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WO1993006529A1 - Composition resineuse photosensible - Google Patents

Composition resineuse photosensible Download PDF

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Publication number
WO1993006529A1
WO1993006529A1 PCT/JP1992/001166 JP9201166W WO9306529A1 WO 1993006529 A1 WO1993006529 A1 WO 1993006529A1 JP 9201166 W JP9201166 W JP 9201166W WO 9306529 A1 WO9306529 A1 WO 9306529A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
group
resin composition
photosensitive resin
meta
Prior art date
Application number
PCT/JP1992/001166
Other languages
English (en)
Japanese (ja)
Inventor
Shigeru Hagio
Kazuhiko Kohda
Shinichi Uehara
Original Assignee
San Nopco Limited
Ibiden 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
Priority claimed from JP26270191A external-priority patent/JPH0572735A/ja
Priority claimed from JP26270491A external-priority patent/JPH0695379A/ja
Priority claimed from JP26270391A external-priority patent/JPH0683052A/ja
Application filed by San Nopco Limited, Ibiden Co., Ltd. filed Critical San Nopco Limited
Publication of WO1993006529A1 publication Critical patent/WO1993006529A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates to a photosensitive resin composition.
  • the present invention relates to a photosensitive resin composition suitable as a register used in manufacturing a printed wiring board.
  • a photosensitive resin composition has been widely used as a register, such as an electroless plating register or a solder register, used in the production of a printed wiring board.
  • This resist is exposed to an electroless copper plating solution at about PH12, 70 for a long time, for example, so that it can withstand highly concentrated aqueous alkali solutions.
  • liquid properties are required, conventional registries are only resistant to low concentration or low temperature alkaline.
  • circuits have become finer as the density of printed wiring boards has increased, and registers have been required to have excellent sensitivity, resolution, and developability.
  • conventional registries do not always satisfy all requirements.
  • an organic solvent is conventionally used as a developer, but the organic solvent poses a risk of air pollution or ignition.
  • JP-A-64-36545 discloses a photosensitive resin composition comprising a polymerizable unsaturated oligomer having a carboxy group and a vinyl group, an epoxy compound, and a photopolymerization initiator.
  • Japanese Patent Application Laid-Open No. 1-105240 describes a photosensitive resin composition comprising urethane (meth) acrylate, a linear polymer, and a polymerization initiator.
  • the photosensitive resin composition described in Japanese Patent Application Laid-Open No. 2-247564 has a pH of 8,70. Although resistant to C plating, it cannot be used with PHI 2, 70 ° C plating.
  • the photosensitive resin composition described in JP-A-64-36545 can sufficiently withstand the electroless copper plating solution at PH12 and PH70, but has a poor resolution of 170 ⁇ m and a fine resolution. Cannot be used for circuit processing applications.
  • the photosensitive resin composition described in JP-A No. 11052/40 is resistant to an electroless copper plating solution of pH 12 and 70 and has a good resolution of 70 ⁇ , There is a drawback that the developer is an organic solvent.
  • the present invention provides a photosensitive resin composition having developability with an aqueous alkaline solution and having excellent sensitivity, resolution, and electroless plating resistance.
  • the above-mentioned problems include (A) a polymer having a carboxyl group, a polymer having an anhydrous carboxyl group, polyvinylphenols, a saponified polyvinyl acetate polymer, a novolak resin, and a hydroxyl resin.
  • (D) (i) A homopolymer of one or more monomers selected from the group consisting of alkyl (meth) acrylate, acrylonitrile, and styrene Alternatively, the copolymer is used as a trunk polymer, and a hydroxy-containing (meta) acrylate, an amino group or an alkylamino group-containing (meta) acrylate is used. Relates, carboxyl group-containing (meta) acrylates, bulesters, bulue
  • N Vinylpyrrolidone, vinylpyridines, and at least one selected from the group consisting of monomers represented by the following general formula (I): Also, a graft polymer using a homopolymer or a copolymer of a monomer as a branch polymer,
  • thermosetting compound comprising:
  • thermosetting composition (ii) a mixture of (a) the above-mentioned graphite polymer and (b) a block-isolated compound having at least two substituents represented by the following general formula (II):
  • a further thermosetting composition (ii) a mixture of (a) the above-mentioned graphite polymer and (b) a block-isolated compound having at least two substituents represented by the following general formula (II):
  • R 3 represents an alkoxy group, an aryloxy group, an alkyl aryloxy group, an alkylidene aminooxy group, an amino group, a lactam group or ] 8 — Represents a dicarbylmethyl group.
  • R 4 and R 7 are aliphatic hydrocarbons having 1 to 6 carbon atoms or aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond, and R 5 and R 6 are carbon atoms. Represents an aliphatic hydrocarbon of the formulas 1 to 6.
  • a photosensitive resin composition comprising such a composition.
  • a binder polymer capable of forming a film which is soluble or swellable in an aqueous solution of the component (A) is a curing of the photosensitive resin composition. It serves as a binder for the product and gives the photosensitive resin composition developability to an aqueous alkali solution.
  • a polymer having a carboxyl group examples include a polymer having a carboxyl group, a polymer having an anhydrous carboxyl group, polyvinylphenols, and saponified acetic acid. Examples include a vinyl polymer, a novola, a sock resin, and a (meth) acrylate copolymer having a hydroxyl group.
  • polymer having a carboxyl group examples include monomers having a carboxyl group and (meth) acrylic acid esters, styrenes, and acrylic polymers. Examples include copolymers with vinyl monomers such as nitriles.
  • the weight average molecular weight is preferably from 500 to 200,000.
  • the monomer having a carboxyl group examples include (meth) acrylic acid, itaconic acid, crotonic acid, sorbic acid, fumaric acid, and promal acid. Piolic acid, maleic acid, cinnamic acid, and the like.
  • (meth) acrylyl esters include methyl (meth) acrylate, ethyl (meta) acrylate, and isobutyl (meta) acrylate.
  • Metal acrylate, etc.-Tenoré (meta) acrylate, 2-Chlorocinole (meta) acrylate, 2-Cloth Isopropyl (meta) acrylate, 2-bromoethyl (meta) acrylate, 2,3-dibromopropyl (meta) acrylate, tribromo Phenyl (meta) acrylate, trifluoroethyl (meta) acrylate, tetrafluoropropyl (meta) acrylate, octa Fluoropentyl (meta) acrylate, heptadecafluorodecyl (meta) acrylate, and rogenchialkyl (meta) acrylate, 2 — Hidlo Ki Shechill
  • Metal acrylate, 2-hydroxypropyl (meta) acrylate, 3-hydroxypropyl (meta) acrylate, 4-hydroxy Xyl butyl (meta) acrylate, 5—hydroxypentyl (meta) acrylate, 6—hydroxy hexyl (meta) acrylate, 2 — Hydroxy 3 — Fenoxypropyl (meta) acrylate, 3 — Chloro 2 — Hydroxypropyl (meta) acrylate, 3 — Black mouth 2 — Hydroxybutyl (meta) acrylate, etc. Meta) acrylate, 2-cyanoethyl acrylate, tetrahydrol Ruffled (meta) clear rate.
  • styrenes include styrene, ⁇ -methylstyrene, ⁇ -isopropenylstyrene, vinyltoluene, and the like.
  • acrylonitriles include acrylonitrile and ⁇ -methylacrylonitrile.
  • vinyl formate vinyl acetate, vinyl butyrate, vinyl propionate, vinyl laurate, vinyl benzoate, vinyl benzenesulfonate, vinyl isopropyl ether, vinyl pyrrolidone, Use chloride bur etc.
  • polymer having an anhydrous carboxyl group examples include a monomer having an anhydrous hydroxyl group and a (meth) acrylic acid ester, styrene, acrylonitrile, and the like. And a copolymer of a vinyl monomer and.
  • the weight-average molecular weight is preferably from 2000 to 1.00;
  • the monomer having a carboxyl anhydride group examples include 2,3—dichloromaleic anhydride, 2—cyclomouth maleic anhydride, citrate anhydride, and citrate anhydride. Dodecenyl succinic acid, anhydrous nonenyl succinic acid, bromomaleic anhydride, maleic anhydride and the like.
  • Polyvinylphenols include homopolymers of vinylphenol, or vinylphenol and (meth) acrylic acid esters, styrenes, and Copolymers with vinyl monomers such as acrylonitriles, monomers having a carboxyl group, and monomers having an anhydrous carboxyl group are exemplified.
  • the weight average molecular weight of the polyvinyl phenols is preferably from 2000 to 500,000.
  • Examples of the saponified vinyl acetate polymer include a completely saponified vinyl acetate polymer, a partially saponified vinyl acetate polymer having a saponification degree of 88 to 99 mol%, and the like.
  • the weight average molecular weight of the saponified vinyl acetate polymer is preferably from 500 to 500,000.
  • the novolac resin examples include a phenol novolac resin and a cresol novolac resin which are swollen or soluble in an aqueous alkali solution.
  • the weight average molecular weight of the nopolak resin is preferably from 500 to 500.
  • (meth) acrylate copolymer having a hydroxy group a mono (meth) acrylate having a hydroxy group and a (meth) acrylate copolymer having a hydroxy group can be used.
  • the weight average molecular weight of the copolymer is 50,000 to: L 0000 is preferred.
  • non-polar polymer are polyvinylphenols and a (meth) acrylate copolymer having a hydroxyl group.
  • two or more binder polymers can be used in combination.
  • the content of the binder polymer in the photosensitive resin composition is preferably from 20 to 80% by weight. No. When the amount is less than 20% by weight, the developing property is deteriorated, and when the amount exceeds 80% by weight, the electroless plating resistance is deteriorated.
  • an acrylic compound having at least two ethylenically unsaturated bonds as the component (B) constituting the photosensitive resin composition of the present invention and capable of being polymerized has an activity of It has the property of being hardened by energies, and gives the composition of the present invention excellent sensitivity to active energy rays. For this reason, the photosensitive resin composition of the present invention exhibits excellent resolution.
  • the acrylic compound a known monomer which is preferably cured by irradiation with an active energy ray having a boiling point of 100 or more at atmospheric pressure, can be used.
  • Such a monomer include, for example, 1) Ethylene glycol (meta) acrylate, propane diol (meta) acrylate Butanediol di (meta) acrylate, pentanedioldi (meta) acrylate, hexanedioldi (meta) acrylate, neopentyl glycol (meta) ) Clearate, hydroxypivalate neopentyl glycolate (meta) clearate, polyethylene glycolate (meta) clearate, vol.
  • metal Principal recollection (meta) cryate, porphyra transcript Refrigerant collage (meta) acrylate, trimethyl propane Re (meta) Multi-valued alcohol, such as penta-erythritol, penta-erythritol, pentaerythritol, and terephthalate (meta) acrylic (Meth) acrylic acid esters; 2) Trade name ARONIX M-1 100, Aronix M — 120 0, Aronix M — 6
  • the terminal is made up of an isolanet and a polyol.
  • a reaction product of a polymer and a (meta) acrylate containing a hydroxy group is exemplified.
  • the trade names Sumijur N a biuret derivative of hexamethylene diisocyanate
  • Sumijur L the trimethyl tertiary mouth of the trimethylisocyanate
  • propanol a hydroxy group-containing (meta) acrylate
  • the used reactants can be used.
  • the hydroxy group-containing (meta) crelet includes a branch polymer of a graph polymer (D-i) described later. .
  • the monomers that constitute the (D-i) graphite polymer can also be used. Furthermore, mixtures of the above-mentioned acrylic compounds can also be used.
  • the content of the acrylic compound in the photosensitive resin composition is preferably from 20 to 80% by weight. When the content is less than 20% by weight, the sensitivity is lowered and the resolution is deteriorated. When the content is more than 80% by weight, the adhesion is deteriorated.
  • photopolymerization initiator of the component (C) in the photosensitive resin composition of the present invention include: 11- (41-isopropylpropyl) 12-hydroxy2-medium Chilpro non-one
  • Siben Phenonone 41-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3'-bis (N, N-diethylamino) benzopheno , 4,4'-bis (N, N-Jetylamino) Benzofuenonon, 4 ', 4 "-Jet-Louisofta mouth phenon, 3,3', 4,4'1- Benzofu, such as tetra (t-butyl peroxycarbonyl) benzophenone, 41-benzoyl 4'-methinoresifeninoresulfide, acriluhibenzofufenon, etc.
  • Nonones thioxanthone, 2—methylthioxanthone, isopropylthioxanthone, 2,4—dimethinolethioxanthone, 2,4—getinolexanthonthone, 2 , 4 — diisopropirchioxanthon Xanthones such as chloroxanthontone and 2,4-dichlorothioxanthon; diketones such as diacetyl and benzyl; 2—ethylethyl Trakinon, 2—t Thizolean trakinonone, 2, 3 — diphenyl anthraquinone, 1, 2 — benzanthrakinonone, octamethylan anthraquinone, camphorquino Quinones such as benzophenone, dibenzosuberone, 9,10-phenanthrene quinone, and the like.
  • the content of the photopolymerization initiator in the photosensitive resin composition is 0.
  • the alkyl (meta) acrylate, acrylonitrile, and styrene having 1 to 4 carbon atoms in the phenol group.
  • the stem polymer is derived from only the above-mentioned monomer.
  • 2-merethylhexyl (meth) acrylate, glycidyl (meta) ac Polymers using a copolymer such as lilate or vinyl acetate in the range of 0 to about 50% by weight may be used.
  • the monomer constituting the branch polymer of the graphite polymer in the present invention include a hydroxy group-containing (meta).
  • acrylates are 2-hydroxyethyl (meta) acrylate, 2-hydroxypropyl (meta) acrylate, and 3-chlorolate.
  • TONEM 100 Power product creator, manufactured by Union Carbide Co., Ltd.] Ester H0-mpp [manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.], Light Ester M-60 OA [2—Hydroxy 3—Phenoxypropiryl Cleitol And divalent alcohols, for example, 1,10-decanediol, neopentylglycol, bis (2-hydrogen). (Meth) acrylic acid, such as addition reaction product of telephthalate, bisphenol A and ethylene oxide or propylene oxide Monoesters with acids can be used.
  • Examples of the (meth) acrylate containing an amino group or an alkylamino group include (meth) acrylamide, ⁇ , ⁇ -dimethinoleaminoethyl (meta). ) Acrynoreamid, ⁇ , ⁇ — dimethyl (meta) acrylamide, ⁇ , ⁇ ⁇ — dimethylaminop pill (meta) acrylamide, ⁇ , ⁇ — Di-t-butyl Aminoethyl (meta) acrylamide.
  • As the (meth) acrylate containing a carboxy group (meta)
  • vinyl esters examples include vinyl formate, vinyl acetate, butyl butyrate, vinyl propionate, vinyl laurate, vinyl benzoate, vinyl benzenesulfonate, and the like.
  • vinyl ethers examples include vinyl isopropyl ether and vinyl isopropyl ether.
  • vinyl pyridines examples include 2-vinyl pyridine, 4-vinyl pyridine, 2-vinyl-6-methyl pyridine, 4-1 vinyl-1 meth-iso-le- pyridine, and 2-vinyl-5-ethyl pyridine.
  • Examples include lysine and (4-pidinolinoethyl) pyridine.
  • Each of the above monomers has a hydrophilic property, and in particular, a homopolymer or a copolymer of these monomers is used as a branch polymer of a graphite polymer. It is effective at times. That is, the graphite polymer imparts strong adhesion when the composition of the present invention is adhered to a support such as glass, ceramics, or plastic. In addition, a random polymer of these monomers or a photosensitive resin composition using a block polymer cannot exhibit sufficient adhesion.
  • These monomers have a hydrophilic property and a condensation cross-linking property, in which water or alcohol is eliminated by heating.
  • Graphite polymers in which the copolymer is a branched polymer, are generally crosslinked at a temperature of 100 ° C or higher to form a polymer network structure, and the electroless polymerized cured product is obtained.
  • the present invention can further improve the fluidity and make the present invention more effective.
  • hydrophilic monomers preferred are a hydroxy group-containing (meth) acrylate and an acrylamide derivative represented by the general formula (I).
  • the branched polymer is not only derived from the hydrophilic monomer as described above, but also includes various hydrophobic monomers that exert various other functions, such as 0 to 100. Up to about 25% by weight may be used as a component for copolymerization.
  • a specific example of the hydrophobic monomer is the stem polymer described above. Monomers to be formed can be mentioned.
  • the graphite polymer used in the present invention has excellent adhesiveness and electroless plating resistance, a pattern formed using the composition of the present invention has excellent resolution. .
  • Examples of the method for producing a graphite polymer include a chain transfer method, an oxidized graph polymerization method, an ion-graft polymerization method, a radiation-graft polymerization method, and a macromolecular method.
  • the macromer method is preferred in terms of design.
  • the weight average molecular weight of the trunk polymer is preferably from 500 to 500,000, and the weight average molecular weight of the branch polymer is preferably from 500 to 100,000.
  • the weight average molecular weight of the graphite polymer is preferably from 500 to 500,000.
  • the content of the graphite polymer in the photosensitive resin composition is preferably from 10 to 60% by weight. If the content is less than 10% by weight, the adhesion to the substrate surface is reduced, and the resolution and the electroless plating resistance are deteriorated. If it exceeds 60% by weight, the imageability deteriorates.
  • the compound having at least two substituents represented by the general formula ( ⁇ ) in (D-ii), which is one of the components (D) of the photosensitive resin composition of the present invention, is a resin composition of the present invention.
  • Heating the active energy after irradiation with active energy generates an isocyanate group, which reacts with the carboxy group or Z in the polymer and the anhydrous lipoxy group to form an amide bond or a nitro or imine. Bond to improve the adhesion of the registry and the resistance to electroless plating.
  • Specific examples of such compounds include tolene isocyanate, xylene isocyanate, hexamethylene diisocyanate, and diphenylmethyl isocyanate.
  • Tungsten isolation, 1, 5 — naphthalene isolation, isophorone isolation, triphenylmethanthry A multifunctional isocyanate such as a reaction product of a polypropylene glycol having a netol or isocyanate group at the end thereof with a toluenediisocyanate; Alcohols such as methanol, ethanol, etc., phenols such as phenol, methylphenol, methylethyl ketone, dimethyl alcohol, etc.
  • Oxims such as oxosim, getylamine, triglyceride
  • examples thereof include compounds having a 13-dicarbonylmethyl group, such as ethylamine, aniline, and other amides, cabrolactam, ethyl malonate, and ethyl acetate ethyl acetate.
  • Desmodur AP Stable, Desmodur CT Stable [manufactured by Sumitomo Bayer Urethane Co., Ltd.], NO-KNOCK D—500 [Dainippon Ink Chemical Industry Manufactured by Nippon Polyurethane Industrial Co., Ltd.], Adiron VXL 8 1 (made by Hext).
  • the content of the pro-isocarbonate compound having at least two substituents represented by the general formula (II) in the photosensitive resin composition is preferably 5 to 50% by weight. Yes. If the amount is less than 5% by weight, sufficient adhesion and electroless plating resistance cannot be obtained, and if the amount exceeds 50% by weight, developability deteriorates. Further, the epoxy compound having at least two epoxy groups in (D-iii-la) as the component (D) of the photosensitive resin composition of the present invention is a component of the present invention. By heating the object after irradiating it with an active energy ray, a cross-linking reaction is caused to form a strong bond, thereby improving the adhesiveness of the resist and the resistance to electroless plating.
  • the pattern formed using the photosensitive resin composition of the present invention has excellent resolution.
  • Specific examples of such epoxy compounds include: 1) DER3311J, DER337J, DER6661J, DER6664J, DER6667J Chemical Co., Ltd.], Epicron 800 [Dai Nippon Ink Chemical Industry Co., Ltd.], Epicourt 1001, Epicolate 1002, Co.
  • the content of the epoxy compound having at least two epoxy groups in the photosensitive resin composition is preferably 5 to 50% by weight. If it is less than 50% by weight, sufficient adhesion and electroless plating resistance cannot be obtained, and if it exceeds 50% by weight, the developability deteriorates.
  • the epoxy curing agent (D-iii-i b) in the present invention reacts with the epoxy compound by heating the photosensitive resin composition of the present invention after irradiation with active energy, and initiates a crosslinking reaction.
  • an epoxy curing agent include boron trifluoride n-hexylamine complex and trifluoroboron monoethyl.
  • R 4 and R 7 are aliphatic hydrocarbons having 1 to 6 carbon atoms or aliphatic hydrocarbons having 1 to 6 carbon atoms having an ether bond
  • R 5 and R 6 are Represents an aliphatic hydrocarbon having 1 to 6 carbon atoms.
  • the content of the epoxy curing agent in the photosensitive resin is preferably 0.1 to 10% by weight. If the amount is less than 0.1% by weight, the curing of the epoxy compound does not proceed sufficiently, and if it exceeds 10% by weight, the developability deteriorates.
  • the photosensitive resin composition of the present invention essentially contains the components (A), (B), (C) and (D), and furthermore, the photosensitive resin composition of the present invention If necessary, a condensation-crosslinking catalyst, a thermal polymerization inhibitor, a filler, a colorant such as a dye or pigment, a heat stabilizer, an adhesion promoter, a plasticizer, a pigment such as silica or talc, A leveling agent or the like which provides workability may be added in the range of 0.1 to 50% by weight.
  • the photosensitive resin composition of the present invention can be dissolved in a solvent and used as a liquid registry.
  • dipping method, spray method, flow coating method, screen method A photosensitive layer having a thickness of 10 to 15 ⁇ m can be formed by directly applying the composition on a substrate by a method such as lean printing.
  • the solvent used at this time may be any solvent that dissolves the photosensitive resin composition, for example, ketones such as acetone, methylethylketone, methylisobutylketone, and the like.
  • Glycol ethers such as methylcellosolve, ethyl cellulose solvent, propylene glycol methyl ether, propylene glycol ethyl ether, methyl ethyl solvent solve acetate, ethyl acetate
  • Glycol esters such as rosacea acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, methanol, ethanol, etc.
  • Alcohols such as alcohol, dichloromethane, 1,1,1,1-trichloroethane and other chlorine-containing aliphatic solvents, toluene, There are aromatic hydrocarbon solvents such as styrene. These solvents are used alone or as a mixture.
  • the photosensitive resin composition of the present invention can be used as a dry film resist.
  • supporting films when used as a dry-soles-registry are, for example, polyethylene terephthalate, polypropylene, and polypropylene. Films consisting of polyethylene etc. are used, and particularly preferred are polyethylene phthalates.
  • the thickness of the film is preferably 5 to 100 ⁇ m. Also, one of these phenols may be used as a protective film for the photosensitive layer.
  • the solvent used for converting the photosensitive resin composition into a liquid when producing the dry film resist those described above can be used. Liquid
  • the photosensitive resin composition is uniformly coated on a supporting film, and the solvent is removed by heating or hot-air drying to form a photosensitive layer.
  • the thickness of the photosensitive layer is preferably from 100 to 100 / m.
  • the dry film resist having the photosensitive layer formed on the support film is left as it is or a protective film is laminated on the photosensitive layer and rolled up. Will be saved.
  • the photosensitive layer of the photosensitive resin composition of the present invention is formed on a substrate by laminating a photosensitive layer on the substrate by a conventional laminating method. After that, the photosensitive layer is irradiated with active energy rays through a negative mask or a posimask.
  • the active energy rays include, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, tungsten lamps, etc. UV lasers, argon lasers, helium cadmium lasers, Krypton lasers, etc. are used.
  • Developers include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, carbonated lithium, hydrogencarbonate. Um, sodium bicarbonate, sodium hydrogen carbonate, sodium phosphate, potassium phosphate, pyrrolium Sodium phosphate, potassium pyrophosphate, sodium silicate, potassium silicate, sodium metasilicate, lithium metasilicate, Ammonia, monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, triethylamine For example, an aqueous solution is used. Further, an antifoaming agent, an organic solvent, and the like may be added to the developer.
  • the cured product formed with the pattern obtained in this way has excellent electroless plating liquid resistance.
  • Photosensitive resin compositions having the compounding ratios shown in Table 1 were prepared.
  • This photosensitive resin composition solution was applied on a 25 m thick polyethylene terephthalate film, and was heated and dried for 10 minutes with a normal air dryer at 80 to obtain a thickness of 4 mm.
  • a photosensitive layer of 0 / m was obtained.
  • This photosensitive layer was coated with a 20-m-thick polyethylene film to form a dry film.
  • the photosensitive layer was laminated on a glass epoxy resin substrate provided with an electroless copper plating catalyst by a laminating apparatus while peeling off the polyethylene film, and then using a high-pressure mercury lamp through a negative mask. Exposure at mJ / cm2 was performed.
  • a step page having an optical density step of 0.15 was used, and the number of steps of the negative image remaining after the development was regarded as the sensitivity.
  • the minimum width ( ⁇ m) that can be formed without breaking or meandering one independent pattern is Adhesion was adopted.
  • the heat-cured resist was immersed in an electroless copper plating solution at 70 ° C for 15 hours at PH12, and the appearance was observed.
  • Solution 1 was prepared by uniformly dissolving the following compounds.
  • a resin composition was prepared. ⁇ Rele 2
  • Solution 2 was prepared by uniformly dissolving the following compounds.
  • a photosensitive resin composition having the composition shown in Table 4 was prepared. The mixing ratio described below is% by weight. Table 4
  • the present invention has the following effects.
  • a resist using a conventional photosensitive resin composition has poor adhesion to the substrate surface, and is therefore 70%.
  • the photosensitive resin composition of the present invention provides a resist having excellent electroless plating resistance by forming a strong bond by thermal crosslinking and improving the adhesion to the substrate surface. can do .
  • a resist using a conventional photosensitive resin composition could not be used for fine processing with a line width of 100 ⁇ m or less due to inferior sensitivity and resolution.
  • the photosensitive resin composition of the present invention forms a strong bond by thermal crosslinking to improve the adhesion to the substrate surface, and also has a binder polymer excellent in developability. By using, a register with excellent sensitivity and resolution can be provided.
  • a conventional resist using a photosensitive resin composition which has the above two effects, uses an organic solvent as a developer. Since the photosensitive resin composition of the present invention uses a binder polymer having excellent image resilience to an aqueous solution of an alkaline solution, it is possible to use an aqueous solution of an aqueous solution for the developing solution. No worries about air pollution.
  • the photosensitive resin composition of the present invention can be used in a solder register or a full-additive method used in the production of a printed wiring board. Suitable for applications such as resists, etching resists, and interlayer insulating materials, as well as fine processing of metal, PS plates, photosensitive liquids for screen printing, and resist inks. It is.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention se rapporte à une composition résineuse photosensible, qui a la capacité de se développer sous l'action d'une solution alcaline aqueuse et qui possède d'excellentes caractéristiques de sensibilité, de résolution et de résistance contre les solutions de plaquage sans courant, cette composition comprenant un polymère greffé comportant, comme polymères de ramification, un polymère d'un monomère contenant des groupes hydrophiles, et un polymère de liaison qui est soluble ou gonflable dans une solution alcaline aqueuse et qui a la propriété de former un film. Une telle composition comprend un polymère greffé qui comporte, comme polymères de ramification, un polymère d'un monomère contenant des groupes hydrophiles, un polymère de liaison qui est soluble ou gonflable dans une solution alcaline aqueuse, un composé éthyléniquement insaturé, et un initiateur de photopolymérisation.
PCT/JP1992/001166 1991-09-14 1992-09-11 Composition resineuse photosensible WO1993006529A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP3/262701 1991-09-14
JP3/262703 1991-09-14
JP26270191A JPH0572735A (ja) 1991-09-14 1991-09-14 感光性樹脂組成物
JP26270491A JPH0695379A (ja) 1991-09-14 1991-09-14 感光性樹脂組成物
JP26270391A JPH0683052A (ja) 1991-09-14 1991-09-14 感光性樹脂組成物
JP3/262704 1992-09-14

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WO1993006529A1 true WO1993006529A1 (fr) 1993-04-01

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WO (1) WO1993006529A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US6558875B1 (en) 1999-07-27 2003-05-06 Mitsubishi Chemical Corporation Method for treating photosensitive lithographic printing plate

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JPS60121444A (ja) * 1983-12-06 1985-06-28 Nippon Soda Co Ltd アルカリ現像型感光性樹脂組成物
JPS62121445A (ja) * 1985-11-21 1987-06-02 Kuraray Co Ltd 感光性組成物
JPS62293237A (ja) * 1986-06-06 1987-12-19 バスフ　アクチェン　ゲゼルシャフト 感光性記録素子
JPH01219734A (ja) * 1988-02-27 1989-09-01 Nippon Synthetic Chem Ind Co Ltd:The 画像形成方法

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Publication number Priority date Publication date Assignee Title
JPS60121444A (ja) * 1983-12-06 1985-06-28 Nippon Soda Co Ltd アルカリ現像型感光性樹脂組成物
JPS62121445A (ja) * 1985-11-21 1987-06-02 Kuraray Co Ltd 感光性組成物
JPS62293237A (ja) * 1986-06-06 1987-12-19 バスフ　アクチェン　ゲゼルシャフト 感光性記録素子
JPH01219734A (ja) * 1988-02-27 1989-09-01 Nippon Synthetic Chem Ind Co Ltd:The 画像形成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6558875B1 (en) 1999-07-27 2003-05-06 Mitsubishi Chemical Corporation Method for treating photosensitive lithographic printing plate
US6861202B2 (en) 1999-07-27 2005-03-01 Lastra S.P.A. Method for treating photosensitive lithographic printing plate

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