WO2002023275A1 - Composition de resine a sechage ultraviolet et encre reserve soudure photo - Google Patents

Composition de resine a sechage ultraviolet et encre reserve soudure photo Download PDF

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Publication number
WO2002023275A1
WO2002023275A1 PCT/JP2001/007944 JP0107944W WO0223275A1 WO 2002023275 A1 WO2002023275 A1 WO 2002023275A1 JP 0107944 W JP0107944 W JP 0107944W WO 0223275 A1 WO0223275 A1 WO 0223275A1
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WO
WIPO (PCT)
Prior art keywords
curable resin
ethylenically unsaturated
ultraviolet
resin composition
unsaturated monomer
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PCT/JP2001/007944
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English (en)
Japanese (ja)
Inventor
Hiroko Daido
Soichi Hashimoto
Original Assignee
Goo Chemical Co., Ltd.
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Publication date
Application filed by Goo Chemical Co., Ltd. filed Critical Goo Chemical Co., Ltd.
Priority to AU2001286219A priority Critical patent/AU2001286219A1/en
Priority to JP2002527862A priority patent/JP4705311B2/ja
Publication of WO2002023275A1 publication Critical patent/WO2002023275A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/141—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/144—Polymers containing more than one epoxy group per molecule
    • 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

  • UV curable resin composition Photo solder resist ink containing the same
  • the present invention relates to an ultraviolet-curable resin composition used for a photo solder resist ink, a protective film for a color filter, an image element, and the like, which has an ultraviolet-curing property and a thermosetting property and can be developed with a dilute alkaline aqueous solution.
  • the liquid photo solder resist ink disclosed in Japanese Patent Publication No. 61-2436969 can be imaged with a dilute alkaline aqueous solution, and is an ultraviolet-curable, soluble in dilute alkaline aqueous solution. It consists of a resin, a photopolymerization initiator and an epoxy compound. A sufficient amount of lipoxyl groups is introduced into the ultraviolet curable resin to enable development with a dilute aqueous alkali solution.
  • the ultraviolet-curable resin composition of the present invention has been made in view of the above problems, and an object of the present invention is to provide an ultraviolet-curable resin yarn composition excellent in developability, resolution, development width, and heat resistance. . That is, the ultraviolet-curable resin composition of the present invention:
  • An epoxy compound component containing the derivative (b) is reacted with an ethylenically unsaturated monomer (c) having a carboxyl group, and the resulting intermediate product is added to a saturated or unsaturated polybasic anhydride.
  • UV-curable resin obtained by reacting (d);
  • the ultraviolet curable resin as the component (A) can improve the heat resistance, the developability and the softening point of the resin composition.
  • a further object of the present invention is to provide a photosolder resist ink containing the above resin composition.
  • This photo solder resist ink can be developed with a dilute alkaline aqueous solution and provides a solder resist on a substrate that exhibits excellent substrate adhesion and electrolytic corrosion resistance, and excellent solder heat resistance and gold plating resistance.
  • the development width means a range of predrying conditions that can maintain the developability, and is also referred to as a predrying control width or a predrying allowable range.
  • the ultraviolet-curable resin (A) used in the present invention contains an epoxy group-containing monomer obtained by polymerizing an ethylenically unsaturated monomer component containing an ethylenically unsaturated monomer (i) having an epoxy group.
  • the polymer (a) and an epoxy compound component (b) containing an epoxy group-containing disocyanurate derivative are reacted with an ethylenically unsaturated monomer (c) having a carboxyl group to obtain an intermediate product.
  • a saturated or unsaturated polybasic acid anhydride (d) By reacting the product with a saturated or unsaturated polybasic acid anhydride (d).
  • Examples of the epoxy group-containing polymer (a) include an ethylenically unsaturated monomer (i) having an epoxy group, and an ethylenically unsaturated monomer copolymerizable with the monomer (i).
  • a copolymer obtained by polymerizing an ethylenically unsaturated monomer component containing (ii) can be used.
  • an ethylenically unsaturated monomer (i) having an epoxy group and a compound (iii) having two or more ethylenically unsaturated groups in one molecule are used as the epoxy group-containing polymer (a).
  • Polymerizing the ethylenically unsaturated monomer component contained A copolymer obtained by the above method may be used.
  • an ethylenically unsaturated monomer having an epoxy group (i), a compound having two or more ethylenically unsaturated groups in one molecule (iii), A copolymer obtained by polymerizing an ethylenically unsaturated monomer component containing an ethylenically unsaturated monomer (ii) copolymerizable therewith may be used.
  • the ethylenically unsaturated monomer (i) having an epoxy group introduces an epoxy group into the epoxy group-containing polymer (a).
  • the addition of the ethylenically unsaturated monomer having a carboxyl group imparts photocurability to the epoxy group-containing polymer (a) by an ethylenically unsaturated double bond.
  • an ethylenically unsaturated monomer having an epoxy group (i) a compound having two or more ethylenically unsaturated groups in one molecule (iii), and an ethylenically unsaturated monomer copolymerizable therewith.
  • an ethylenically unsaturated monomer component containing the polymer (ii) the content of the ethylenically unsaturated monomer (i) is determined by the amount of ethylene used in the production of the epoxy group-containing polymer (a). It is preferably in the range of 40 to 99.9 mol%, more preferably 55 to 95 mol%, based on the total amount of the unsaturated monomer components.
  • the content of the ethylenically unsaturated monomer (i) should be It is 100 mol% in the total amount of the ethylenically unsaturated monomer component used for producing the group-containing polymer (a).
  • the ultraviolet curable resin composition of the present invention exhibits particularly excellent photocurability and resolution, and a cured film finally formed using the composition has excellent heat resistance.
  • it can be particularly preferably used as a permanent film.
  • this permanent film is used as a solder resist Shows particularly excellent solder heat resistance and electric corrosion resistance.
  • Examples of the ethylenically unsaturated monomer (i) include, for example, glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methinole (meth) acrylate, and the like.
  • Derivatives alicyclic epoxy derivatives of (meth) acrylate, —methyldaricidyl (meth) acrylate and monoaryldiglycidyl isocyanurate and the like can be used. These can be used alone or in combination.
  • (meth) acrylic acid is a general term for acrylic acid and methacrylic acid
  • (meth) atari is a general term for atari and methacrylic.
  • the compound (iii) having two or more ethylenically unsaturated groups in one molecule is an optional component, and is intended to further improve the heat resistance and softening point of the ultraviolet-curable resin composition of the present invention. Used for primary purposes. When this compound (iii) is used, its content should be 0.1 to 1 (3 mol%) in the total amount of the ethylenically unsaturated monomer component used for producing the epoxy group-containing polymer (a). Within this range, the polymerization reaction for producing the epoxy group-containing polymer (a) can proceed in good conditions, and is particularly effective in preventing gelation.
  • the cured film formed by the UV-curable resin composition of the present invention has excellent heat resistance, and particularly when used as a solder resist, exhibits particularly excellent solder heat resistance. %, It is optimal because it has both the effect of improving heat resistance and good polymerizability.
  • Compounds having two or more ethylenically unsaturated groups in one molecule include, for example, diethylene glycol di (meth) acrylate, triethylene Polyglycol (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di-resin (meth) acrylate, polypropylene glycol / resid (meth) acrylate, ⁇ ⁇ ⁇ Modified dimethacrylate, bisphenol ⁇ ⁇ ⁇ Adduct di (meth) acrylate, bisphenol FEO adduct di (meth) acrylate, bisphenol A ⁇ ⁇ Adduct di (meth) acrylate, bisphenol AEOPO adduct Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol
  • a compound having three or more ethylenically unsaturated groups in one molecule such as trimethylolpropane tri (meth) acrylate, pentaerythritol noretri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythryl Tonorepenta (meth) acrylate, dipent taerythritol hexa (meth) acrylate, polybasic acid and hydroxy
  • the compound (iii) contained in the epoxy group-containing polymer (a) reinforces the main chain thereof, and has effects such as improvement of solder heat resistance, adjustment of softening point, and improvement of development width.
  • di (meth) acrylate is used in the above compound (iii). Is preferred.
  • the di (meth) acrylate it is particularly preferable to use, for example, those having at least one oxyanolekilen unit such as oxyethylene and oxypropylene in the molecule.
  • the solder heat resistance of the curable resin composition can be improved, and a particularly excellent development width can be provided.
  • the preferred number of oxyalkylene units in one molecule of di (meth) atarylate is 1 to 40, preferably 4 to 30, and more preferably 4 to 10.
  • the reactivity during the production of the ultraviolet-curable resin (A) is stabilized, the development range of the ultraviolet-curable resin composition of the present invention is widened, and the cured film has excellent solder heat resistance. It will be shown.
  • a di (meth) acrylate having a bisphenol skeleton together with an oxyalkylene unit is used, it is preferable since it has particularly excellent solder heat resistance and particularly excellent development width.
  • di (meth) acrylate having an oxyalkylene unit usable as the compound (iii) ethylene glycol methacrylate or polyethylene glycol dimethacrylate represented by the following general formula (1) can be used. :
  • n in the formula is an integer of 1 to 40.
  • propylene glycol dimethacrylate or polypropylene glycol dimethacrylate represented by the following general formula (2) may be used.
  • CH 2 C-CO-0-(CH-CH z O) m (CH 2 -CHO)
  • n -OC-C CH 2 (2)
  • n and m are each an integer of 0 or more.
  • n and m are each an integer of 0 or more.
  • ethylene glycol diacrylate or polyethylene glycol diacrylate represented by the following general formula (3) can be used:
  • n in the expression is an integer of 1 to 40.
  • di (meth) acrylate having an oxyalkylene unit and a bisphenol skeleton a compound represented by the following general formula (4) may be used.
  • n and m in the equation are integers greater than or equal to 0, and + of n + m is
  • Compounds of this type include, for example, 2,2-bis [4- (methacryloxyethoxy) pheninole] propane, 2,2,1-bis [41- (methacryloxy ethoxy) phenyl] propane, or 2-bis [4- (methacryloxy.polyethoxy) phenyl] propane.
  • n and m in the formula are integers of 0 or more, respectively, and the value of n + m is 1 to 40.
  • Compounds of this type include, for example, 2,2-bis [4- (ataryloxyethoxy) pheninole] propane, 2,2-bis [4-1 (a-acryloxy'dietkin) pheninole] propane, or 2 , 2-bis [4- (acryloxy'polyethoxy) phenyl] propane, and dimethacrylate of bisphenol A polyethylene glycol polypropylene glycol adduct.
  • NK ester 4G represented by the formula (1) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 200 dimethacrylate) Rate (average value of n: 4)
  • NK ester 9G represented by the formula (1) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene dalicol # 400 dimethacrylate (average value of ⁇ : 9))
  • Ester 9 PG represented by the formula (2) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polypropylene glycol # 400 dimethacrylate (average value of m + n: 7)
  • NK S represented by the formula (3) Ter A-200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 200 diacrylate (average value of n: 4)
  • NK ester A-400 represented by formula (3) (trade name, new
  • NK ester A- 600 (trade name of the formula (3), Shin-Nakamura Chemical Co., Ltd., average polyethylene glycol # 600 Jiatarireto (n Value: 14)).
  • NK ester mono-BPE-100 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., 2 , 2-screw [4 Tacryloxyethoxy) phenyl] propane (average value of m + ri: 2.6)
  • NK ester-one BPE—20 ⁇ (trade name, manufactured by Shin-Nakamura Ihgaku Kogyo Co., Ltd., 2, 2-bis [41- (Methacryloxy 'ethoxy) feninole] propane (average of m + n: 4)
  • NK ester-one BPE-50 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., 2,2-bis [4-1 ( Methacryloxy.polyethoxy) phenyl] propane (strictly average value of m + n: 10)
  • NK ester A—BPE—4 represented by the formula
  • Jetoxy) feninole] propane (average value of m + n: 4)
  • Blemmer 43DB-40B (Nippon Yushi Co., Ltd. Bisphenol / A polyethylene glycol polypropylene glycol adduct dimethacrylate).
  • the ethylenically unsaturated monomer (ii) copolymerizable with the ethylenically unsaturated monomer (i) having an epoxy group and the compound (iii) having two or more ethylenically unsaturated groups in one molecule is It is an optional component and is used for adjusting the photocurability of the ultraviolet-curable resin composition of the present invention and adjusting the physical properties of the cured film, if necessary.
  • Such ethylenically unsaturated monomers (ii) are not particularly limited. Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and ptynole (meth) acrylate.
  • linear or branched aliphatic, aromatic, or alicyclic but may have some unsaturated bonds in the ring
  • acrylates, alkoxyalkyl (meth) atalylates, maleimide compounds, etc. can control the hardness and oiliness of the film of the ultraviolet curable resin composition and the hardness of the finally formed resist. It is suitable because it is easy to adjust.
  • ethylenically unsaturated monomer (ii) As described above, Is not particularly limited content, ethylenically unsaturated monomer component total amount of 1-6 0 mole 0/0, more preferably from 1 'to 5 5 mol%, particularly preferably 1 0-5
  • the content is preferably 0 mol%, and within this range, the amount of ethylenically unsaturated groups introduced into the ultraviolet-curable resin (A) can be sufficiently ensured.
  • the hardness, hydrophilicity, and the like of the cured film can be particularly easily adjusted.
  • the epoxy group-containing polymer (a) can be obtained by a known polymerization method, for example, solution polymerization emulsion polymerization.
  • solution polymerization for example, an ethylenically unsaturated monomer comprising the above-mentioned ethylenically unsaturated monomer (i) and, if necessary, ethylenically unsaturated monomer (ii) or compound (iii)
  • a polymerization initiator is added to a body component in an appropriate organic solvent, and the mixture is heated and stirred under a stream of water. Further, a polymerization method under reflux may be employed.
  • Examples of the organic solvent used in the above polymerization method include ketones such as methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene, and ethyl acetate, butyl acetate, and cellosolve acetate.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • aromatic hydrocarbons such as toluene and xylene
  • ethyl acetate, butyl acetate, and cellosolve acetate such as sorbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and dialkyl glycol ethers can be used. These can be used alone or in combination.
  • polymerization initiator for the polymerization examples include t-butylhydronoxide, g-butylinoleoxide, lauroinoleoxide, benzoinolenoside, and diisopropinoleno.
  • Peroxy acids such as peroxydicarbonate and azo compounds such as azobisisobutyronitrile, 2,2,2-methylbisazobisisobutyrate, and azobiscyanovaleronitrile can be used. These are used alone or in combination be able to.
  • the ultraviolet-curable resin (A) of the present invention comprises, as an epoxy compound component containing the epoxy group-containing polymer (a) obtained as described above and an epoxy group-containing isocyanurate derivative (b), a carboxyl group. It can be produced by reacting a group-containing ethylenically unsaturated monomer (c) with an addition reaction of the resulting intermediate product with a saturated or unsaturated polybasic acid anhydride (d).
  • the addition of the ethylenically unsaturated monomer (c) having a carboxyl group allows the ethylenically unsaturated monomer to be added to the epoxy compound component containing the epoxy group-containing isocyanate, the rate derivative (b) and the epoxy group-containing polymer (a). Photocurability due to heavy bonds is imparted.
  • the epoxy group-containing isocyanurate derivative (b) and the epoxy group-containing isocyanurate derivative (b) used for producing the ultraviolet-curable resin (A) were used to remarkably evolve the characteristics of the epoxy group-containing isocyanurate derivative (b). ),
  • the amount of the epoxy group-containing cyanurate derivative (b) is preferably 1 to 50% by weight, more preferably 1 to 35% by weight, and particularly preferably 2 to 20% by weight. % By weight.
  • the amount of the epoxy group-containing polymer ( a ) is preferably 50 to 9%. It is 9% by weight, more preferably 65 to 99% by weight, particularly preferably 80 to 98% by weight.
  • the epoxy compound component used for producing the ultraviolet-curable resin (A) may contain another epoxy compound together with the component (a) and the component (b).
  • the epoxy group-containing isocyanuric acid in the epoxy compound component used to produce the ultraviolet-curable resin (A) The preferred amount of the derivative (b) is within the above range.
  • epoxy group-containing isocyanurate derivative (b) examples include triglycidyl isocyanurate, monoaryldiglycidyl isocyanurate U ⁇ , and diaryl monoglycidyl isocyanurate. These can be used alone or in combination.
  • TEP IC (trade name, manufactured by Nissan Chemical Co., Ltd., triglycidyl isocyanurate), monoallyl diglycidyl isocyanuric acid (trade name, manufactured by Shikoku Chemicals Co., Ltd., monoaryl diglycidyl isocyanate) Cyanurate), diaryl monoglycidyl isocyanuric acid (trade name, diaryl monoglycidyl isocyanurate, manufactured by Shikoku Chemicals Co., Ltd.) and the like.
  • triglycidyl isocyanate as the epoxy group-containing isocyanurate derivative (b).
  • epoxy compounds in the epoxy compound component used for producing the ultraviolet-curable resin (A), if necessary, together with the epoxy group-containing polymer ( a ) and the epoxy group-containing isocyanurate derivative (b) include: For example, phenol novolak epoxy resin, cresol nopolak epoxy resin, bisphenol A epoxy resin, bisphenol A-novolak epoxy resin, bisphenol F epoxy resin, YX4000 (Yuka Shell Epoxy Co., Ltd.) ), Alicyclic epoxy resin (for example, “E HPE-3150” manufactured by Daicel Chemical Industries, Ltd.), and tris (hydroxyphenyl) methane-based multifunctional epoxy resin (EPPN-502H, manufactured by Nippon Kayaku Co., Ltd., and Dow Chemica) Textex-1 742 and XD—9053 manufactured by Le Co., Ltd.), hydrogenated bisphenol A type epoxy resin, Tajen - a phenol type epoxy resin and naphthalene type epoxy resin or the like can be used.
  • phenol novolak epoxy resin
  • —As a carboxyl-containing ethylenically unsaturated monomer (C) Is, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxetylsuccinic acid, 2- (meth) acryloyloxetil phthalic acid, —carboxyethyl Atarilate, Atariloyloxyshetti / Resuccinate, 2-Propernoic Acid, 3- (2-Norboxoxytoxy) -13-Oxypropylester, 2- (Meth) 'acryloyloxyshethyltetrahydrophthalic acid, 2- Those having only one ethylenically unsaturated group such as (meth) acryloylonoxetyl hexahydrophtalic acid, and pentaerythritol tri (meth) acrylate, trimethylol lipepandi (meth) acrylate, dip
  • the compounding amount of the carboxyl group-containing ethylenically unsaturated monomer (c) is determined based on the amount of ethylenically unsaturated monomer per mole of epoxy group in the epoxy compound component used for producing the above-mentioned ultraviolet curable resin ( ⁇ ).
  • the amount of the carboxyl group of the compound (c) is 0.7 to 1.2 mol, more preferably 0.9 to 1.1 mol, particularly preferably 0.95 to 1.1 mol. It is preferable to be decided. Within this range, the ultraviolet-curable resin composition ( ⁇ ) of the present invention exhibits a particularly wide development width, and is less affected by the residual unreacted ethylenically unsaturated monomer (c) having a carboxyl group.
  • saturated or unsaturated polybasic anhydride (d) for example, succinic anhydride, methinoresuccinic anhydride, maleic anhydride, citraconic anhydride, gnophthalic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride Dibasic acid anhydrides such as methinoletetrahydrophthalic anhydride, ice-free methylnadic acid, hexahydrohydrous phthalic anhydride, and methylhexahydrophthalic anhydride; and trimellitic anhydride, pyromellitic anhydride, and anhydride Acid anhydrides of three or more basic acids such as benzophenone tetracarboxylic acid, methylcyclohexenetetracarboxylic anhydride and the like can be used. These can be used alone or in combination. ⁇
  • the above-mentioned saturated or unsaturated polybasic acid anhydride (d) has a main purpose of giving an acid value to the ultraviolet-curable resin, redispersing with a dilute alkali aqueous solution, providing remelting needles, and providing thermosetting properties.
  • Used as The amount used can be selected so that the acid value of the UV-curable resin obtained by adding the polybasic acid anhydride is in the range of 25 to 15 Omg KOH / g, particularly preferably 45 to: LO Omg KOHZg. preferable. Within this range, the UV-curable resin composition of the present invention exhibits particularly good 3 ⁇ 4 developability, and the cured film formed thereby has particularly excellent electrical properties, corrosion resistance or water resistance. . Optimum results are obtained when the acid value is in the range of 50 to 85 mg KOHZg.
  • the ultraviolet-curable resin (A) of the present invention comprises an epoxy compound containing the epoxy group-containing polymer (a) obtained as described above and an epoxy group-containing isocyanurate derivative (b).
  • the ethylenically unsaturated monomer having a ropoxyl group (c) is reacted, and at least two isocyanate groups are added to the resulting intermediate product in addition to a saturated or unsaturated polybasic anhydride (d).
  • the compound can be produced by reacting the isocyanate compound (e).
  • Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. , 4,1-diphenylemethane diisocyanate, tonoleidine diisocyanate, lysine diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl to Xamethylene diisocyanate, trifluoromethane triisocyanate, polymethylene polyphenyl polyisocyanate, and the like can be used.
  • the amount of the isocyanate compound (e) used is a secondary hydroxyl group in a medium product obtained by reacting the above-mentioned epoxy compound component with an ethylenically unsaturated monomer (c) having a propyloxyl group.
  • the amount of the isocyanate group of the isocyanate compound (e) is preferably 0.01 to 0.90 mol, more preferably 0.05 to 0.40 mol, per 1 mol of the hydroxyl group. Is preferably performed. Within this range, the solubility of the ultraviolet curable resin (A) in the diluent (D) is particularly good.
  • the addition reaction of the ethylenically unsaturated monomer (C) having a carboxyl group and the saturated or unsaturated polybasic anhydride (d) can be carried out by using a known method.
  • the addition reaction of an ethylenically unsaturated monomer having a carboxyl group (C) is carried out, for example, by adding an epoxy compound containing an epoxy group-containing polymer (a) and an epoxy group-containing isocyanurate derivative (b) to an epoxy compound component.
  • the optional isocyanate compound (e) is reacted in addition to the above-mentioned saturated or unsaturated polybasic acid anhydride (d), for example, the epoxy group-containing polymer (a) and the epoxy group-containing isocyanurate derivative (b ) Is reacted with a solvent solution of the epoxy compound component containing the carboxyl group-containing ethylenically unsaturated monomer (c), and then a saturated or unsaturated polybase is added to the resulting intermediate product.
  • the isocyanate compound (e) is reacted before, after or at the same time as the reaction of the addition reaction of the acid anhydride (d).
  • This reaction can be carried out, for example, by adding an organotin compound such as dibutyltin diallate or a tertiary amine such as benzyldimethylamine as a catalyst by a conventional method, or under a catalyst blended in the previous reaction with or without addition.
  • the reaction may be carried out by heating and stirring at a reaction temperature of 20 to 100 ° C.
  • the weight average molecular weight of the ultraviolet-curable resin (A) prepared as described above is not particularly limited, but a preferable range is a weight average molecular weight of 3,000 to 400,000. Within this range, the ultraviolet-curable resin composition of the present invention is: Particularly, it has both excellent sensitivity and resolution.
  • the compounding amount of the ultraviolet-curable resin (A) is simultaneously adjusted so as to ensure good sensitivity and working characteristics of the ultraviolet-curable resin composition of the present invention and good physical properties of the finally formed resist. It is desirably 10 to 80% by weight based on the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent in the diluent (D). Within this range, the ultraviolet-curable resin composition of the present invention has particularly excellent ultraviolet-curability, and the tackiness of the preliminary dried film is particularly reduced.
  • Examples of the epoxy compound (B) having two or more epoxy groups in one molecule include a poorly solvent-soluble epoxy compound, a solvent-soluble epoxy compound, and the like.
  • a phenol novolak epoxy resin and a cresol novolak epoxy Resin bisphenol A type epoxy resin, bisphenol A-nopolak type epoxy resin, bisphenol F type epoxy resin, triglycidyl isocyanurate, monolinoleic glycidyl isocyanurate, YX400 (oiled shell epoxy) Sorbitol polyglycidyl ether, N-glycidyl type epoxy resin, alicyclic epoxy resin (for example, "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd.), polyol polyglycidyl ether / le compound, glycidyl ester compound , N-glycidyl type epoxy resin Tris (hydroxyphenyl) methane-based polyfunctional epoxy resin (EPPN-502H manufactured by Nippon Kayaku Co., Ltd.
  • iced bisphenol A A type epoxy resin a dicyclopentadiene-phenol-type epoxy resin, a naphthalene type epoxy resin, a butyl polymer having an epoxy group, and the like can be used. These can be used alone or in combination, or after cross-linking modification.
  • phenol nopolak epoxy resin It is preferable to use cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolak type epoxy resin, triglycidyl isocyanurate, and YX400.
  • the compounding amount of the epoxy compound (B) in the ultraviolet-curable resin composition of the present invention is based on the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent in the diluent (D) that is simultaneously mixed.
  • the content is preferably 0.1 to 50% by weight. Within this range, the ultraviolet-curable resin composition of the present invention exhibits particularly excellent thermosetting properties and has a particularly wide development width.
  • Examples of the photopolymerization initiator (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl oleate / re, benzoin ethie / leate phenol, benzoin isopropynoleate, and acetophenone, 2,2-dimethoxy.
  • 2-pheninoleacetophenone 2,2-diethoxy 2-phenienoleacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphen-2-acetophenones such as hexylphenic / reketone, and 2-methylanthraquinone, 2-amyl Anthraquinones such as anthraquinone, and 2,4-dimethinorethioxanthone, 2,4-getylthioxanthone,
  • photopolymerization accelerators such as benzoic acid or tertiary amines such as P-dimethylaminobenzoic acid ethyl ester, P-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. It may be used in combination with an agent.
  • photopolymerization initiators are blended alone or in combination with one another as appropriate.
  • sensitizers for laser exposure methods for example, coumarin derivatives such as 7-ethylamino-4-methyl coumarin, 4,6-ethylamino 7-ethylaminocoumarin, carbocyanine dyes, xanthene dyes, bis ( . eta 5 one 2, 4-cyclopentadiene-1 one ⁇ f le) - bis (2, 6-Jifunore silo one 3- (1 H- pyro one Norre one 1- Inore) Single-phenylene Honoré) titanium, etc. It is also possible to appropriately use meta-methacrylates and the like, and the ultraviolet-curable resin composition of the present invention can be made into a visible or near-infrared curable resin composition.
  • the amount of the photopolymerization initiator (C) in the ultraviolet-curable resin composition of the present invention may be adjusted so as to obtain a good balance between the photocurability and the physical properties of the obtained solder resist. It is desirable that the content is 0.1 to 30% by weight based on the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent in D). Within this range, the ultraviolet-curable resin composition of the present invention exhibits particularly excellent ultraviolet-curability, and also has particularly excellent heat resistance and electric corrosion resistance of the cured film.
  • a photopolymerizable ethylenically unsaturated monomer or an organic solvent can be used alone or in combination.
  • the photopolymerizable ethylenically unsaturated monomer include, for example, 2-hydroxyxethyl (meth) acrylate, 2-hydroxypropinole (meth) acrylate, and N-bininolepyro. Ridone, (meth) acryloyl morpholine, methoxy tedolaethylene glycol.
  • Organic solvents include, for example, ethanol, pulp alcohol, Linear, branched, secondary or polyhydric alcohols such as isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butynoleanol, hexanol, ethylene glycol, etc., and methyl alcohol Ketones such as tyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; petroleum oils such as the Suzul series (manufactured by Maruzen Petrochemical) and the Solbesso series (manufactured by Exxon Chemical) Aromatic mixed solvents and cellosolves such as cellosolve and butyl sorbitol, and power rubitols such as carbitol and butyl carbitol; and propylene glycol oleanol quinoleate ethereol such as propylene daricol methyl ether; and ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • the photopolymerizable ethylenically unsaturated monomer used as the diluent (D) dilutes the UV-curable resin (A), etc. to make it easy to apply, and adjusts the acid value to improve photopolymerizability. give.
  • the organic solvent used as the diluent (D) is prepared by dissolving and diluting the ultraviolet-curable resin (A), etc., so that it can be applied as a liquid and dried to form a film.
  • the diluent (D) and the above-mentioned photopolymerizable ethylenically unsaturated monomer and other components having photosensitivity must be added to the ultraviolet-curable resin composition of the present invention.
  • the total amount in the case of blending is 50% by weight in the total amount of the components of the ultraviolet-curable resin composition of the present invention excluding the organic solvent similarly blended as the diluent (D). It is desirable that the ratio be less than / 0 . this If more than 50% by weight of 0 / o is added, the pre-dried film will have too high surface tack and the negative mask on which the pattern is drawn will be applied directly to the dried film surface to expose it. This may cause problems such as soiling.
  • the organic solvent used as the diluent (D) ′ like the above photopolymerizable ethylenically unsaturated monomer is the ultraviolet-curable resin composition of the present invention, particularly, It is an essential component when used as a developable photo solder resist ink. It must be selected so that it volatilizes quickly during pre-drying and does not remain on the pre-dried film.
  • the amount of the organic solvent in the composition is desirably 5% or more of the total components of the ultraviolet-curable resin composition of the present invention. If the amount is less than this, application of the composition tends to be difficult. Note that the preferable amount is different depending on the application method, and it is necessary to appropriately adjust the amount according to the application method. Therefore, the upper limit of the amount is not particularly limited.
  • the UV-curable resin composition of the present invention includes, in addition to the above-mentioned components, thermosetting components such as block dissociates and amino resins, and UV-curable epoxy (meth) atalylates such as bisphenol A type and phenol novolak.
  • thermosetting components such as block dissociates and amino resins
  • UV-curable epoxy (meth) atalylates such as bisphenol A type and phenol novolak.
  • Type cresol nopolak type, alicyclic epoxy resin to which (meth) acrylic acid is added, or furthermore maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc.
  • the ultraviolet curable resin composition of the present invention may contain an epoxy resin curing agent, a curing accelerator, a filler, a coloring agent, a leveling agent, an adhesion promoter, a thixotropic agent, and a polymerization inhibitor, if necessary.
  • Various additives such as an antihalation agent, a flame retardant, an antifoaming agent, a dispersion stabilizer, a polymer dispersant, and an antioxidant may be added.
  • the ultraviolet-curable resin composition of the present invention is prepared, for example, by a known kneading method using a three-roll, ball mill, sand mill or the like with respect to each compounding component and additives.
  • a part of the above components (A) to (D) for example, a part of the component (D) and the component (B) are mixed and dispersed in advance to obtain a first mixture.
  • A), (C) and a part of the components (D) are preliminarily mixed and dispersed to obtain a second mixture.
  • the first and second mixtures are mixed and prepared so as to have the above composition. May be adopted.
  • an ultraviolet curable resin composition can be used as a photo solder resist ink suitably used for manufacturing a printed wiring board having a fine and high-density conductor pattern.
  • a resist pattern can be formed on a printed wiring board or a substrate.
  • this photo solder-resist ink is cured and molded into an appropriate pattern on a printed wiring board or substrate.
  • a film is formed, and a resist pattern is formed by the cured film.
  • An example for forming a resist pattern on a substrate will be described below.
  • the photo solder resist ink is immersed on the substrate by spraying, spin coating, roll coating, curtain coating or screen printing.
  • preliminary drying is performed at, for example, 60 to 120 ° C. to form a preliminary dried film.
  • a negative mask with a pattern is placed directly or indirectly on the surface of the pre-dried film, and a chemical lamp, low-pressure mercury lamp, medium-pressure, mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, or metal halide is applied through the negative mask.
  • a pattern is formed by development. Further, for example, 120 to 180.
  • a resist pattern consisting of a cured film having excellent film strength, hardness and chemical resistance can be obtained.
  • Examples of the alkaline solution used in the above-mentioned developing step include a 15% aqueous solution of sodium carbonate, an aqueous solution of carbonic acid carbonate, an aqueous solution of ammonium carbonate, an aqueous solution of sodium hydrogencarbonate, an aqueous solution of potassium hydrogencarbonate, an aqueous solution of ammonium hydrogencarbonate, an aqueous solution of sodium hydroxide.
  • aqueous solution of a hydroxide power, an aqueous solution of ammonium hydroxide, or an ice solution of lithium hydroxide can be used.
  • the alkali: monoethanolamine ⁇ Min other than, diethanol ⁇ Min, triethanolamine ⁇ 20 Min, mono isopropanoyl no Honoré amine, diisopropanolamine ⁇ Min, may be used organic amines such as Torii isopropanol ⁇ Min. These can be used alone or in combination.
  • the solvent for the alkaline solution not only water alone, but also a mixture of water and a hydrophilic organic solvent such as lower alcohols can be used.
  • the ultraviolet curable resin composition or the photo solder resist of the present invention A so-called dry film resist can be formed by forming a film of the ink on the surface of the support.
  • the thickness of the film is preferably 10 to 100 / im, and a film having a thickness of 5 to 100 ⁇ such as polyethylene terephthalate can be used as the support.
  • the coating film of the ultraviolet curable resin composition or the photo solder resist ink can be formed by applying a purple ray curable resin composition or a photo solder resist ink on a support film and drying it.
  • the ultraviolet-curable resin composition of the present invention is particularly preferably used for a photo solder resist ink, but is not limited thereto.
  • a color filter protective film for example, an azo lake-based resin.
  • Organic pigments such as insoluble azo and phthalocyanine, and inorganic pigments such as miril blue, iron oxide and cobalt, and appropriate pigments or dyes such as oil-soluble dyes, basic dyes and dispersible dyes. It can also be used as a composition for preparing a color filter element.
  • the polymerization was carried out at 80 ° C for 5 hours while heating and stirring under a nitrogen stream to obtain a 50% epoxy group-containing copolymer solution.
  • TEP IC-S triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd.
  • hydroquinone 50 parts of acrylic acid
  • dimethylbenzylamine 0 parts
  • Add 2 parts perform addition reaction at 100 ° C for 24 hours, then add 45 parts of tetrahydrophthalic anhydride and 115 parts of carbitol acetate, and react at 100 ° C for 3 hours to obtain 50%
  • An ultraviolet curable resin solution (A-2) was obtained.
  • TEP IC— was added to the above 50% epoxy group-containing copolymer solution.
  • 56 parts of tetrahydrophthalic anhydride and 178 parts of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 50% UV-curable resin solution (A-4). .
  • Epiclone N-680 (trade name; One lunovolak epoxy resin, epoxy equivalent: 214) 214 parts of carbitol acetate heated and dissolved in 214 parts were stirred and mixed with 74 parts of acryloyl acid, 0.1 part of hydroquinone and 0.1 part of benzyldimethylamine. 7 parts were added, and the reaction was carried out at 90 to 100 ° C for 24 hours by a conventional method. To this reaction solution, 95 parts of carbitol acetate was added, and the mixture was stirred and cooled to obtain an epoxy acrylate solution. Subsequently, 76 parts of tetrahydrophthalic anhydride and 87 parts of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 60% UV-curable resin solution (E-2).
  • UV curable resin liquids (A-1) to (A-6) produced in the above synthesis examples
  • Example 1 A liquid photo solder resist ink that can be developed with a dilute aqueous alkaline solution was prepared.
  • UV curable resin solution (E- 2) 50 Dipentaerythritol 55 55 55 55 55 55 55 55 55 55 55 55 55
  • Epiclone N-695 (trade name) is Cresol novolac epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.
  • YX4 000 (trade name) has an epoxy equivalent of 195 Epoxy compound manufactured by Yuka Shell Epoxy Co., Ltd.
  • TEP IC-S (trade name) is a triglycidyl isocyanurate manufactured by Nissan Chemical Industries, Ltd. having an epoxy equivalent of 100.
  • Irgacure I-907 (trade name) is a photopolymerization initiator (2-methyl-11- [4-methylthio (phenyl)] — 2-morpholinopropane 111-one) manufactured by CHIPAGIGI CORPORATION.
  • “Kyakua I DETX-S” (trade name) is a photopolymerization initiator (2,4 getylthioxanthone) manufactured by Nippon Kayaku Co., Ltd.
  • “Modaflow” (trade name) is Monsantone Earth leveling agent.
  • Susol 1 500 (trade name) is a petroleum-based aromatic mixed solvent manufactured by Maruzen Petrochemical Co., Ltd.
  • ORC HMW680GW Model No., manufactured by Oak Manufacturing Co., Ltd., 'Depressurized contact type double-sided exposure machine'
  • the mask on which the pattern was drawn was placed directly on the pre-dried film surface and adhered under reduced pressure, and irradiated with 150m jZcni 2 ultraviolet rays. The degree of adhesion when the mask was removed under each drying condition was evaluated.
  • the evaluation method of surface tackiness is as follows.
  • a resist ink is applied by screen printing to the entire surface of a copper-clad laminate consisting of a 35- ⁇ m-thick copper-foil glass-epoxy base material to volatilize the solvent80.
  • Pre-drying was performed under drying conditions of 10, 20, 30, 40, 50, 60, 70, 80 minutes and 90 minutes at C, and eight types of test specimens having a pre-dried film with a thickness of 20 m were obtained. It was created for each ink. Then, a mask on which the pattern was drawn was directly placed on the surface of the pre-dried film and brought into close contact with each other, and the resist ink was irradiated with an optimal exposure amount of ultraviolet light. Next, develop with 1% aqueous sodium carbonate solution as a developing solution to form developability and pattern The condition was observed.
  • the evaluation method of the development width is as follows.
  • the resist ink is applied by screen printing to the entire surface of a copper-clad laminate made of a 35- ⁇ m-thick copper foil glass-epoxy substrate, and dried at 80 ° C for 20 minutes to volatilize the solvent.
  • test pieces having a preliminary dried film having a thickness of 20 ⁇ 2 were prepared for each ink.
  • ORC HMW 680 GW model number, reduced pressure contact type double-sided exposure machine manufactured by Oak Manufacturing Co., Ltd.
  • step tablet PHOTEC 2 1-stage exposure test mask manufactured by Hitachi Chemical Co., Ltd.
  • vacuum adhesion is thereby arranged and irradiated with each of 5 0 and 1 5 0 mj Z cm 2 ultraviolet.
  • the number of steps remaining after the development was determined by developing with an aqueous 1% sodium carbonate solution as a developer, and used as a measure of exposure sensitivity.
  • test pieces were prepared by the following steps (1) to (4).
  • a liquid photo solder resist ink is applied by screen printing to the entire surface of a copper-clad laminate made of a glass epoxy base material of copper foil with a thickness of 35 ⁇ , and a printed wiring board that has been etched and patterned in advance. Thus, a resist ink layer was obtained on the substrate surface. 2 Pre-drying process>
  • predrying was performed at 80 ° C. for 20 minutes to volatilize the solvent in the resist ink layer on the substrate surface, and a predry film having a film thickness of 20 ⁇ was obtained.
  • the mask on which the pattern was drawn was placed directly on the surface of the pre-dried film, and the resist film was irradiated with the optimal exposure amount of ultraviolet light to selectively expose the pre-dried film on the substrate surface.
  • a 1% aqueous solution of sodium carbonate was used as a developing solution to remove unexposed portions by developing, and a pattern of the exposed and cured pre-dried film was formed on the substrate.
  • the substrate having the pre-dried film was heated at 150 ° C. for 30 minutes, and the pre-dried film was cured to obtain a test piece having a resist composed of the cured film.
  • Fiber property Fiber property
  • the formation state of a pattern formed by a mask pattern composed of concentric circles having both a line width and a line interval of 40 ⁇ was observed.
  • the evaluation method for resolution is as follows.
  • a pattern could be formed, but part of it was missing.
  • ⁇ A sharp pattern could be formed.
  • LONCO 3 3 5 5-1 1 (trade name, London First, a flux was applied to a test piece using Mical Corporation's water-soluble flux (raw flux), then immersed in a molten solder bath at 260 ° C for 15 seconds, and then washed with water. After this cycle was repeated once or five times, the degree of surface whitening was observed. In addition, a cellophane adhesive tape peeling test using a cross-cut was performed in accordance with JISD 202, and changes in the adhesion state were observed.
  • the evaluation method of surface whitening is as follows.
  • the method for evaluating the adhesion is as follows.
  • the pencil hardness was measured and evaluated in accordance with JIS 540, and the other items were evaluated by a common method.
  • test pieces were plated using commercially available electroless nickel plating baths and electroless plating baths, and the adhesion of the coating films was observed.
  • the method for evaluating the gold plating resistance is as follows.
  • a test printed circuit board was prepared under the above conditions using a coupon electrode B of IPCB-25 instead of the test piece. ° (: The presence of migration after 500 hours under the conditions of 90% R.H. was evaluated.
  • the method for evaluating the corrosion resistance was as follows.
  • an ultraviolet curable resin composition having excellent developability, resolution, development width, and heat resistance can be provided.
  • a photo solder resist ink containing this composition can be developed with a dilute aqueous solution, and has excellent substrate adhesion and electrolytic corrosion resistance, and excellent solder heat resistance and gold plating resistance.

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Abstract

L'invention concerne une composition de résine à séchage ultraviolet qui contient (A) une résine à séchage ultraviolet. On prépare cette composition en faisant réagir un composant époxy, contenant (a) un polymère époxy préparé par polymérisation d'un composant monomère éthyléniquement insaturé à base (i) d'un monomère époxydique éthyléniquement insaturé et (b) d'un dérivé d'isocyanurate époxydique, avec (c) un monomère carboxylique éthyléniquement insaturé et en faisant réagir l'intermédiaire obtenu avec (d) un anhydride d'acide polybasique saturé ou insaturé. Ladite composition contient également (B) un composé époxy présentant deux ou plusieurs groupes époxydiques dans la molécule, (C) un initiateur de photopolymérisation et (D) un diluant. Une encre réserve soudure photo contenant cette composition peut être élaborée à l'aide d'une solution aqueuse dissoute d'un alcali et peut former sur un substrat une réserve de soudure d'excellente résistance à la dorure et à la chaleur de soudage.
PCT/JP2001/007944 2000-09-14 2001-09-13 Composition de resine a sechage ultraviolet et encre reserve soudure photo WO2002023275A1 (fr)

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JP2016098377A (ja) * 2014-11-18 2016-05-30 奇美實業股▲分▼有限公司 アルカリ可溶性樹脂およびそれを含む感光性樹脂組成物ならびにその応用

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US10317796B2 (en) * 2014-12-10 2019-06-11 Goo Chemical Co., Ltd. Solder resist composition and covered printed wiring board
CN107709388B (zh) 2015-06-26 2020-07-07 日产化学工业株式会社 光固化性树脂组合物
CN108124387B (zh) * 2017-12-20 2019-12-03 厦门市铂联科技股份有限公司 一种fpc线路图形制作方法
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CN102033428A (zh) * 2009-10-07 2011-04-27 住友化学株式会社 着色感光性树脂组合物
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
JP2014067025A (ja) * 2012-09-05 2014-04-17 Nippon Shokubai Co Ltd フォトスペーサー用感光性樹脂組成物およびフォトスペーサー
KR20150053761A (ko) * 2012-09-05 2015-05-18 가부시기가이샤 닛뽕쇼꾸바이 포토 스페이서용 감광성 수지 조성물 및 포토 스페이서
KR102149152B1 (ko) * 2012-09-05 2020-08-28 가부시기가이샤 닛뽕쇼꾸바이 포토 스페이서용 감광성 수지 조성물 및 포토 스페이서
JP2015075499A (ja) * 2013-10-04 2015-04-20 株式会社日本触媒 硬化性樹脂組成物
JP2016098377A (ja) * 2014-11-18 2016-05-30 奇美實業股▲分▼有限公司 アルカリ可溶性樹脂およびそれを含む感光性樹脂組成物ならびにその応用
US10088612B2 (en) 2014-11-18 2018-10-02 Chi Mei Corporation Alkali-soluble resin, photosensitive resin composition for color filter containing the same and uses thereof

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AU2001286219A1 (en) 2002-03-26
CN1231815C (zh) 2005-12-14

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