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WO2000068740A1 - Composition d'encre resistant au soudage - Google Patents

Composition d'encre resistant au soudage Download PDF

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Publication number
WO2000068740A1
WO2000068740A1 PCT/JP2000/002936 JP0002936W WO0068740A1 WO 2000068740 A1 WO2000068740 A1 WO 2000068740A1 JP 0002936 W JP0002936 W JP 0002936W WO 0068740 A1 WO0068740 A1 WO 0068740A1
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WO
WIPO (PCT)
Prior art keywords
parts
acid
unsaturated
epoxy
diluent
Prior art date
Application number
PCT/JP2000/002936
Other languages
English (en)
Japanese (ja)
Inventor
Masami Matsumura
Yuhta Ogawa
Original Assignee
Taiyo 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 Taiyo Ink Manufacturing Co., Ltd. filed Critical Taiyo Ink Manufacturing Co., Ltd.
Priority to JP2000616466A priority Critical patent/JP3924431B2/ja
Publication of WO2000068740A1 publication Critical patent/WO2000068740A1/fr
Priority to HK03100802.5A priority patent/HK1048666B/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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 solder resist ink composition, and more particularly, to an undercoating layer that satisfies the solder resist heat resistance and the inherent characteristics required of a solder resist such as adhesion to a wiring board and has good wettability with solder.
  • the present invention relates to a solder resist ink composition for a printed wiring board which is suitable for a stable supply of a conductor pad formed with a good adhesion.
  • Photo solder resist is generally used in the manufacture of high-density printed wiring boards, and dry film type photo solder resist and liquid photo solder resist have been developed.
  • a dry film type photo solder resist for example, JP-A-57-55914 discloses a urethane di (meth) acrylate, a linear polymer compound having a specific glass transition temperature, and a photosensitizer.
  • a photosensitive resin composition for a dry film comprising:
  • dry film type photo-resist resists are hardly used in practice because they do not have sufficient solder heat resistance and adhesiveness to wiring boards and lack reliability.
  • Japanese Patent Application Laid-Open No. 61-243,695 discloses a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic anhydride.
  • a photocurable and thermosetting liquid resist ink composition comprising an active energy ray-curable resin, a photopolymerization initiator, a diluent, and an epoxy compound obtained by reacting a product is disclosed.
  • This composition is The above-mentioned required characteristics as a solder resist, that is, solder heat resistance, adhesion to a wiring board, and the like can be satisfied.
  • a solder-resist using such a composition when a solder body such as a solder bump is supplied to a conductor pad (solder pad) formed on the solder resist, poor adhesion between the conductor pad and the solder body is obtained. It is possible that this may be caused, and improvement is strongly desired.
  • an electroless plating layer base plating layer is formed on the conductor pad surface. If formed, poor adhesion between the conductor pad and the electroless plating layer and / or between the electroless plating layer and the solder body, especially poor adhesion between the conductor pad and the electroless plating layer was remarkable.
  • an object of the present invention is to provide a conductor pad having good wettability with a solder body, that is, a solder pad having good wettability with a solder body, while satisfying the inherent requirements of a solder resist such as solder heat resistance and adhesion to a wiring board.
  • An object of the present invention is to provide a solder resist ink composition for a printed wiring board, which is suitable for forming an undercoating layer such as a Ni—Au plating layer having good adhesion with good adhesion. Disclosure of the invention
  • a composition used for forming a solder-resist of a printed wiring board having a configuration in which an undercoating layer is formed on the surface of a conductor pad wherein (A) (B) has a carboxyl group and at least two ethylenically unsaturated bonds, has a solid content acid value of 50 to 150 mg KOH / g, and (B) has a melting point of 100 ° C or more. (C) a diluent; and (D) a thermosetting component containing, as a main component, an epoxy compound having two or more epoxy groups in one molecule.
  • An ink composition is provided.
  • photopolymerization initiator (B) 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -1-butane-11-one and / or bis (7? 5 - 2, 4-Shikuropen evening Gen one 1 one I le) Single-bis (2, 6-Difluoro-3- (1H-pyrroyl-1-yl) -phenyl) titanium is used.
  • thermosetting component (D) further contains an epoxy curing accelerator. Is preferred.
  • the present inventors have found that the aforementioned bonding failure of the solder body to the conductor pad is caused by a mist generated when the solder resist is dried or subjected to stoking, or a mist generated during a baking process after the undercoating. In particular, we have found that it is caused by adhesion to the conductor pad. It was also found that the mist adhering to the conductor pad of the substrate was caused by evaporation of the photopolymerization initiator due to heating.
  • the present inventors have conducted intensive studies based on such findings to achieve the above-mentioned object.
  • a photopolymerization initiator (B) having a melting point of 100 C or more
  • the solder resist was dried or dried. If the occurrence of mist is suppressed during the post cure or during the baking process after the undercoating, the undercoating layer such as a Ni-Au plating layer with good wettability with the solder body is placed on the conductive pads. It has been found that it can be formed with good adhesion, and that the adhesion of the solder body to the conductor pad can be improved.
  • the photopolymerization initiator (B) used in the present invention has a high melting point, It does not evaporate at the temperature at which the coating film of the composition is preliminarily dried (about 60 to 100 ° C.), and the temperature at which the coating film of the composition is thermally cured (about 140 to 15 ° C.). The amount of mist generated is extremely small because it does not evaporate even at 0 ° C). Therefore, by using the composition of the present invention, a resist film can be formed without causing contamination of the substrate by mist, and an undercoating layer such as a Ni—Au plating layer can be formed on the surface of the conductor pad with good adhesion. Can be formed.
  • the cured coating film of the composition does not evaporate during the pass-coating process after the undercoating, so that the wettability between the undercoating layer and the solder body is good. Furthermore, during exposure by the contact method (when selectively irradiating actinic light through a patterned photomask), the coating film of the resist composition and the photomask do not stick. As a result, (i) the workability can be improved, (ii) the photomask is not contaminated by volatilization mist, and (iii) the amount of the photopolymerizable monomer is increased while the amount of the expensive photopolymerization initiator used is suppressed. It has the effect of greatly improving the photocuring properties.
  • photopolymerization initiator (B) having a melting point of 100 ° C. or more a known or common photopolymerization initiator can be used alone or in combination of two or more.
  • 2-dimethylamino-1 one (4 one Morpho Rinofu enyl) over blanking evening Hmm 1 one on and / or bis (7? 5 -2, 4-Shikuropen evening Gen one 1 one I le) Single-bis (2, 6- Difluoro-1- (1H-virol-11-yl) -phenyl) titanium is used.
  • the photopolymerization initiator (B) is a tertiary amine such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like.
  • Such photosensitizers can be used in combination with one or more known photosensitizers such as those described above, and it is preferable that these photosensitizers also have a melting point of 100 ° C or more.
  • the mixing ratio of the photopolymerization initiator (B) is preferably from 1 to 30 parts by weight, and more preferably from 5 to 25 parts by weight, based on 100 parts by weight of the photosensitive prepolymer (A). is there.
  • the reason for this is that if the amount of the photopolymerization initiator (B) used is less than the above range, the photocurability of the composition becomes poor. This is because it is not preferable because the above-mentioned characteristics as a metal are deteriorated.
  • composition of the present invention containing the photopolymerization initiator (B) having a melting point of 100 ° C. or higher, the above-described effects can be obtained, but the composition of the present invention is photocured.
  • the coating film is heated to a temperature near the melting point of the thermosetting component (D) in the thermosetting (post-curing) step, the thermosetting component (D) softens and melts, and the carboxyl group A cross-linking reaction occurs with the photosensitive prepolymer (A) having the above, and a solder resist film having excellent various properties as described above can be obtained.
  • the photosensitive prepolymer (A) has a carboxyl group and at least two ethylenically unsaturated bonds in one molecule, and has a solid content acid value of 50 to 150 mgKOH / g.
  • a terpolymer oligomer or polymer can be used. For example,
  • the copolymer of (meth) acrylic acid and another copolymerizable monomer (d) having an ethylenically unsaturated bond should have an acid value of 50 to 50 mg KOH / g for solid content.
  • the unsaturated monocarboxylic acid (b) is reacted with the copolymer with the copolymerizable monomer (d) having a saturated bond, and the hydroxyl group of the obtained reaction product has a solid acid value of 50 to 150 mg KOH / g.
  • a polycarboxylic acid resin having an unsaturated group such as an unsaturated resin can be preferably used.
  • the photosensitive prepolymer is not limited to those described above, but has both a carboxyl group and at least two ethylenically unsaturated bonds in one molecule.
  • Any photosensitive prepolymer having a solid content acid value of 50 to 150 mg KOH / g can be used in the present invention.
  • Acrylic acid is a generic term for acrylic acid, methacrylic acid and mixtures thereof, as well as for other similar expressions.
  • the composition containing this photosensitive prepolymer is diluted with a dilute alkaline aqueous solution.
  • the coating film is post-heated, so that the epoxy group of the epoxy compound to be added as a thermosetting component (D) and the free carboxyl group of the side chain are separately added.
  • An addition reaction occurs between the two, and a solder resist film having excellent properties such as heat resistance, solvent resistance, acid resistance, adhesion, electroless gold plating resistance, electrical properties, and hardness is obtained.
  • the epoxy resin (a) used in the synthesis of the resins (1) and (4) includes bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, Phenol S type epoxy resin, phenol nopolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol A novolak type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, trisphenol methane type epoxy resin, N-glycidyl type epoxy resin and other commonly used epoxy resins alone or in combination of two or more Can be used.
  • nopolak type epoxy resins such as phenol nopolak type, cresol novolak type, and bisphenol A nopolak type are excellent in solder heat resistance and chemical resistance. It is particularly preferable because a resist film can be obtained.
  • the unsaturated monocarboxylic acid (b) used in the synthesis of the resins (1), (3) and (4) include, for example, acrylic acid, a dimer of acrylic acid, Crylic acid, 5-styrylacrylic acid, furfuryacrylic acid, coutonic acid, monocyanocinnamic acid, cinnamic acid, etc .; and having one hydroxyl group per molecule with saturated or unsaturated dibasic anhydride Half-esters that are reactants with (meth) acrylates or react with saturated or unsaturated dibasic acids and unsaturated monoglycidyl compounds, for example, succinic anhydride, maleic anhydride, fluoric anhydride, Tetrahydrofuranic anhydride, hexahydrophthalic anhydride, methylhexahydrofuranic anhydride, methyltetrahydrofuranic anhydride, itaconic anhydride, methylendomethylenetetrahydrofuranic anhydride S
  • unsaturated monocarboxylic acids may be used alone or in combination of two or more. be able to.
  • acrylic acid or methacrylic acid is preferred from the viewpoint of photocurability.
  • saturated or unsaturated polybasic anhydride (c) used in the synthesis of the resins (1), (3), (4) and (6) representative examples are maleic anhydride and succinic anhydride.
  • Dibasic such as hexahydrofluoric anhydride, methylhexahydrofluoric anhydride, endomethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride Acid anhydrides; aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride; and other accompanying compounds such as 5- (2,5-di) Oxotetrahydrofuryl) poly (carboxylic anhydride) derivatives such as 1,3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
  • aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride
  • other accompanying compounds such as 5- (2,
  • saturated or unsaturated polybasic acid anhydrides (c) can be used alone or in combination of two or more.
  • polybasic acid anhydrides anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid and succinic acid are particularly preferred from the viewpoint of the properties of the cured coating film.
  • the proportion of the polybasic acid anhydride (c) used is preferably in the range where the solid product acid value of the reaction product is 50 to 150 mgKOH / g. If the resulting photosensitive prepolymer has an acid value of less than 50 mgKOH / g, the solubility of the copolymer becomes poor, and the resulting coating film of the composition becomes difficult to be developed with a dilute aqueous alkali solution as described below. If it exceeds 150 mgKOH / g, the resist properties such as the development resistance, alkali resistance, and electrical properties of the photocured film may be reduced, and the photocurable film may not be usable as a solder resist.
  • Representative examples of the copolymerizable monomer (d) having an ethylenically unsaturated bond used in the synthesis of the resins (2) and (3) include styrene, styrene, methyl styrene, and substituents.
  • copolymerizable monomers (d) can be used alone or in combination of two or more.
  • copolymerizable monomers it is preferable to use styrene, 2-hydroxyethyl (meth) acrylate or methyl (meth) acrylate in view of the glass transition point Tg of the obtained copolymer resin and cost. Further, from the viewpoint of light transmittance in the coating film, it is more preferable to use methyl (methyl) acrylate or 2-hydroxyethyl (meth) acrylate containing no benzene.
  • the weight average molecular weight of the resins (2) and (3) is preferably in the range of 50,000 to 20,000.
  • the weight average molecular weight is less than 5,000, it becomes difficult to obtain cured coating properties such as solder heat resistance.
  • the weight average molecular weight exceeds 20,000, development with a dilute alkaline aqueous solution becomes difficult. However, it may not be used as a solder resist.
  • the polyfunctional epoxy resin (a) is reacted with an unsaturated monocarboxylic acid (b) (or compound (e)), and then the compound (e) (or unsaturated monocarboxylic acid) is reacted.
  • an unsaturated monocarboxylic acid (b) or compound (e)
  • the compound (e) or unsaturated monocarboxylic acid
  • There are a first method in which the acid (b)) is reacted and a second method in which the polyfunctional epoxy resin (a), the unsaturated monocarboxylic acid (b) and the compound (e) are simultaneously reacted. Either method may be used, but the second method is preferred.
  • the above reaction is carried out at a ratio such that the total amount of the unsaturated monocarboxylic acid (b) and the compound (e) is about 0.8 to 1.3 mol per 1 equivalent of the epoxy group of the polyfunctional epoxy resin (a).
  • the reaction is preferably carried out, particularly preferably about 0.9 to 1.1 mol.
  • the reaction is performed in the following ratio.
  • the ratio of the unsaturated monocarboxylic acid (b) to the compound (e) used is based on 1 mole of the total amount of the unsaturated monocarboxylic acid (b) and the compound (e).
  • the amount of compound (e) to be used is preferably 0.05 to 0.5 mol, particularly preferably
  • reaction between the reaction product (I) and the polybasic acid anhydride (c) is carried out based on the polybasic acid anhydride (c) per equivalent of the hydroxyl group with respect to the hydroxyl group in the reaction product (I).
  • the reaction is carried out at 0.1 to 0.9 equivalent.
  • the ratio of the unsaturated group-containing monoisocyanate (f) to the hydroxyl group in the unsaturated group-containing polycarboxylic acid resin, which is the reaction product of the above, is 0.05 to 0.5 equivalent per 1 equivalent of the hydroxyl group.
  • the reaction is carried out.
  • At least two hydroxyl groups and one other reactive group other than a hydroxyl group that reacts with an epoxy group include, for example, polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylthiol-lcabroic acid.
  • polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylthiol-lcabroic acid.
  • Dialnol amines such as diethanolamine and disopropanolamine.
  • dimethylolpropionic acid and the like can be mentioned.
  • unsaturated monoisocyanate (f) examples include, for example, methacryloyl isocyanate, methacryloyloxyshethyl isocyanate ⁇ , and organic diisocyanate (for example, tolylene diisocyanate, xylylene dithiocyanate, Reactants obtained by reacting isophorone diisocyanate, hexamethylene diisocyanate, etc.) with (meth) acrylates having one hydroxyl group in one molecule in an approximately equimolar ratio. be able to.
  • organic diisocyanate for example, tolylene diisocyanate, xylylene dithiocyanate, Reactants obtained by reacting isophorone diisocyanate, hexamethylene diisocyanate, etc.
  • unsaturated monoisocyanates (f) can be used alone or in combination of two or more.
  • diluent (C) a photopolymerizable vinyl monomer and / or an organic solvent can be used.
  • Photopolymerizable vinyl monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene.
  • Mono- or diacrylates of glycols such as glycol; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminobutyryl acrylamide; N, N— Aminoalkyl acrylates such as dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, benzoyl erythritol, dipentyl erythritol, tris-one Hydroxyethyl Polyhydric alcohols such as cyanurate, or polyhydric acrylates such as an ethylene oxide adduct or propylene oxide adduct thereof; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide of these phenols Acrylates such as adducts or propylene oxide adducts; glycidyl ether acrylates such as glycer
  • organic solvent examples include ketones such as methylethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methylacetosolve, butylsesolve, carbitol, and methyl carbitol.
  • Glycols such as tall, butyl carbitol, propylene glycol monomethyl ether, diprovylene glycol monomethyl ether, dipropylene glycol getyl ether, and triethylene glycol monoethyl ether; Esters; esters such as ethyl acetate, butyl acetate and acetic acid esters of the above glycol ethers; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; and aliphatic hydrocarbons such as octane and decane.
  • Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc., and have good compatibility with the photosensitive prepolymer (A) and dissolve the thermosetting component (D). Those that do not are preferred.
  • the diluent (C) as described above is used alone or as a mixture of two or more.
  • the preferred range of the amount of the diluent is 40 parts by weight or less based on 100 parts by weight of the photosensitive prepolymer (A) when a photopolymerizable monomer is used. However, it is not preferable because the dryness to the touch deteriorates.
  • the amount of the organic solvent used is not limited to a specific ratio, but is preferably in the range of about 30 to 300 parts by weight with respect to 100 parts by weight of the photosensitive blepolymer- (A). It can be set as appropriate according to the selected coating method.
  • the purpose of use of the diluent (C) is to, in the case of a photopolymerizable vinyl monomer, dilute the photosensitive blepolymer to make it easy to apply and to enhance photopolymerizability.
  • the photosensitive prepolymer is dissolved and diluted, thereby coating as a liquid, and then drying to form a film, thereby enabling contact exposure. Therefore, depending on the diluent to be used, either a contact type or a non-contact type in which the photomask is brought into close contact with the coating film is used.
  • thermosetting component (D) includes an epoxy compound having two or more epoxy groups in one molecule.
  • epoxy compounds examples include EBPS—200 manufactured by Nippon Kayaku Co., Ltd., EPX—30 manufactured by Asahi Denka Kogyo Co., Ltd., and Evicron EXA—15 manufactured by Dainippon Ink and Chemicals, Inc.
  • Bisphenol S-type epoxy resin such as 14; diglycidyl phthalate resin such as Blemma-DGT manufactured by NOF Corporation; TEPIC series manufactured by Nissan Chemical Industries, Ltd .; araldite manufactured by Chipa Specialty Chemicals PT 810 YX-4 manufactured by Yuka Shell Epoxy Co., Ltd.
  • Vixylenol type epoxy resin such as 000; YL manufactured by Yuka Shell Epoxy Co., Ltd.
  • Bisphenol A-type epoxy resin such as ER-673MF, Asahi Denka Kogyo Co., Ltd. EP-5400, EP-5900; hydrogenated bisphenol A-type epoxy resin such as Toto Kasei Co., Ltd. ST-2004, ST-2007 Bisphenol F type epoxy resin such as YD F-2004, YD F-2007 manufactured by Toto Kasei; SR-BBS, SR-TBA-400 manufactured by Sakamoto Pharmaceutical Co., Ltd .; Asahi Denka Kogyo Co., Ltd.
  • Brominated bisphenol A type epoxy such as EP-62, EP-66, AER-755, AER-765, Asahi Kasei Kogyo Co., Ltd., YDB-600, YDB-715, Toto Kasei Co., Ltd. Resin; Nippon Kayaku Co., Ltd. EPPN-201, E0CN-103, EOCN-1020, EOCN-1025, Asahi Kasei Kogyo Co., Ltd.
  • Chelated Eppo Glyoxal type epoxy resin such as YDG-4141 manufactured by Toto Kasei Co., Ltd .; YH-1402, ST-1110 manufactured by Toto Kasei Co., Ltd., YL manufactured by Yuka Shell Epoxy Co., Ltd.
  • Epoxy resin containing amino group such as 931, YL—9333; Ebicron TSR—611, manufactured by Dainippon Ink and Chemicals, Inc. EPX—841-2, EPX—, manufactured by Asahi Denka Kogyo Co., Ltd.
  • Rubber-modified epoxy resin such as 410.1 etc .: Dicyclobenzene-based phenolic epoxy resin such as DCE-400 manufactured by Sanyo Kokusaku Pulp Co., Ltd .; Silicon-modified epoxy resin such as X-135 manufactured by Asahi Denka Kogyo Epoxy resins soluble in diluents, such as epoxy resin; £ -force prolacton-modifying epoxy resins such as Braxel G-402 and G-7110 manufactured by Daicel Chemical Industries, Ltd .; These epoxy resins can be used alone or in combination of two or more, and it is particularly preferable to disperse them in fine particles in the photosensitive blepolymer (A).
  • Dicyclobenzene-based phenolic epoxy resin such as DCE-400 manufactured by Sanyo Kokusaku Pulp Co., Ltd .
  • Silicon-modified epoxy resin such as X-135 manufactured by Asahi Denka Kogyo Epoxy resins soluble in diluents, such as epoxy
  • the solubility should be within the range that does not adversely affect the solubility. That is, it is preferable to use a fine-grained epoxy resin that is hardly soluble in a diluent, or a combination of a hardly soluble epoxy resin and a soluble epoxy resin. At this time, the amount of the epoxy resin soluble in the diluent is preferably less than 50 mol% of the epoxy equivalent of all epoxy compounds as thermosetting components.
  • the resultant composition is temporarily dried. This is not preferred because the dryness to the touch and the development life of the toner deteriorate.
  • the photosensitive prepolymer (A) is used as the main component because the viscosity tends to increase slightly before application to a printed wiring board. It is desirable that the composition is formed into a two-part form of a main agent and a curing agent containing the thermosetting component (D) as a main component, and that both are used in combination.
  • the amount of the epoxy compound (D) as the thermosetting component is desirably 5 to 100 parts by weight based on 100 parts by weight of the light-sensitive polymer (A). Is from 15 to 60 parts by weight.
  • an epoxy curing accelerator or a catalyst can be used together with the epoxy resin.
  • epoxy curing accelerators or catalysts examples include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2 —Imidazole derivatives such as phenylimidazole, 1- (2-cyanoethyl) -12-ethyl-4-methylimidazole; dicyandiamid, benzyldimethylamine, 41- (dimethylamino) -N, N-dimethylbenzylamine, Amine compounds such as 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adivic hydrazide and sebacic hydrazide; phosphorus compounds such as triphenylphosphine Etc., and those that are commercially available For example, 2MZ—A,
  • the present invention is not limited to these, but may be any as long as it is a curing catalyst for an epoxy resin or a catalyst that promotes the reaction between an epoxy group and a carboxyl group, and may be used alone or as a mixture of two or more.
  • S-triazine derivatives such as 2,2-vinyl-4,6 diamino group S-triazine / isocyanuric acid adduct and 2,4-diamino group 6-methacryloyloxyshethyl-S-triazine / isosinuric acid
  • a compound that also functions as an adhesion promoter is used in combination with the curing catalyst.
  • the amount of the curing catalyst to be blended is usually in a sufficient quantitative ratio, for example, 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of the photosensitive prepolymer (A). 15. 0 parts by weight.
  • solder resist ink composition of the present invention which contains the above-described components as essential components, may be used, if necessary, for the purpose of preventing the oxidation of copper circuit circuits, that is, copper, adenine, vinyltriazine, dicyandiamide, Compounds such as trilbiguanide and melamine can be added.
  • the compounding range of these compounds is preferably 20 parts by weight or less based on 100 parts by weight of the photosensitive prepolymer (A). By adding these, the chemical resistance of the formed solder resist film is improved.
  • Barium sulfate, barium titanate, silicon oxide powder, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, etc. may be used to improve properties such as adhesion, hardness, and solder heat resistance.
  • Known and commonly used inorganic fillers such as aluminum oxide, aluminum hydroxide, glass fiber, carbon fiber, and mica powder can be blended.
  • the blending ratio is 3 parts per 100 parts by weight of the photosensitive prepolymer (A). The proportion is preferably not more than 100 parts by weight, more preferably from 5 to 200 parts by weight.
  • composition of the present invention may contain, if necessary, known coloring agents such as phthalocyanine blue, phthalocyanine cyanine 'green, aozin' green, disazojello, crystal violet, titanium oxide, carbon black, and naphthalene black.
  • known coloring agents such as phthalocyanine blue, phthalocyanine cyanine 'green, aozin' green, disazojello, crystal violet, titanium oxide, carbon black, and naphthalene black.
  • thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, virogallol, and phenothiazine; known and commonly used thickeners such as asbestos, finely divided silica, organic bentonite, and montmorillonite; silicone Additives such as antifoaming agents and / or repelling agents such as amides, fluorines and polymers, and known and commonly used adhesion-imparting agents such as imidazoles, thiazoles, triazoles and silane coupling agents. Can be blended.
  • the solder resist ink composition having the composition described above is adjusted to a viscosity suitable for the application method as necessary, and is then screen-printed, curtain-coated, spray-coated, roll-coated on the printed circuit board on which the circuit is formed.
  • the organic solvent contained in the composition is volatilized at a temperature of, for example, about 60 to 100 ° C. By drying (temporary drying), a tack-free coating film with a long development life can be formed. Then, it is selectively exposed to active light through a patterned photomask by a contact method (or a non-contact method), and the unexposed portion is diluted with a dilute aqueous solution (for example, 0.5 to 5% sodium carbonate).
  • a dilute aqueous solution for example, 0.5 to 5% sodium carbonate
  • Aqueous solution to form a resist pattern. Furthermore, by heating to a temperature of about 140 to 180 ° C and thermosetting, for example, adhesion, hardness, solder heat resistance, and chemical resistance Thus, a solder resist film excellent in solvent resistance, electric insulation, electric corrosion resistance and the like is formed.
  • a diluted alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.
  • a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a metal halide lamp is suitable.
  • a laser beam or the like can also be used as an active light beam for exposure.
  • the undercoating layer formed on the conductor pad surface has excellent wettability with the solder.
  • Electrolytic Ni—Au plating layers are preferred. However, the present invention is not limited to this, and other plating can be applied as long as the plating layer has good wettability with the solder body.
  • electroless Ni—AU plating refers to a combination of electroless Ni plating and electroless Au plating.
  • a stirrer and reflux condenser And added 206 parts of carbitol acetate, and dissolved by heating.
  • 0.1 part of hydroquinone was added as a polymerization inhibitor
  • 2.0 parts of triphenylphosphine was added as a reaction catalyst.
  • the mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours.
  • reaction product solution was referred to as A varnish.
  • each of the ink compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was applied on the entire surface of a patterned copper foil substrate by screen printing, and dried at 80 ° C for 20 minutes. Then, applying a negative film on the substrate, exposed to Ri solder resist pattern through, 1 wt spray pressure 1. 5 kg / cm 2.% N a 2 developed in C 0 3 aqueous solution to form a resist pattern. Then, each substrate was heated in a sealed oven under a thermosetting condition of 150 ° C. for 60 minutes to collect mist components generated.
  • the amount of mist generated is measured by dissolving the collected mist components in DMF (N, N-dimethylformamide) and measuring by GPC (JIPO: BIP-I, detector: UV, measurement wavelength 280 nm). And evaluated according to the following criteria.
  • each of the ink compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was applied to the entire surface of the copper foil substrate on which the pattern was formed by screen printing, dried at 80 ° C for 15 minutes, and tack-free. A coating was formed. Then, applying a negative film on the substrate, exposing the solder one resist pattern as a spray pressure 1 is developed with 1 wt.% Na 2 C0 3 aqueous solution 5 kg / cm 2, to form a resist pattern. Further, this substrate was thermally cured at 150 ° C for 40 minutes in a closed drying oven to prepare a test substrate, which was subjected to the following characteristic evaluation tests.
  • test substrate prepared as described above was immersed in a 30 ° C acidic degreasing solution (20 vol.% Aqueous solution of Metex L-5B, manufactured by Nippon MacDermid Co., Ltd.) for 3 minutes to degrease it. It was immersed in running water for 3 minutes and washed. Next, the test substrate was immersed in a 14.3 wt.% Ammonium persulfate aqueous solution at room temperature for 3 minutes, soft-etched, and then immersed in running water for 3 minutes and washed with water. The test substrate was immersed in a 10 vol.% Sulfuric acid aqueous solution at room temperature for 1 minute, immersed in running water for 30 seconds to 1 minute, and washed with water.
  • a 30 ° C acidic degreasing solution (20 vol.% Aqueous solution of Metex L-5B, manufactured by Nippon MacDermid Co., Ltd.
  • Ammonium persulfate aqueous solution at room temperature for 3 minutes
  • test substrate is immersed in a 30 ° C catalyst solution (Metaltex, Inc., 10% aqueous solution of 350% by volume of Metallicactivate 350) for 7 minutes, and the catalyst is applied. It was immersed for 3 minutes and washed with water.
  • the test substrate to which the catalyst was applied was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., Melbrate Ni-865M, 20 vol.% Aqueous solution, pH 4.6) at 85 ° C for 20 minutes. Electrolytic nickel plating was performed.
  • the test substrate was immersed in a 10 vol.% Sulfuric acid aqueous solution at room temperature for 1 minute, and then immersed in running water for 30 seconds to 1 minute and washed with water.
  • test substrate is immersed in a plating solution of 95 ° C (Meltex Co., Ltd., a solution of 15 vol. After plating, they were immersed in running water for 3 minutes and washed with water, and immersed in warm water at 60 ° C for 3 minutes and washed with hot water. After washing thoroughly with water, the water was thoroughly drained, dried, and a test board with electroless gold plating was obtained. After plating the test board in this way, peel it off with cellophane adhesive tape Then, the presence or absence of peeling of the resist layer and the presence or absence of adhesion (adhesion) were evaluated.
  • the criteria are as follows.
  • electroless Ni-Au plating is applied to each test substrate in the same manner as in (4) above, and the thickness of the electroless Ni-Au plating film is measured.
  • the thickness of the electroless Ni-Au plating film is measured.
  • the effect of the plating bath on contamination was evaluated in consideration of the tendency of the mist to adhere to the substrate during thermosetting.
  • the evaluation criteria are as follows.
  • the rosin-based flux After applying the rosin-based flux to the test substrate, it was immersed in a solder bath set at 260 ° C. for 30 seconds, and the flux was washed with trichloroethane. ) 'Peel off. Discoloration was evaluated.
  • the evaluation criteria are as follows.
  • test substrate was immersed in a 10 vol.% Aqueous sulfuric acid solution at room temperature for 30 minutes, washed with water, and subjected to a peel test with a cellophane adhesive tape to evaluate peeling (adhesion) and discoloration of the resist film.
  • the evaluation criteria are as follows.
  • the solder resist ink compositions of Examples 1 to 4 of the present invention generated a small amount of mist, and therefore did not adhere to the substrate. It also had excellent adhesion (adhesion), and also had excellent properties such as touch-drying properties and developability after preliminary drying, and solder heat resistance and acid resistance required for solder resist films. Further, the test substrates of Examples 1 to 4 were subjected to a beer test using cellophane adhesive tape after applying a solder body by performing electroless Ni-Au plating, and there was no peeling of the solder body. It was found that the adhesion to the conductor pad was good. In contrast, comparative examples, especially In the case of Comparative Examples 2 and 3, the solder body peeled off, and the adhesion of the solder body to the conductor pad was poor.
  • solder resist ink composition of the present invention a conductor pad that satisfies the solder resist's essential characteristics such as solder heat resistance and adhesion, and has good wettability with a solder body, that is, a solder body It was confirmed that an underlying plating layer such as a Ni—Au plating layer having good wettability could be formed with good adhesion.
  • Example 4 when a photopolymerization initiator having a melting point of 100 ° C. or higher was used according to the present invention, even if the amount of the photopolymerization initiator was reduced, the photopolymerizable monomer was By increasing the amount, a good resist coating film can be obtained.
  • the resin solution was cooled and glycidyl methacrylate was used at 95 to 105 ° C for 16 hours using methylhydroquinone as a polymerization inhibitor and tetrabutylphosphonium bromide as a catalyst. Then, 20 mol% was added to the mixture, and after cooling, it was taken out.
  • the photosensitive prepolymer having both an ethylenically unsaturated bond and a carboxyl group thus obtained has a nonvolatile content of 65%, an acid value of a solid substance of 12 O mg KOH / g, and a Mw of about 15 and 0. It was 0 0.
  • this resin solution is referred to as B varnish.
  • methyl methacrylate and glycidyl methacrylate were prepared so that the molar ratio was 4: 6.
  • the mixture was stirred at 80 ° C for 4 hours under a nitrogen atmosphere using carbitol acetate as a solvent and AIBN as a catalyst to obtain a resin solution.
  • This resin solution was cooled, and methylacryloquinone was used as a polymerization inhibitor and tetrabutylphosphonium bromide was used as a catalyst.Acrylic acid was added to the epoxy groups of the above resin at 95 to 105 ° C for 16 hours. A 100% addition reaction was performed. The reaction product was cooled to 80 to 90 ° C., reacted with tetrahydrophthalic anhydride for 8 hours, and taken out after cooling.
  • the photosensitive blepolymer thus obtained having both an ethylenically unsaturated bond and a carboxyl group had a nonvolatile content of 65%, an acid value of a solid of 10 OmgKOH / g, and a Mw of about 15,000.
  • this resin solution is referred to as C varnish.
  • 134 parts (1 mol) of dimethylolpropionic acid 648.5 parts (9 mol) of acrylic acid, 4.6 parts of methylhydroquinone, 131 parts of carbitol acetate and 484.9 parts of solvent naphtha
  • the mixture was heated to 90 ° C. and stirred to dissolve the reaction mixture.
  • reaction mixture was cooled to 60 ° C, charged with 13.8 parts of triphenylphosphine, heated to 100 ° C, and reacted for about 32 hours.
  • the reaction product having an acid value of 0.5 mgKOH / g (Hydroxyl group: 12 equivalents) was obtained.
  • 364.7 parts (2.4 moles) of tetrahydrofluoric anhydride, 137.5 parts of carbitol acetate and 58.8 parts of sorbent tonaphtha were charged and heated to 95 ° C.
  • dimethylolpropionic acid 40 Charge 2 parts (3 moles), 504.4 parts (7 moles) of acrylic acid, 4.8 parts of methylhydroquinone, 178 parts of carbitol acetate and 505 parts of solvent naphtha, heat to 90 ° C, stir, and mix the reaction mixture. Was dissolved.
  • reaction solution was cooled to 60 ° C., and triphenylphosphine (14.3 parts) was charged. C was heated and reacted for about 32 hours to obtain a reaction product (hydroxyl group: 16 equivalents) having an acid value of 0.8 mgKOH / g.
  • this Tetorahi mud anhydrous full Yurusan 402.5 parts (2.65 moles) were charged 1 33 parts of carbitol acetate and solvent naphtha 57.3 parts, was heated to 9 5 e C, about 6 hours
  • the reaction was allowed to cool, and an unsaturated group-containing polycarboxylic acid resin having an acid value of 31.6 mg KOH / g (hydroxyl group: 13.35 equivalents) was obtained.
  • E represents CH or C (CH 3 ) 2 or SO 2
  • n represents 1 to 12
  • G represents a hydrogen atom or a glycidyl group.
  • n 1 to 12
  • G represents a hydrogen atom or a glycidyl group.
  • n 1 to 12
  • G represents a hydrogen atom or a glycidyl group.
  • n 2 or more
  • at least one of G represents a glycidyl group.
  • a photocurable and thermosetting solder resist composition that does not generate mist during the heating step is provided.
  • mist generation from the photocured coating film of the solder resist composition during thermosetting is suppressed, and This not only reduces soldering defects during manufacturing, but also improves the working environment. Therefore, good wettability with solder This makes it possible to manufacture printed wiring boards that are suitable for the stable supply of conductor pads having a good undercoating layer with good adhesion.

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Abstract

L'invention concerne une composition d'encre résistant au soudage et destinée à s'utiliser dans les cartes à circuit imprimé, cette composition d'encre étant capable de former, avec une adhérence satisfaisante, une couche de dépôt primaire, par exemple, une couche de dépôt Ni-Au possédant une soudabilité satisfaisante. La composition comprend: (A) un prépolymère photosensible possédant un groupe carboxyle et au moins deux liaisons insaturées de façon éthylénique par molécule, et une valeur acide de 50 à 150 mg-KOH/g sur une base solide; (B) un activateur de photopolymérisation possédant un point de fusion supérieur ou égal à 100°C; (C) un diluant; et (D) un ingrédient thermodurcissable comprenant comme composant principal un composé époxyde possédant deux ou plusieurs groupes époxydes par molécule.
PCT/JP2000/002936 1999-05-06 2000-05-08 Composition d'encre resistant au soudage WO2000068740A1 (fr)

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JP2000616466A JP3924431B2 (ja) 1999-05-06 2000-05-08 ソルダーレジストインキ組成物
HK03100802.5A HK1048666B (zh) 1999-05-06 2003-02-04 印刷線路板

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JP12558599 1999-05-06
JP11/125585 1999-05-06

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WO2000068740A1 true WO2000068740A1 (fr) 2000-11-16

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JP2002234932A (ja) * 2001-02-09 2002-08-23 Nippon Kayaku Co Ltd アルカリ水溶液可溶性エポキシカルボキシレート化合物及びそれを用いた感光性樹脂組成物並びにその硬化物
JP2002293877A (ja) * 2001-03-29 2002-10-09 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びその硬化物
WO2003010602A1 (fr) 2001-07-26 2003-02-06 Ciba Specialty Chemicals Holding Inc. Composition de resine photosensible
SG100761A1 (en) * 2001-09-28 2003-12-26 Nanya Plastics Corp Photosensitive thermosetting resin composition
WO2006004158A1 (fr) * 2004-07-07 2006-01-12 Taiyo Ink Mfg. Co., Ltd. Composition de resine photopolymerisable/thermodurcissable, film sec utilisant celle-ci et produit polymerise correspondant
WO2007108555A1 (fr) * 2006-03-22 2007-09-27 Fujifilm Corporation Procédé de production d'un film de compensation optique, plaque polarisante comprenant un film de compensation optique produit par ledit procédé et dispositif d'affichage à cristaux liquides
JP2009250985A (ja) * 2008-04-01 2009-10-29 Kansai Paint Co Ltd 樹脂組成物、レジスト組成物及びレジストパターン形成方法
JP2018063405A (ja) * 2016-10-14 2018-04-19 互応化学工業株式会社 感光性樹脂組成物
WO2019128257A1 (fr) * 2017-12-27 2019-07-04 太阳油墨（苏州）有限公司 Composition de résine durcissable, film sec, article durci et carte de circuit imprimé
JP2019174751A (ja) * 2018-03-29 2019-10-10 株式会社タムラ製作所 感光性樹脂組成物
CN110895381A (zh) * 2019-11-20 2020-03-20 深圳市容大感光科技股份有限公司 感光阻焊油墨组合物、其用途及含有其的线路板
EP4215551A4 (fr) * 2020-09-18 2024-03-13 Konica Minolta, Inc. Composition durcissable, encre pour réserve de soudure et carte de circuit imprimé

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JP4559892B2 (ja) * 2005-03-28 2010-10-13 太陽インキ製造株式会社 着色感光性樹脂組成物及びその硬化物
KR100787341B1 (ko) * 2005-09-06 2007-12-18 다이요 잉키 세이조 가부시키가이샤 수지 조성물 및 그의 경화물 및 그것을 이용하여 얻어지는인쇄 배선판
JP4849860B2 (ja) * 2005-10-04 2012-01-11 太陽ホールディングス株式会社 光硬化性・熱硬化性樹脂組成物及びその硬化物並びにそれを用いて得られるプリント配線板
JP4994922B2 (ja) * 2007-04-06 2012-08-08 太陽ホールディングス株式会社 ソルダーレジスト組成物およびその硬化物
CN105517364B (zh) * 2014-09-25 2018-10-23 深南电路有限公司 一种用于印刷电路板的电镀金方法
CN106318019B (zh) * 2015-07-06 2020-03-17 南亚塑胶工业股份有限公司 印刷电路板用低介电抗焊光阻油墨组合物
US10527936B2 (en) 2016-06-17 2020-01-07 Nan Ya Plastics Corporation Low Dk/Df solder resistant composition use for printed circuit board
CN111684011B (zh) * 2018-02-08 2023-09-01 关西涂料株式会社 抗蚀剂组合物和抗蚀膜
CN117003933B (zh) * 2023-08-14 2024-01-19 江门市金桥新材料有限公司 一种无皂聚合阳离子分散体及其制备方法
CN117363089A (zh) * 2023-09-25 2024-01-09 深圳市首骋新材料科技有限公司 改性硫酸钡的制备方法、xbc电池用绝缘油墨及xbc电池

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JPH07301918A (ja) * 1992-01-06 1995-11-14 Taiyo Ink Mfg Ltd レジストインキ組成物及びソルダーレジスト膜形成法
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Cited By (19)

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Publication number Priority date Publication date Assignee Title
JP2002234932A (ja) * 2001-02-09 2002-08-23 Nippon Kayaku Co Ltd アルカリ水溶液可溶性エポキシカルボキシレート化合物及びそれを用いた感光性樹脂組成物並びにその硬化物
JP2002293877A (ja) * 2001-03-29 2002-10-09 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びその硬化物
JP4713753B2 (ja) * 2001-03-29 2011-06-29 太陽ホールディングス株式会社 光硬化性熱硬化性樹脂組成物及びその硬化物
WO2003010602A1 (fr) 2001-07-26 2003-02-06 Ciba Specialty Chemicals Holding Inc. Composition de resine photosensible
SG100761A1 (en) * 2001-09-28 2003-12-26 Nanya Plastics Corp Photosensitive thermosetting resin composition
US7585611B2 (en) 2004-07-07 2009-09-08 Taiyo Ink Mfg. Co., Ltd. Photocurable and thermosetting resin composition, dry film using the same, and cured product thereof
JPWO2006004158A1 (ja) * 2004-07-07 2008-04-24 太陽インキ製造株式会社 光硬化性・熱硬化性樹脂組成物とそれを用いたドライフィルム、及びその硬化物
KR100845657B1 (ko) 2004-07-07 2008-07-10 다이요 잉키 세이조 가부시키가이샤 광 경화성·열 경화성 수지 조성물과 그것을 사용한 건식필름, 및 그의 경화물
WO2006004158A1 (fr) * 2004-07-07 2006-01-12 Taiyo Ink Mfg. Co., Ltd. Composition de resine photopolymerisable/thermodurcissable, film sec utilisant celle-ci et produit polymerise correspondant
WO2007108555A1 (fr) * 2006-03-22 2007-09-27 Fujifilm Corporation Procédé de production d'un film de compensation optique, plaque polarisante comprenant un film de compensation optique produit par ledit procédé et dispositif d'affichage à cristaux liquides
US7872695B2 (en) 2006-03-22 2011-01-18 Fujifilm Corporation Process of producing optical compensation sheet, polarizing plate comprising an optical compensation sheet produced by said process, and liquid crystal display device
JP2009250985A (ja) * 2008-04-01 2009-10-29 Kansai Paint Co Ltd 樹脂組成物、レジスト組成物及びレジストパターン形成方法
JP2018063405A (ja) * 2016-10-14 2018-04-19 互応化学工業株式会社 感光性樹脂組成物
WO2019128257A1 (fr) * 2017-12-27 2019-07-04 太阳油墨（苏州）有限公司 Composition de résine durcissable, film sec, article durci et carte de circuit imprimé
CN109970953A (zh) * 2017-12-27 2019-07-05 太阳油墨（苏州）有限公司 固化性树脂组合物、干膜、固化物、及印刷电路板
CN109970953B (zh) * 2017-12-27 2021-04-09 太阳油墨（苏州）有限公司 固化性树脂组合物、干膜、固化物、及印刷电路板
JP2019174751A (ja) * 2018-03-29 2019-10-10 株式会社タムラ製作所 感光性樹脂組成物
CN110895381A (zh) * 2019-11-20 2020-03-20 深圳市容大感光科技股份有限公司 感光阻焊油墨组合物、其用途及含有其的线路板
EP4215551A4 (fr) * 2020-09-18 2024-03-13 Konica Minolta, Inc. Composition durcissable, encre pour réserve de soudure et carte de circuit imprimé

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CN1821876A (zh) 2006-08-23
CN1821876B (zh) 2010-10-06
HK1048666B (zh) 2007-12-07

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