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WO2003059975A1 - Composition de resine photosensible et cartes imprimees - Google Patents

Composition de resine photosensible et cartes imprimees Download PDF

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Publication number
WO2003059975A1
WO2003059975A1 PCT/JP2001/011645 JP0111645W WO03059975A1 WO 2003059975 A1 WO2003059975 A1 WO 2003059975A1 JP 0111645 W JP0111645 W JP 0111645W WO 03059975 A1 WO03059975 A1 WO 03059975A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
parts
mass
unsaturated
Prior art date
Application number
PCT/JP2001/011645
Other languages
English (en)
Japanese (ja)
Inventor
Yuan Chien Lin
Kazunori Nishio
Toru Nakada
Original Assignee
Taiyo Ink Mfg. 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 Mfg. Co., Ltd. filed Critical Taiyo Ink Mfg. Co., Ltd.
Priority to JP2003560073A priority Critical patent/JPWO2003059975A1/ja
Priority to PCT/JP2001/011645 priority patent/WO2003059975A1/fr
Priority to AU2002217554A priority patent/AU2002217554A1/en
Priority to TW091120620A priority patent/TWI263115B/zh
Publication of WO2003059975A1 publication Critical patent/WO2003059975A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to a photosensitive resin composition and a printed wiring board, and more particularly, to an image forming method capable of forming an image by ultraviolet exposure and development with a dilute aqueous solution of an aqueous solution, and developing properties of an unexposed portion.
  • Various characteristics such as heat resistance, chemical resistance, and electrical insulation, especially in air bubble resistance, and excellent in explosion hole resistance for printed wiring boards.
  • the present invention relates to a photosensitive resin composition suitable for a solder resist film.
  • the printed wiring board is formed by forming a conductor circuit pattern on a base material, and electronic components are mounted on the land portion of the conductor circuit by soldering.
  • the circuit part is covered with a solder resist film to protect the conductor.
  • the solder resist film not only prevents solder from adhering to unnecessary parts when mounting electronic components on the printed wiring board, but also oxidizes and corrodes the circuit. It has the function of preventing
  • a photosensitive resin composition used for such a solder resist film is required to have excellent resolution and dimensional accuracy as the density of printed wiring boards increases. ing.
  • various liquid resist compositions excellent in resolution, dimensional accuracy, edge covering properties, and the like have been proposed, and are widely used as solder resist films.
  • alkaline developable Developed liquid solder resist composition with excellent heat resistance and resolution, using cresol no-volak type epoxy-modified resin as the main component as a suitable UV curable material See Japanese Patent Application Laid-Open No. Sho 61-244 869).
  • the formed solder resist is required.
  • the film is a phenomenon in which the periphery of the through hole is lifted up during solder leveling (hereinafter simply referred to as “bubble”), or the through hole is formed during post level soldering or solder leveling.
  • explosion hole the phenomenon that the coating film protrudes easily
  • Taiwan and the Asian region the number of wiring boards in which all through-holes of wiring boards such as copper through-hole wiring boards are filled with a liquid solder resist composition is increasing, and the above-mentioned voids And the problem of the explosion was remarkable.
  • the present invention has been made to solve the above-mentioned problems of the prior art, and the main purpose of the present invention is to provide a solder resist for a printed wiring board having excellent air bubble resistance and explosion hole resistance.
  • An object of the present invention is to provide a photosensitive resin composition suitable for a film.
  • the coating required for the solder resist It has excellent properties such as heat resistance, solvent resistance, solvent resistance, adhesion, electrical insulation, and other properties, such as heat resistance, drying properties, tackiness, photocurability, developability, pot life, and shell fly.
  • a liquid photo-solder resist that can be developed with dilute aqueous solutions, it has excellent resistance to electroless gold plating, as well as excellent air bubble resistance and explosion hole resistance, which were insufficient with conventional technologies.
  • An object of the present invention is to provide a useful photosensitive resin composition.
  • Another object of the present invention is to provide a printed wiring board having a solder resist layer excellent in air bubble resistance and explosion hole resistance.
  • the inventors conducted intensive research to achieve the above-mentioned purpose in order to provide a solder resist composition that is excellent in air bubble resistance and explosion hole resistance even in the hole filling specification, which is the mainstream in Taiwan and the Asian region. As a result, the inventors have completed the invention having the following content as a summary.
  • the photosensitive resin composition of the present invention comprises (A) an active energy linear curable resin, (B) a photopolymerization initiator, (C) a reactive diluent, and (D) a compound having an epoxy group.
  • a composition comprising (A) an esterified product of an epoxy group formed by an esterification reaction between a novolak type epoxy compound and an unsaturated rubonic acid; The esterification of an epoxy group generated by the esterification reaction of a prepolymer (a) obtained by reacting a saturated polybasic anhydride with a bisphenol-type epoxy compound and an unsaturated carboxylic acid
  • the mixing ratio of (a), (b) and (c) in the active energy linear curable resin (A) is (a) 100 parts by mass and (b) 20 to 300 parts by mass, more than (0) 0 parts by mass and 150 parts by mass or less.
  • the preferred mixing ratio of each component is (B):! To 30 parts by mass, more preferably 10 to 25 parts by mass, with respect to 100 parts by mass of (A).
  • the photosensitive resin composition of the present invention as an active energy linear curable resin (A) constituting the composition, is obtained by an esterification reaction between a novolak type epoxy compound and an unsaturated carboxylic acid.
  • (A) obtained by reacting the resulting esterified product of the epoxy group with a saturated or unsaturated polybasic anhydride, and an unsaturated carboxylic acid such as a bisphenol type epoxy compound.
  • a prepolymer (b) obtained by reacting an esterified product of an epoxy group formed by an esterification reaction with a saturated or unsaturated polybasic anhydride with an unsaturated monobasic acid copolymer resin The greatest feature is that a mixture of a prepolymer (c) obtained by the reaction of a compound with an alicyclic epoxy group-containing unsaturated compound is used.
  • a photosensitive resin composition which is excellent as a liquid photo-solder resist which can be developed with a dilute aqueous alkaline solution and has excellent heat resistance and explosion hole resistance can be provided. Each component in the composition will be described.
  • an esterified product of an epoxy group which is formed by an esterification reaction between a novolak type epoxy compound and an unsaturated carboxylic acid, which constitutes the active energy ray-curable resin (A) of the present invention.
  • the prepolymer ( a ) obtained by reacting a saturated or unsaturated polybasic acid anhydride will be described.
  • Novolak type epoxy compounds used for the synthesis of the prepolymer (a) include, for example, phenols such as phenol, cresol, and alkynolephenol.
  • phenols such as phenol, cresol, and alkynolephenol.
  • novolaks obtained by the reaction of aldehydes with formaldehyde in the presence of an acidic catalyst and epihalohydrin such as epichlorohydrin Yes but not limited to.
  • Unsaturated carboxylic acids added to the epoxy group of the novolak type epoxy compound include acrylic acid, a dimer of acrylic acid, metaacrylic acid, and hydroxy. Kisechil (meta) acrylate, hydroxypropyl (meta) acrylate, hydroxybutyl (meta) acrylate, phenyldalicydil (meta) ) Athalylate, (meta) ata linolenic acid-protolatone adducts, etc. Unsaturated dibasic acid anhydride adducts of hydroxyl-containing acrylates, etc. Is mentioned. Particularly preferred here are acrylic acid and metaacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or as a mixture.
  • a saturated or unsaturated polybasic acid anhydride which reacts with an alcoholic hydroxyl group in an esterification product formed by an esterification reaction between the novolak type epoxy compound and the unsaturated carboxylic acid.
  • examples thereof include aliphatic or aromatic dibasic anhydrides such as oleic acid, phthalic anhydride, and itaconic anhydride.
  • the amount of the saturated or unsaturated polybasic acid anhydride to be used should be within a range where the acid value of the obtained prepolymer (a) is 50 to 120 mg KOH / g. Is preferred.
  • Examples of the bisphenol type epoxy resin used in the production of the prepolymer (b) include, for example, bisphenol A type or bisphenol F type epoxy resin. Resin, or a bisphenol-type epoxy resin obtained by adding an epoxynohydrin such as epichlorohydrin to the alcoholic hydroxyl group of the epoxy resin. However, it is not limited to these.
  • unsaturated carboxylic acids that can be produced include acrylic acid, dimers of acrylic acid, meta-atalinoleic acid, hydroxyshethyl (meta) acrylate, and hydridic acid.
  • unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as acid prolatatotone adducts.
  • Particularly preferred here are acrylic acid and metaacrylic acid.
  • a saturated or unsaturated polybasic anhydride which reacts with an alcoholic hydroxyl group in an ester formed by an esterification reaction of the bisphenol type epoxy compound with the unsaturated carboxylic acid.
  • Examples include methyltetrahydrophthalic anhydride, tetrahydrofuran phthalanoic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and Examples thereof include aliphatic or aromatic dibasic anhydrides such as novic acid, maleic anhydride, phthalic anhydride, and itanic anhydride.
  • the amount of the saturated or unsaturated polybasic acid anhydride to be used should be such that the acid value of the resulting prepolymer (a) is within a range of 50 to 130 mg KOH / g. Is preferred.
  • the unsaturated monobasic acid copolymer resin used in the production of the prepolymer (c) preferably contains an acid group.
  • Acrylic resins include (meth) acrylic acid, 2-carboxyethyl (meta) acrylate, 2-carboxypropyl (meta) acrylate, and maleic anhydride.
  • a generally known copolymer obtained by copolymerizing one or more monomers selected from a saturated compound, a polyolefin-based compound and other monomers can be used.
  • This unsaturated monobasic acid copolymer resin reacts a part of the acid groups of the resin with the epoxy group of the alicyclic epoxy group-containing unsaturated compound to introduce an unsaturated group into the resin, and to give the resin a resin. It is necessary to provide photocurability. Accordingly, the acid value of the unsaturated monobasic acid copolymer resin must be appropriately controlled, and is preferably in the range of 30 to 260.
  • Examples of the alicyclic epoxy group-containing unsaturated compound to be reacted with the unsaturated monobasic acid copolymer resin include a compound having one radically polymerizable unsaturated group and one alicyclic epoxy group in one molecule.
  • a compound having both an alicyclic epoxy group and an acryl group is preferable.
  • Ali rug In addition to the compounds having the alicyclic epoxy group and the acryl group at the same time, for example, glycidyl (meth) acrylate,] 3-methyldicydyl (meta) a Tally rate, Ali rug An aliphatic epoxy group-containing unsaturated compound such as ricidyl ether may be used in combination.
  • the number average molecular weight of the unsaturated group-containing resin is desirably from 300 to 3000.
  • the mixing ratio of the prepolymer (a), the prepolymer (-b) and the prepolymer (c) is preferably 100 parts by mass.
  • the amount of the prepolymer (b) is from 20 to 300 parts by mass, the amount of the prepolymer (c) is more than 0 parts by mass and not more than 150 parts by mass.
  • the photopolymerization initiator (B) is not limited to compounds known in the art as photopolymerization initiators, and also absorbs light in the ultraviolet or visible light range, and It includes those capable of radically polymerizing an unsaturated group such as a riloil group.
  • photopolymerization initiators include, for example, benzoin, benzoin quinoleate ether, benzoin ethylenate ether, benzoin isopropylinole ether, and other benzoin and benzoin alkynoleate ethers;
  • 2 methinorea Traquinone, 2—ethylantraquinone, 2 —
  • photopolymerization initiators can be used alone or as a mixture of two or more kinds.
  • N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylmethylaminobenzoic acid Photoinitiating aids such as tertiary amines such as disoamiyl ester, pentyl-4, dimethylaminobenzoate, triethylamine and triethanolamine can be added.
  • a titanocene compound such as CGI-1784 (manufactured by Ciba Specialty 'Chemicals Inc.) that absorbs in the visible light region can be added to promote the photoreaction. You.
  • preferred photopolymerization initiators are 2-methyl-1- [41- (methylthio) phenyl] -12-morpholinoamino-prononon-1,2-benzyl-12-dimethyl Chilamino 1- (4-morpholinophenyl) -butane-111-one, etc., but not particularly limited to them, and light in the ultraviolet or visible light region.
  • photopolymerization initiators and photoinitiating assistants can be used alone or in combination of two or more as long as they absorb radicals and radically polymerize unsaturated groups such as (meth) acryloyl groups. Can be used.
  • the amount of the photopolymerization initiator (B) is preferably 1 to 30 parts by mass, more preferably 100 to 100 parts by mass of the active energy ray-curable resin (A). Is from 10 to 25 parts by mass.
  • the photosensitive (meta) acrylate compound (C) may be a liquid, solid or solid at room temperature having one or more (meta) aryloyloxy groups in one molecule.
  • Semi-solid photosensitive (meta) acrylate compounds can be used. Specifically, for example, '2—Hydroxy Shechilure Crate, 2—HydroxyPropyl Cleate, Pentaerythritol Triaraterate, Dipentaeryte Hydroxyl-containing acrylates such as thoritol pentaacrylate; water-soluble creatures such as polyethylene glycol diacrylate and polypropylene glycol diacrylate.
  • Trimethylol promontory acrylate pentaerythritol tertratalate, dipentaerythritol Polyfunctional alcohol polyfunctional alcohol Stearate acrylates; polymethyl alcohol such as trimethylolpronone, hydrogenated bisphenol A, or bisphenol A, biphenyl phenol, etc.
  • polyfunctional (meta) acrylate compounds having two or more (meta) acryloyloxy groups in one molecule are preferred.
  • Such a photosensitive (meta) acrylate compound (C) is used for the purpose of improving the photorefractive property of the composition.
  • a photosensitive (meta) acrylate compound which is liquid at room temperature is used for the purpose of increasing the photoreactivity of the composition, adjusting the composition to a viscosity suitable for various coating methods, and preparing an aqueous alkali solution. It also serves to help the solubility of
  • a large amount of a photosensitive (meta) acrylate compound which is liquid at room temperature is used in a large amount, the dryness of the coating film to the touch is not obtained, and the characteristics of the coating film tend to be deteriorated. It is not preferred to use it.
  • the compounding amount of the photosensitive (meth) acrylate compound (C) is preferably based on 100 parts by mass of the active energy ray-curable resin (A). It is preferably 2 to 40 parts by mass, more preferably 10 to 30 parts by mass.
  • Epicron 830 manufactured by Dainippon Ink & Chemicals, Inc .
  • Epiko manufactured by Japan Epoxy Resin 807, Toto Kasei Co., Ltd. YDF — 170, YDF — 175, YDF — 204, Ciba's specialty chemicals, Inc.
  • XPY Bisphenol F-type epoxy resin such as 310 (all trade names); Toto Kasei Co., Ltd. ST-204, ST-207, ST- Hydrogenated bisphenol A type epoxy resin such as 300 (trade name); Epoxy resin 604, manufactured by Epoxy Resin, YH-434, manufactured by Toto Kasei Co., Ltd., Araldide MY720, manufactured by Chemicals, Inc.
  • Glycidylamine-type epoxy resin such as Sumiepoxy ELM-120 (trade name) manufactured by Ciba, Inc .; Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals Hydantine type epoxy resin; Celloxide 2101, manufactured by Daicel Chemical Industries, Ltd., Araldide CY175, CY177, manufactured by Chino Specialty Chemicals, Inc. Alicyclic epoxy resins (all trade names); YL-933 manufactured by Japan Epoxy Resin, T.E.N., EPPN-501 manufactured by Dow Chemical Co., £ 1, £? 1 ⁇ — 502, etc.
  • Epicoat 1 manufactured by Japan Epoxy Resin Bisphenol A Novolak type epoxy resin such as 5 7S (trade name); Epicoat YL—931, manufactured by Japan Epoxy Resin, manufactured by Ciba Specialty Chemical Kaname Taltra-Roll-Ethan-type Epoxy of Araldide 16 3 etc. (all are trade names) Heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Co., Ltd. (all trade names); Jiglycidyl phthalate resin such as Blenmer DGT manufactured by K.K .; Tetra-Dasidyl xylenol such as ZX-1063 manufactured by Toto Kasei Co., Ltd.
  • Ethane resin ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd., HP-430, EXA-4750, EXA-47, manufactured by Ink Chemical Industry Co., Ltd.
  • Epoxy resin having a dicyclopentagen skeleton, such as Naphtalene group-containing epoxy resin such as HP-720, HP-720OH manufactured by Dainippon Ink & Chemicals, Inc.
  • Glycidylmethacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by Nippon Oil & Fats Co., Ltd .; Examples include, but are not limited to, co-polymerized epoxy resins of sidylmethacrylate, and polybutanes containing one or more internal epoxide groups.
  • the compound (D) having an epoxy group also includes a compound having a cyclic ether group other than the glycidyl group. Compound (D) can be used alone or in combination of two or more.
  • the compounding amount of the compound (D) having an epoxy group can be any amount according to the required coating film properties. Preferably, it is 2 to 50 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the active energy linear curing resin (A).
  • the photosensitive resin composition of the present invention may contain, as necessary, other additives such as a thermal polymerization inhibitor, a surfactant, an ultraviolet absorber, a thixotropic agent, and a coloring agent. Further, a thermoplastic resin or the like can be blended. .
  • the photosensitive resin composition of the present invention is diluted as necessary to adjust the viscosity to be suitable for a coating method, and this is applied, for example, to a printed wiring board on which a circuit is formed by a screen.
  • the composition is applied by a printing method, a curtain coating method, a spray coating method, a roll coating method, or the like, and then contained in the composition at a temperature of, for example, 70 to 90 ° C.
  • the organic solvent is evaporated and dried to form a tack-free coating film.
  • the tack-free coating film thus formed is selectively exposed to active energy rays through a photomask forming a pattern, and the unexposed portions are diluted.
  • the pattern is developed by developing with an aqueous solution of alkali metal, and then the pattern is cured. Furthermore, irradiation with active energy rays is followed by heat hardening or heat curing followed by irradiation with active energy, or heat curing alone to final cure (this work). By curing, a cured film (solder resist film) with excellent heat resistance, adhesion, electroless plating resistance, and electrical properties is obtained.
  • the printed wiring board on which the circuit is formed is coated with the solder resist film composed of the cured coating of the photosensitive resin composition of the present invention, and the printed wiring board of the present invention is formed. A plate is obtained.
  • the aqueous alkali solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate.
  • Aqueous solutions of lithium, ammonia, amines, etc. 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.
  • the printed wiring board of the present invention which can be used as a line of active energy for one ray or the like, is excellent in air bubble resistance and explosion hole resistance. The effect of the present invention is particularly remarkable when a base is used in such a manner that the solder resist composition is filled in the through holes of the wiring board.
  • Resin A—1 Prepolymer (a)>
  • the hydroxyl group of bisphenol A-type epoxy resin with a softening point of 65 to 75 ° C is epoxidized, acrylic acid is added to the epoxy group, and then succinic anhydride is added to the hydroxyl group. Resin adjusted to 100
  • UV curable resin cyclomer ACA 250 (manufactured by Daicel Chemical)
  • KS-66 Silicone defoamer manufactured by Shin-Etsu Chemical Co., Ltd.
  • the photosensitive resin composition according to the present invention does not impair various properties required for the solder resist and has an air bubble resistant explosion resistance. It can be seen that the pore resistance is excellent.
  • the evaluation criteria are as follows.
  • the evaluation criteria are as follows.
  • the coating film was subjected to crosscut and tape peeling according to the test method of JISDO202, and the state of peeling was visually judged.
  • the evaluation criteria are as follows.
  • the coating film after boss release is applied to the JISK540 test method. Accordingly, the hardness was measured under a load of 1 kg. . (Solder heat resistance)
  • the paint film after post cure was immersed twice in a solder bath at 260 ° C for 10 seconds using rosin-based and water-soluble flux according to the test method of JISC 6481. Then, the state of the coating film was confirmed.
  • the evaluation criteria are as follows.
  • the coating film has no abnormalities such as peeling
  • the coating after the boss release was solder leveled by a horizontal leveler, and the peeling state of the through holes after tape peeling was confirmed.
  • the evaluation criteria are as follows.
  • the coating after the boss cure was solder leveled with a horizontal leveler, and the ink condition in the through hole was visually observed.
  • the evaluation criteria are as follows.
  • the coating film was immersed in propylene glycol monomethyl ether acetate at 20 ° C for 30 minutes, and the condition of the coating film was obtained. It was confirmed.
  • the evaluation criteria are as follows.
  • ⁇ There is no abnormality such as whitening on the coating film surface, and there is no peeling at the edge.
  • the coated film after boss clearing was immersed in a 10% aqueous solution of 1% sulfuric acid at 20 ° C. for 30 minutes to confirm the state of the coated film.
  • the evaluation criteria are as follows.
  • the coating film surface has an abnormality such as whitening, or the edge has peeled off
  • the coating film after the boss preparative Kiyu A dipped 1 0 W t% 3 0 minutes at 2 0 ° C to hydroxide Na Application Benefits ⁇ anhydrous solution confirmed the status of the coating film.
  • the evaluation criteria are as follows.
  • a solder resist for a printed wiring board having excellent air bubble resistance and explosion hole resistance without impairing various characteristics required for the solder resist.
  • a photosensitive resin composition suitable for a thin film can be provided.

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Abstract

L'invention concerne une composition de résine photosensible comprenant (A) une résine durcissable par rayons artiniques, (B) un initiateur de photopolymérisation, (C) un diluant réactif et (D) un composé époxy. La résine (A) est composée a) d'un prépolymère produit par estérification d'un composé époxy de type Novolaque avec un acide carboxylique insaturé et par réaction du produit d'estérification époxy résultant avec un anhydride d'acide polybasique saturé ou insaturé, b) un prépolymère produit par estérification d'un composé époxy de type bisphénol avec un acide carboxylique insaturé et par réaction du produit d'estérification époxy résultant avec un anhydride d'acide polybasique saturé ou insaturé et (c) un prépolymère produit par réaction d'une résine copolymère d'acide monobasique insaturé avec un composé insaturé contenant de l'époxy alicyclique.
PCT/JP2001/011645 2001-12-28 2001-12-28 Composition de resine photosensible et cartes imprimees WO2003059975A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2003560073A JPWO2003059975A1 (ja) 2001-12-28 2001-12-28 感光性樹脂組成物およびプリント配線板
PCT/JP2001/011645 WO2003059975A1 (fr) 2001-12-28 2001-12-28 Composition de resine photosensible et cartes imprimees
AU2002217554A AU2002217554A1 (en) 2001-12-28 2001-12-28 Photosensitive resin composition and printed wiring boards
TW091120620A TWI263115B (en) 2001-12-28 2002-09-10 Photosensitive resin composition and printed wiring boards

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JP2006190848A (ja) * 2005-01-07 2006-07-20 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性の一液型ソルダーレジスト組成物及びそれを用いたプリント配線板
JP2009269994A (ja) * 2008-05-07 2009-11-19 Taiyo Ink Mfg Ltd プリント配線板の穴埋め用熱硬化性樹脂組成物及びそれを用いたプリント配線板
US8361605B2 (en) 2007-04-24 2013-01-29 Mitsui Chemicals, Inc. Photosensitive resin composition, dry film, and processed product made using the same
WO2013021734A1 (fr) * 2011-08-11 2013-02-14 互応化学工業株式会社 Composition de résine pour résists
JP2014169377A (ja) * 2013-03-04 2014-09-18 Tamura Seisakusho Co Ltd 活性エネルギー線硬化性樹脂組成物
KR20140123971A (ko) 2012-03-23 2014-10-23 타이요 잉크 (쑤저우) 컴퍼니 리미티드 감광성 수지 조성물 및 그의 경화물, 및 프린트 배선판
EP3243854A1 (fr) * 2016-05-13 2017-11-15 Nan-Ya Plastics Corporation Faible dk/df composition résistant de soudure utilisé pour carte de circuit imprimé
US10527936B2 (en) 2016-06-17 2020-01-07 Nan Ya Plastics Corporation Low Dk/Df solder resistant composition use for printed circuit board

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JPH04151158A (ja) * 1990-05-18 1992-05-25 Arakawa Chem Ind Co Ltd アルカリ現像型液状フォトソルダーレジストインキ組成物
JPH04166944A (ja) * 1990-10-31 1992-06-12 Mitsubishi Kasei Corp 感光性樹脂組成物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006190848A (ja) * 2005-01-07 2006-07-20 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性の一液型ソルダーレジスト組成物及びそれを用いたプリント配線板
US8361605B2 (en) 2007-04-24 2013-01-29 Mitsui Chemicals, Inc. Photosensitive resin composition, dry film, and processed product made using the same
JP2009269994A (ja) * 2008-05-07 2009-11-19 Taiyo Ink Mfg Ltd プリント配線板の穴埋め用熱硬化性樹脂組成物及びそれを用いたプリント配線板
KR101561054B1 (ko) * 2011-08-11 2015-10-16 고오 가가쿠고교 가부시키가이샤 레지스트용 수지 조성물
JP2013040233A (ja) * 2011-08-11 2013-02-28 Goo Chemical Co Ltd レジスト用樹脂組成物
CN103748131A (zh) * 2011-08-11 2014-04-23 互应化学工业株式会社 抗蚀剂用树脂组合物
US9128375B2 (en) 2011-08-11 2015-09-08 Goo Chemical Co., Ltd. Resin composition for masks
WO2013021734A1 (fr) * 2011-08-11 2013-02-14 互応化学工業株式会社 Composition de résine pour résists
CN103748131B (zh) * 2011-08-11 2016-02-24 互应化学工业株式会社 抗蚀剂用树脂组合物
KR20140123971A (ko) 2012-03-23 2014-10-23 타이요 잉크 (쑤저우) 컴퍼니 리미티드 감광성 수지 조성물 및 그의 경화물, 및 프린트 배선판
JP2014169377A (ja) * 2013-03-04 2014-09-18 Tamura Seisakusho Co Ltd 活性エネルギー線硬化性樹脂組成物
EP3243854A1 (fr) * 2016-05-13 2017-11-15 Nan-Ya Plastics Corporation Faible dk/df composition résistant de soudure utilisé pour carte de circuit imprimé
US10527936B2 (en) 2016-06-17 2020-01-07 Nan Ya Plastics Corporation Low Dk/Df solder resistant composition use for printed circuit board

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JPWO2003059975A1 (ja) 2005-05-19
TWI263115B (en) 2006-10-01

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