2016-05-06 昭和電工株式会社 Résine polyuréthane contenant un groupe hydroxyle, résine polyuréthane et résine (méth)acrylate d'uréthane utilisant ladite résine polyuréthane contenant un groupe hydroxyle à titre de matériau de départ, procédés de production desdites résines, composition protectrice, et composition de résine durcissable par uv
KR102366946B1 (ko) 2016-11-18 2022-02-25 가부시키가이샤 아리사와 세이사쿠쇼 감광성 수지 조성물, 해당 감광성 수지 조성물을 사용한 솔더 레지스트 필름, 플렉시블 프린트 배선판 및 화상 표시 장치
CN110268325B (zh) * 2017-02-07 2023-06-06 株式会社有泽制作所 感光性树脂组合物及使用其的阻焊膜、柔性印刷布线板
KR102444761B1 (ko) * 2017-02-07 2022-09-20 가부시키가이샤 아리사와 세이사쿠쇼 감광성 수지 조성물, 해당 감광성 수지 조성물을 사용한 솔더 레지스트 필름, 플렉시블 프린트 배선판 및 화상 표시 장치
JP7348177B2 (ja) * 2018-06-29 2023-09-20 株式会社カネカ パターン印刷用レジスト組成物及びパターン形成方法
CN109100918B (zh) * 2018-07-25 2020-08-04 深圳市华星光电技术有限公司 一种感光性树脂组合物及其制备方法和应用
TWI662014B (zh) * 2019-01-02 2019-06-11 Daxin Materials Corporation 寡聚物及包含其之感光性樹脂組成物、感光性間隙物與塗料
CN111072962B (zh) * 2019-12-20 2022-11-04 上海维凯光电新材料有限公司 耐高温光纤涂料用光敏聚酰亚胺的合成与应用
JP7441528B2 (ja) * 2021-08-30 2024-03-01 互応化学工業株式会社 接着剤

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02296819A (ja) * 1989-05-10 1990-12-07 Hitachi Maxell Ltd ポリウレタン樹脂およびその製造方法
JP2002311579A (ja) * 2001-04-12 2002-10-23 Okamoto Kagaku Kogyo Kk 感光性組成物
JP2003122001A (ja) * 2001-10-15 2003-04-25 Nippon Kayaku Co Ltd 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
JP2003192760A (ja) * 2001-12-25 2003-07-09 Showa Highpolymer Co Ltd 感光性樹脂および感光性レジストインキ組成物
WO2005014682A1 (fr) * 2003-08-07 2005-02-17 Huntsman Advanced Materials (Switzerland) Gmbh Polyurethanes photoreticulables
JP2005048143A (ja) * 2003-07-31 2005-02-24 Fuji Photo Film Co Ltd 重合性組成物
JP2007002030A (ja) * 2005-06-21 2007-01-11 Fujifilm Holdings Corp エラストマー、感光性ソルダーレジスト組成物及び感光性ソルダーレジストフィルム、並びに、永久パターン及びその形成方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4462500B2 (ja) * 2003-03-06 2010-05-12 日本化薬株式会社 感光性樹脂組成物及びその硬化物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02296819A (ja) * 1989-05-10 1990-12-07 Hitachi Maxell Ltd ポリウレタン樹脂およびその製造方法
JP2002311579A (ja) * 2001-04-12 2002-10-23 Okamoto Kagaku Kogyo Kk 感光性組成物
JP2003122001A (ja) * 2001-10-15 2003-04-25 Nippon Kayaku Co Ltd 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
JP2003192760A (ja) * 2001-12-25 2003-07-09 Showa Highpolymer Co Ltd 感光性樹脂および感光性レジストインキ組成物
JP2005048143A (ja) * 2003-07-31 2005-02-24 Fuji Photo Film Co Ltd 重合性組成物
WO2005014682A1 (fr) * 2003-08-07 2005-02-17 Huntsman Advanced Materials (Switzerland) Gmbh Polyurethanes photoreticulables
JP2007002030A (ja) * 2005-06-21 2007-01-11 Fujifilm Holdings Corp エラストマー、感光性ソルダーレジスト組成物及び感光性ソルダーレジストフィルム、並びに、永久パターン及びその形成方法

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010523756A (ja) * 2007-10-11 2010-07-15 エルジー・ケム・リミテッド ウレタン基を含むフルオレン系樹脂重合体、その製造方法、およびこれを含むネガ型感光性樹脂組成物
JP2009173848A (ja) * 2008-01-22 2009-08-06 Shinrikibi Kagi Kofun Yugenkoshi 放射により硬化・現像可能なポリウレタンとそれを含有する放射線により硬化・現像可能なフォトレジスト組成物
JP2009230076A (ja) * 2008-03-25 2009-10-08 Kaneka Corp 新規な感光性樹脂組成物、それから得られる感光性樹脂組成物溶液、感光性フィルム、絶縁膜及び絶縁膜付きプリント配線板
JP2010053231A (ja) * 2008-08-27 2010-03-11 Aica Kogyo Co Ltd 樹脂組成物および成型物
WO2010110338A1 (fr) * 2009-03-27 2010-09-30 東洋インキ製造株式会社 Composition colorante photosensible et filtre coloré
JP2010230957A (ja) * 2009-03-27 2010-10-14 Toyo Ink Mfg Co Ltd カラーフィルタ用着色組成物及びカラーフィルタ
CN102365586A (zh) * 2009-03-27 2012-02-29 东洋油墨Sc控股株式会社 感光性着色组合物及滤色器
CN102365586B (zh) * 2009-03-27 2013-10-30 东洋油墨Sc控股株式会社 感光性着色组合物及滤色器
CN102414617B (zh) * 2009-04-27 2014-04-30 太阳控股株式会社 光固化性热固化性树脂组合物
CN102414617A (zh) * 2009-04-27 2012-04-11 太阳控股株式会社 光固化性热固化性树脂组合物
JP2013522687A (ja) * 2010-03-22 2013-06-13 エルジー・ケム・リミテッド 光硬化性及び熱硬化性を有する樹脂組成物、並びにドライフィルムソルダレジスト
JP2011227246A (ja) * 2010-04-19 2011-11-10 Tokyo Ohka Kogyo Co Ltd ネガ型感光性樹脂組成物、感光性ドライフィルム、及び受光装置
JP2012042601A (ja) * 2010-08-17 2012-03-01 Jsr Corp 感光性接着剤組成物、前記組成物を用いる積層体または固体撮像素子の製造方法、および固体撮像素子
JP2014209260A (ja) * 2014-06-25 2014-11-06 日立化成株式会社 感光性樹脂組成物、感光性フィルム、レジストパターンの形成方法及び永久レジスト
JP2018203820A (ja) * 2017-05-31 2018-12-27 凸版印刷株式会社 水性ウレタン樹脂分散体及びそれを用いたフィルム及びシート
JP2020537706A (ja) * 2017-10-20 2020-12-24 エルジー・ケム・リミテッド インク組成物
US11214699B2 (en) 2017-10-20 2022-01-04 Lg Chem, Ltd. Ink composition
JP7118145B2 (ja) 2017-10-20 2022-08-15 エルジー・ケム・リミテッド インク組成物
JP2019211540A (ja) * 2018-05-31 2019-12-12 太陽インキ製造株式会社 光導波路形成用光硬化性熱硬化性樹脂組成物、その硬化物および光導波路、並びに、光導波路を備えた光電気混載基板、導波路型光スプリッタ、および光モジュール
JP2020079359A (ja) * 2018-11-13 2020-05-28 株式会社Adeka 硬化性樹脂組成物
JP7203577B2 (ja) 2018-11-13 2023-01-13 株式会社Adeka 硬化性樹脂組成物
WO2020148237A1 (fr) * 2019-01-14 2020-07-23 Voestalpine Stahl Gmbh Revêtement de vernis à base de phosphate ayant une bonne résistance aux agents d'estampage alcalins

Also Published As

Publication number Publication date
KR20090082264A (ko) 2009-07-29
KR101536366B1 (ko) 2015-07-13
JPWO2008053985A1 (ja) 2010-02-25
CN101535896B (zh) 2012-06-13
CN101535896A (zh) 2009-09-16
JP5298855B2 (ja) 2013-09-25
TW200844657A (en) 2008-11-16
TWI432897B (zh) 2014-04-01

Similar Documents

Publication Publication Date Title
WO2008053985A1 (fr) Composition de résine photosensible, produit durci de celle-ci et procédé de production de résine photosensible
JP4683182B2 (ja) 感光性熱硬化性樹脂組成物、並びにレジスト被覆プリント配線板及びその製造法
TWI704169B (zh) 硬化性樹脂組成物，乾薄膜，硬化物及印刷電路板
JP5384149B2 (ja) 難燃性を有する反応性化合物を用いた活性エネルギー線硬化型樹脂組成物並びにその硬化物
CN106814538B (zh) 固化性树脂组合物、干膜、固化物和印刷电路板
JP2010117452A (ja) 感光性難燃樹脂組成物
WO2010117056A1 (fr) Résine photodurcissable et composition de résine photodurcissable
KR20180129868A (ko) 경화성 수지 조성물, 드라이 필름, 경화물 및 프린트 배선판
JP2009271290A (ja) リジッドプリント配線板用感光性樹脂組成物
JP5056749B2 (ja) 難燃剤および難燃性樹脂組成物
WO2007032326A1 (fr) Composition de résine photosensible et objet durci obtenu à partir de cette composition
JP2013076833A (ja) 感光性樹脂組成物とその硬化物、及び感光性樹脂の製造方法
TWI819431B (zh) 阻焊劑組合物、乾膜、印刷線路板及其製造方法
JP5493347B2 (ja) 難燃性樹脂組成物
JP7066634B2 (ja) 硬化性組成物、主剤および硬化剤、ドライフィルム、硬化物、および、プリント配線板
JP2013182174A (ja) 感光性樹脂組成物
JP2019179232A (ja) ドライフィルム、硬化物およびプリント配線板
JP2013137373A (ja) 感光性樹脂組成物とその硬化物、及び感光性樹脂の製造方法
CN111708251B (zh) 固化性树脂组合物、干膜、固化物和电子部件
CN114945611A (zh) 固化性组合物、其干膜和固化物
WO2021200258A1 (fr) Composition durcissable, produit durci et carte de circuit imprimé
JP7498549B2 (ja) 積層硬化体、硬化性樹脂組成物、ドライフィルム、および、積層硬化体の製造方法
WO2023163209A1 (fr) Composition de résine durcissable, film sec, produit durci et carte imprimée
WO2023190393A1 (fr) Produit durci et carte de circuit imprimé
WO2021210570A1 (fr) Composition de résine durcissable, film sec, article durci et carte à circuits imprimés

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780040953.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07831107

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008542192

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1020097011224

Country of ref document: KR

122 Ep: pct application non-entry in european phase

Ref document number: 07831107

Country of ref document: EP

Kind code of ref document: A1