EP1644777A2 - Composition de matiere de reserve - Google Patents

Composition de matiere de reserve

Info

Publication number
EP1644777A2
EP1644777A2 EP04747446A EP04747446A EP1644777A2 EP 1644777 A2 EP1644777 A2 EP 1644777A2 EP 04747446 A EP04747446 A EP 04747446A EP 04747446 A EP04747446 A EP 04747446A EP 1644777 A2 EP1644777 A2 EP 1644777A2
Authority
EP
European Patent Office
Prior art keywords
resist composition
organic solvent
group
resist
ester
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP04747446A
Other languages
German (de)
English (en)
Inventor
Satoru c/o Corp. R&D Center Ishigaki (kawasaki)
Kunio c/o Corp. R&D Center Matsuki (kawasaki)
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
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 Showa Denko KK filed Critical Showa Denko KK
Publication of EP1644777A2 publication Critical patent/EP1644777A2/fr
Withdrawn legal-status Critical Current

Links

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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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

Definitions

  • the present invention relates to a resist composition used for the production of printed boards and, more particularly, to a water-based solution or dispersion type resist composition, and a method of producing a resist-coated substrate using the same.
  • a printed circuit board has hitherto been produced by forming a resist coating film on an insulating substrate comprising a conductive metal layer such as copper foil (which may contain metal other than copper, hereinafter referred merely to a "copper-clad substrate"), exposing to light through a photomask having a prescribed pattern, developing with water or alkali water, etching the conductive metal layer at the portion where no resist is remained with an etching solution, and removing the resist to form a prescribed wiring pattern.
  • Examples of the method of forming a resist layer on a copper-clad substrate include a dry film method and a liquid resist coating method.
  • a dip coating method in addition to a method of coating a liquid resist on a copper-clad substrate by means of roll coating or screen printing.
  • This method comprises dipping a copper-clad substrate in a large amount of a resist composition solution (commonly in the form of a solution), pulling up the copper-clad substrate, and drying it thereby to vaporize the solvent, thus forming a resist coating film on the copper-clad substrate.
  • a high volatile organic solvent has conventionally been used as a solvent in a liquid resist composition to be used in a dip coating method.
  • a resist composition containing water as a solvent disclosed in Japanese Unexamined Patent Publication (Kokai) No. 53-97416 has recently been proposed.
  • the resist composition containing water When applying the resist composition containing water to the dip coating method, there arises a problem that copper ions eluted from a copper plate accumulate in a resist solution thereby to cause ion crosslinking.
  • the dip coating method the operation of dipping a copper-clad substrate in large excess of a resist solution for a given time and pulling up the copper-clad substrate is performed, and metal ions such as copper ions are eluted during the dipping operation.
  • Severe problem such as accumulation of metal ions into the resist solution arises in the dip coating method, and may also arise in other resist layer forming methods such as liquid resist coating method.
  • the addition of a chelating agent in a water- based electrodeposition coating composition is proposed in Japanese Examined Patent Publication (Kokoku) No. 6- 44150.
  • the compound disclosed in the patent document has a problem that it exerts insufficient effect and deteriorates sensitivity to ultraviolet light.
  • An object of the present invention is to improve storage stability of a solution or dispersion type resist composition containing water as a solvent during a repeating dip coating operation while maintaining sensitivity of the resist composition.
  • a resist composition comprising (A) a resin component, (B) a photopolymerization initiator, (C) water and (D) an organic solvent, wherein the organic solvent (D) contains: (D-l) at least one organic solvent selected from the group consisting of an ⁇ -hydroxycarboxylate ester, a ⁇ - alkoxycarboxylate ester, a 1,3-diol compound and a 1,3- diol compound derivative, and (D-2) an organic solvent having a hydroxyl group other than (D-l) .
  • a method of producing a print circuit board which comprises using the resist composition according to any one of [1] to [3] .
  • a resist composition for dip coating comprising (A) a resin component, (B) a photopolymerization initiator, (C) water and (D) an organic solvent, wherein the organic solvent (D) contains: (D-l) at least one organic solvent selected from the group consisting of an ⁇ -hydroxycarboxylate ester, a ⁇ - alkoxycarboxylate ester, a 1,3-diol compound and a 1,3- diol compound derivative.
  • a method of producing a resist-coated substrate which comprises dipping an insulating substrate comprising a conductive metal in the resist composition according to [6].
  • a method of producing a print circuit board which comprises using the resist composition according to [6].
  • the present invention will now be described in detail.
  • the resin component (A) used in the resist composition of the present invention is soluble in a developer and is slightly soluble in an etching solution, and is preferably a component containing a resin having a carboxyl group or an anhydride group thereof in the molecule.
  • Examples of the resin having a carboxyl group or an anhydride group thereof in the molecule include an acrylic resin, which is a copolymer containing (meth) acrylic acid and (meth)acrylate as a monomer, a copolymer of (meth) acrylic acid and ethylene, and a copolymer of aleic anhydride and ethylene or styrene, and the acrylic resin is particularly preferable in view of adhesion and tack.
  • the (meth) acrylic acid means methacrylic acid and/or acrylic acid.
  • the resin component (A) is preferably a photopolymerizable resin which can cause photopoly erization by means of irradiation with ultraviolet light, X-ray or electron beam in the presence or absence of a photopolymerization initiator, and examples thereof include those having a plurality of polymerizable groups such as ethylenically unsaturated bonds in the molecule.
  • a photopolymerizable resin publicly known photopolymerizable resins can be used alone or in combination and, for example, it can be selected from the following groups (1) to (5).
  • a reaction product of an unsaturated isocyanate compound and a resin having at least one functional group selected from the group consisting of a carboxyl group, a carboxylic anhydride group, an amino group, a hydroxyl group and an epoxy group.
  • the weight-average molecular weight and acid value (mgKOH/g) of these photopolymerizable resins are not specifically limited, the weight-average molecular weight is preferably within a range from 500 to 100,000, more preferably from 1,000 to 50,000, and most preferably from 2,000 to 20,000, and the acid value is preferably within a range from 20 to 350, more preferably from 50 to 250, and most preferably from 80 to 200.
  • the weight-average molecular weight is measured by gel permeation chromatography and the acid value is measured by the procedure defined in JIS K5601.
  • Specific examples of the unsaturated hydroxyl compound include 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate, polyethylene glycol mono (meth)acrylate (e.g. diethylene glycol monoacrylate) , polyethylene glycol mono(meth)aerylate (e.g. triethylene glycol mono (meth) aerylate) , 1, 4-butanediol mono(meth)acrylate, ethylene glycol mono (meth) allyl ether, polyethylene glycol mono(meth) allyl ether (e.g.
  • diethylene glycol mono (meth) allyl ether N- methylolacrylamide
  • allyl alcohol methallyl alcohol
  • hydroxystyrene hydroxymethylstyrene
  • allyl phenol N- methylolacrylamide
  • unsaturated epoxy compound include glycidyl (meth)acrylate, allyl glycidyl ether, and 3 ,4-epoxycyclohexylmethyl (meth)acrylate.
  • unsaturated carboxylic acid and anhydride thereof for example, there can be used (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, sorbic acid, tetrahydrophthalic acid, cinnamic acid, nadic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, licanoic acid, ricinoleic acid, arachidonic acid, and anhydrides thereof.
  • the unsaturated amino compound examples include allylamine, diallylamine, a inostyrene, aminomethylstyrene, acrylamide, and a reaction product of an unsaturated carboxylic acid or a derivative thereof and polyamine such as ethylenediamine.
  • the unsaturated isocyanate compound for example, there can be used 2-isocyanate ethyl (meth)acrylate, allyl isocyanate, and a reaction product of an unsaturated hydroxyl compound and polyisocyanate such as tolylene diisocyanate or xylylene diisocyanate.
  • the resin having at least one functional group used in (1) to (5) is at least one homopolymer or copolymer selected from among the above-mentioned unsaturated carboxylic acid, unsaturated carboxylic anhydride, unsaturated isocyanate compound, unsaturated epoxy compound, unsaturated hydroxy compound and unsaturated amino compound.
  • the resin having a carboxyl group as a functional group include poly(meth) acrylic acid, a
  • (meth) acrylic acid-methyl (meth)acrylate copolymer a (meth) acrylic acid-styrene copolymer, a styrene-maleic anhydride copolymer, an ethylene- (meth) acrylic acid copolymer, terminal carboxylated polybutadiene, a terminal carboxylated butadiene-acrylonitrile copolymer, and an (anhydrous) polyhydric carboxylic acid adduct of a phenol resin.
  • the resin having a hydroxyl group include polyhydroxyethyl (meth) aerylate, a hydroxyethyl (meth)acrylate-styrene copolymer, a hydroxyethyl
  • (meth) aerylate-methyl methacrylate copolymer a novolak type phenol resin
  • polyvinyl alcohol a partially saponified ethylene-vinyl acetate copolymer
  • polyglycerin polyvinyl phenol
  • carboxylic acid adduct of an epoxy resin polyethylene glycol, polypropylene glycol, terminal hydroxylated (hydrogenated) polybutadiene, terminal hydroxylated (hydrogenated) petroleum resin, and a reaction product of polyhydric alcohol and polyhydric isocyanate.
  • Examples of the resin having an epoxy group include polyglycidyl (meth)acrylate, a glycidyl (meth)acrylate- styrene copolymer, a glycidyl (meth)acrylate-methyl methacrylate copolymer, a reaction product of a novolak type phenol resin and epichlorohydrin, a reaction product of polyhydric phenol and epichlorohydrin, and a reaction product of polyhydric alcohol and epichlorohydrin.
  • Examples of the resin having an amino group include polyacrylamide, polyallylamine, saponified polyvinyl formamide, saponified polyvinyacetamide, polyaminostyrene, an aminostyrene-styrene copolymer, a reaction product of a carboxyl group-containing resin and polyvalent amine, an urea resin, and a melamine resin.
  • Examples of the resin having an isocyanate group include poly-2-isocyanate ethyl (meth) aerylate, a 2- isocyanate ethyl (meth)acrylate-methyl (meth) aerylate copolymer, and a reaction product of a polyhydric isocyanate compound and a polyhydric hydroxyl compound. More specifically, preferable examples of (1) to (5) include:
  • (1-1) a reaction product of an unsaturated hydroxyl compound and a resin having a carboxylic anhydride group, for example, a reaction product of hydroxyethyl aerylate and a styrene-maleic anhydride copolymer, and those obtained by further reacting these reaction products with a base; (1-2) a reaction product of an unsaturated hydroxyl compound and a resin having an isocyanate group;
  • (2-1) a reaction product of an unsaturated epoxy compound and a resin having a carboxyl group for example, a reaction product of glycidyl aerylate and a methacrylic acid-methyl methacrylate copolymer, a reaction product of 3 , 4-epoxy-cyclohexylmethyl aerylate and a methacrylic acid-methyl methacrylate copolymer, and those obtained by further reacting these reaction products with a base; and (3-1) a reaction product of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride and a resin having an epoxy group, for example, a reaction product of acrylic acid and polyglycidyl methacrylate, and a reaction product of acrylic acid and a glycidyl methacrylate methyl methacrylate copolymer.
  • a reaction product of an unsaturated epoxy compound and a resin having a carboxyl group for example, a reaction product of glycidyl aerylate and
  • an acrylic resin composed of a copolymer of (meth) acrylic acid and an ester thereof, or a modified product thereof are particularly preferable, and specific examples thereof include a reaction product of glycidyl aerylate and a methacrylic acid-methyl methacrylate copolymer, a reaction product of 3, 4-epoxy-cyclohexylmethyl aerylate and a methacrylic acid-methyl methacrylate copolymer, and those obtained by further reacting these reaction products with a base.
  • the photopolymerizable resin which can be used, in addition to (1) to (5) include:
  • a polymerizable unsaturated resin obtained by adding an unsaturated dicarboxylic acid or an anhydride thereof to an unsaturated bond in a fatty acid chain in an esterified product of an epoxy resin and an unsaturated fatty acid;
  • Photopolymerization initiator As the photopolymerization initiator (B), for example, publicly known photopolymerization initiators can be used.
  • photopolymerization initiators may be used alone, but are preferably used in combination.
  • the content of these photopolymerization initiators is within a range from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, and most preferably from 0.5 to 10% by weight, based on the total weight (containing the solvent) of the resist composition of the present invention.
  • the content of the photopolymerization initiator (B) is less than 0.01% by weight, photopolymerization does not proceeds sufficiently, and thus making it difficult to maintain performances as the resist.
  • the content exceeds 20% by weight storage stability and properties of the coating film may deteriorate.
  • the resist composition of the present invention contains water (C) as the solvent.
  • the resist composition contains water (C), it is made possible to decrease the amount of a high volatile organic solvent and to increase a flash point of the resist composition and to improve safety during storage and transportation.
  • the content of water (C) in the resist composition of the present invention is within a range from 5 to 80% by weight, preferably from 10 to 75% by weight, more preferably from 20 to 70% by weight, still more preferably from 25 to 65% by weight, and most preferably from 30 to 60% by weight, based on the resist composition.
  • the organic solvent (D) of the present invention contains at least one organic solvent (D-l) selected from the group consisting of an ⁇ -hydroxycarboxylate ester, a ⁇ -alkoxycarboxylate ester, a 1,3-diol compound and a 1,3- diol compound derivative, and a hydroxyl group-containing organic solvent (D-2) other than the organic solvent (D- 1) .
  • organic solvent (D-l) selected from the group consisting of an ⁇ -hydroxycarboxylate ester, a ⁇ -alkoxycarboxylate ester, a 1,3-diol compound and a 1,3- diol compound derivative, and a hydroxyl group-containing organic solvent (D-2) other than the organic solvent (D- 1) .
  • the organic solvent (D-l) is selected from the group consisting of an ⁇ -hydroxycarboxylate ester, a ⁇ - alkoxycarboxylate ester, a 1,3-diol compound and a 1,3- diol compound derivative, and these compounds may be used alone or in combination.
  • the content of the organic solvent (D-l) is within a range from 0.1 to 40% by weight, preferably 0.5 to 30% by weight, more preferably from 1.0 to 20% by weight, and most preferably from 1.0 to 15% by weight, based on the resist composition of the present invention. When the content of the organic solvent (D-l) is less than 0.1% by weight, the effect of the present invention is not recognized.
  • the organic solvent (D-l) in the present invention is not specifically limited and publicly known esters can be used.
  • ⁇ -hydroxycarboxylate ester examples include glycolate esters such as methyl glycolate, ethyl glycolate, n-propyl glycolate, isopropyl glycolate, n-butyl glycolate, isobutyl glycolate, n-pentyl glycolate, n-hexyl glycolate, and cyclohexyl glycolate; lactate esters such as methyl lactate, ethyl lactate, n- propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, n-hexyl lactate, cyclohexyl lactate, and benzyl lactate; ⁇ -hydroxybutyrate esters such as methyl ⁇ - hydroxybutyrate , ethyl ⁇ -hydroxybutyrate, n-propyl ⁇ - hydroxybutyrate, isopropyl ⁇ -hydroxybutyrate
  • the ⁇ -alkoxycarboxylate ester is not specifically limited and publicly known esters can be used.
  • Specific examples of the ⁇ -alkoxycarboxylate ester include methyl 3-methoxy-propionate, ethyl 3-methoxy- propionate, methyl 3-methoxy-butyrate, ethyl 3-methoxy- butyrate, methyl 3-methyl-3-methoxy-butyrate, ethyl 3- methyl-3-methoxy-butyrate, methyl 2-methoxy-cyclohexane- carboxylate, and those wherein a methoxy group is replaced by the other alkoxy group such as ethoxy group.
  • the 1,3-diol compound is not specifically limited and publicly known compounds having a 1,3-diol structure can be used. Also it may have the other functional group other than the diol structure, for example, hydroxyl group.
  • 1,3- diol compound examples include 1,3-propanediol, 1 , 3-butanediol, 2- methyl-1 ,3-propanediol, 2,2-dimethyl-l,3-propanediol, 2- methyl-l,3-butanediol, 3-methyl-l,3-butanediol, 1,3- pentanediol, 2 ,4-pentanediol, 1,3-hexanediol, 2,4- hexanediol, trimethylolpropane, and pentaerythritol.
  • the 1,3-diol compound derivative is a compound having such a structure that at least one hydroxyl group among two hydroxyl groups of a 1,3-diol structure is etherified or esterified, and publicly known compounds can be used without any limitation.
  • 1,3-diol compound derivative examples include 3-methoxy-l- propanol, 2-methyl-3-methoxy-l-propanol, 2 , 2-dimethyl-3- methoxy-1-propanol, 3-methoxy-l-butanol, 3-methoxy-3- methyl-1-butanol, and those wherein a methoxy group is replaced by an ethoxy group or the other alkoxy group; 3-acetoxy-l-propanol, 2-methyl-3-acetoxy-l-propanol, 2,2- dimethyl-3-acetoxy-l-propanol, 3-acetoxy-l-butanol, 3- acetoxy-3-methyl-l-butanol, and those wherein an acetoxy group is replaced by the other acyloxy group; and 3-methoxy-l-propyl acetate, 2-methyl-3-methoxy-l-propyl acetate, 2,2-dimethyl-3-methoxy-l-propyl
  • the flash point of the organic solvent (D-l) is commonly 40 °C or higher, preferably within a range from 45 to 120°C, and more preferably from 50 to 110°C.
  • the organic solvent (D-2) of the present invention namely a hydroxyl group-containing organic solvent other than the organic solvent (D-l), is a compound having one or more hydroxyl groups in the molecule and publicly known organic solvents can be used without any limitation. These organic solvents can be used alone or in combination.
  • the content of the organic solvent (D-2) is within a range from 1.0 to 40% by weight, preferably from 3.0 to 30% by weight, more preferably from 5.0 to 20% by weight, and most preferably from 7.0 to 15% by weight, based on the resist composition of the present invention.
  • the content is preferably within the above range because a remarkable effect of the present invention is exerted even if the content of the organic solvent (D-l) is low.
  • the content of the organic solvent (D-2) is less than 1.0% by weight, the dispersion state of the resist composition may be unstable in case of low content of the organic solvent (D-l).
  • organic solvent (D-2) Specific examples include methanol, ethanol, 1-propanol, isopropanol, 1- butanol, 1-pentanol, ethylene glycol, propylene glycol, glycerin, 1 , 2-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monoacetate, diethylene glycol monoacetate, triethylene glycol
  • organic solvents such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and tetramethylbenzene; glycol ethers (e.g.
  • acetate esters e.g. methyl acetate, ethyl acetate, and butyl acetate
  • aliphatic hydrocarbons e.g.
  • the resist composition of the present invention preferably contains a polymerizable monomer (E), in addition to the above components (A) to (D).
  • the polymerizable monomer (E) is not specifically limited as far as it is a compound which can cause polymerization in the presence of the photopolymerization initiator (B), and publicly known polymerizable monomers can be used alone or in combination.
  • Examples of the polymerizable monomer (E) include the above-mentioned unsaturated hydroxyl compound, unsaturated epoxy compound, unsaturated carboxylic acid or unsaturated carboxylic anhydride, unsaturated amino compound and unsaturated isocyanate compound, and styrene, vinyltoluene, divinylbenzene, alkyl (meth) aerylate such as methyl methacrylate, allyl ester, (meth) aerylate ester of polyhydric alcohol, and allyl ether of polyhydric alcohol.
  • Examples of the (meth) aerylate of polyhydric alcohol include ethylene glycol di(meth) aerylate, diethylene - 10 -
  • glycol di (meth) aerylate triethylene glycol di (meth) aerylate, polyethylene glycol di (meth) aerylate, trimethylolpropane tri (meth) aerylate, ethoxylated trimethylolpropane tri (meth) aerylate, glycerin tri (meth) aerylate, pentaerythritoltetra (meth) aerylate, and ethoxylated pentaerythritoltetra (meth) aerylate.
  • allyl ether of polyhydric alcohol examples include ethylene glycol diallyl ether, diethylene glycol diallyl ether, diallyl ether, polyethylene glycol diallyl ether, trimethylolpropane triallyl ether, glycerin triallyl ether, and pentaerythritol tetraallyl ether.
  • F Thixotropic agent
  • the resist composition of the present invention can also contain a thixotropic agent (F) .
  • the thixotropic agent is a compound which can impart thixotropic properties to the resist composition, and publicly known thixotropic agents can be used alone or in combination.
  • the content of the thixotropic agent is commonly within a range from 0.01 to 10.0% by weight, preferably from 0.1 to 5.0% by weight, and more preferably from 0.2 to 2.0% by weight, based on the resist composition.
  • the thixotropic agent is not specifically limited and publicly known thixotropic agents can be used.
  • Examples thereof include inorganic compounds such as calcium stearate, zinc stearate, aluminum stearate, aluminum oxide, zinc oxide, magnesium oxide, glass, diatomaceous earth, titanium oxide, zirconium oxide, silicon dioxide, talc, mica, feldspar, kaolinite (kaolin clay), pyrophyllite (agalmatolite clay), sericite, bentonite, smectites/vermiculites (e.g.
  • thixotropic agents can be used alone or in combination.
  • Examples of commercially available inorganic thixotropic agent include Crown Clay, Burgess Clay #60, Burgess Clay KF, and OptiWhite (manufactured by Shiraishi Calcium Kaisha LTD.); Kaolin JP-100, NN Kaolin Clay, ST Kaolin Clay, and Hardsil (manufactured by Tsuchiya Kaolin Ind., Ltd.); ASP-072, Satintonplus , Translink 37, and Hydrousdelami NCD (manufactured by Angel Hard Corporation); SY Kaolin, OS Clay, HA Clay, and MC Hard
  • Examples of commercially available organic thixotropic agent include Disparon #6900-20X, Disparon #4200, Disparon KS-873N, and Disparon #1850 (manufactured by Kusumoto Chemicals); BYK-405 and BYK-410 (manufactured by BYC Che ie Japan Co.); Primal RW-12W (manufactured by Rohm&Haas Co.); and A-S-AT-20S, A-S-AT-350F, A-S-AD-10A, and A-S-AD-160 (manufactured by Itoh Oil chemicals Co., Ltd.). These compounds may be dispersed in the solvent.
  • a silicate compound represented by xM(I) 2 0 »ySi0 2 (also including those corresponding to M(II)0 or M(III) 2 0 3 wherein oxidation number is 2 or 3, x and y each represent a positive integer) is preferable and a swelling layer clay mineral such as hectorite, bentonite, smectite or vermiculite is more preferable.
  • an amine-modified silicate mineral (organic smectite: obtained by replacing an interlayer cation of sodium by an organic amine compound) can be preferably used and preferred examples thereof include those obtained by replacing a sodium ion of sodium/magnesium silicate (hectorite) by an ammonium ion.
  • ammonium ion examples include monoalkyltrimethylammonium ion having a C6-18 alkyl chain, dialkyldimethylammonium ion, trialkylmethylammonium ion, dipolyoxyethylene coconut oil alkylmethylammonium ion whose oxyethylene chain has 4 to 18 carbon atoms, bis (2-hydroxyethyl) coconut oil alkylmethylammonium ion, and polyoxypropylene methyldiethylammonium ion whose oxopropylene chain has 4 to 25 carbon atoms. These ammonium ions can be used alone or in combination.
  • polymerization inhibitors can also be used in combination.
  • conventionally known inhibitors can be used and examples thereof include phenols (e.g. 3,5-ditert-butyl-4- hydroxytoluene) , hydroquinones (e.g. hydroquinone, hydroquinonemono ethyl ether) and catechols (e.g. catechol, tert-butylcatechol, and pyrogallol).
  • publicly known inorganic fillers such as barium sulfate, barium titanate, silicon oxide powder, amorphous silica, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, glass fibers and carbon fibers can be optionally added to the photosensitive composition of the present invention.
  • publicly known coloring agents such as acid blue, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black
  • silicone, fluorine and polymeric defoaming agents and/or leveling agents such as imidazole, thiazole, triazole and silane coupling agents.
  • surfactants can be added to the resist composition of the present invention.
  • the surfactant is not specifically limited and publicly known surfactants can be used. Examples thereof include anionic surfactants (e.g. sodium dodecylbenzene sulfonate, sodium laurate, and ammonium salt of polyoxyethylene alkyl ether sulfate), nonionic surfactants (e.g. polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide) and acetylene glycol surfactants.
  • anionic surfactants e.g. sodium dodecylbenzene sulfonate, sodium laurate, and ammonium salt of polyoxyethylene alkyl ether sulfate
  • nonionic surfactants e.g. polyoxyethylene alkyl ether, polyoxyethylene alkyl este
  • the viscosity at 25 °C of the resist composition of the present invention is preferably within a range from 5 to 500 mPa «s, more preferably from 10 to 300 mPa «s, still more preferably from 15 to 200 mPa «s, and most preferably from 20 to 150 mPa «s.
  • the viscosity is measured by using a commercially available B-type rotary viscometer.
  • the flash point of the resist composition of the present invention is commonly 40 °C or higher, preferably 55 °C or higher, more preferably 60 °C or higher, and most preferably 70 °C or higher.
  • the resist composition of the present invention can be produced by mixing the components described above by an arbitrary method, for example, a method of adding the respective components in a container equipped with a stirring blade while stirring.
  • the respective components may be simultaneously added in a container in which the components are mixed, or may be successively added.
  • the respective components may be added at a time, or may be added by plural portions .
  • the temperature upon mixing is not specifically limited and is commonly within a range from 5 to 50 °C, and preferably from 10 to 40 °C.
  • the mixing operation may be conducted at a given temperature, or may be conducted while varying the temperature.
  • the resist composition of the present invention can be applied to an arbitrary coating method and is particularly useful for a dip coating method. According to the resist composition of the present invention, it is made possible to suppress a problem of ion crosslinking due to metal ions including copper ions eluted from a copper plate while maintaining sensitivity.
  • the dip coating method is a publicly known method and a coated substrate is produced by charging a resist composition in a container, dipping an insulating substrate comprising a conductive metal layer such as copper-clad laminate therein, and pulling up at an arbitrary rate.
  • the temperature of the resist composition in the container can be set to an arbitrary temperature and is preferably within a range from 10 to 50°C.
  • An apparatus used is not specifically limited and a publicly known apparatus can be used, and the apparatus is preferably an apparatus capable of varying a climbing rate during pulling-up so as to form a uniform film. Examples of commercially available dip coating apparatus include full-automatic dip coater AD-7200, semi-automatic dip coater SD-6200, and five coater SZC-720 (manufactured by SATUMA Communication Industry Co., Ltd.).
  • a printed circuit board having a prescribed wiring pattern is commonly produced from a copper-clad substrate obtained by the dip coating method through the processes of drying, exposure, development, etching and removal of a resist film and optional other processes.
  • EXAMPLES Example 1 1) Preparation of resist composition While vigorously stirring of a uniform mixture of the respective components (A) to (F) described below, 41.8 parts by weight of water (C) was added dropwise to the mixture over 15 minutes, followed by stirring for 15 hours. To the resulting solution, 3.0 parts by weight of ethyl lactate (D-l) and 0.3 parts by weight of an aqueous 10 wt% polyvinyl alcohol solution were added, followed by stirring for one hour to prepare a resist composition.
  • D-l ethyl lactate
  • D-l ethyl lactate
  • an aqueous 10 wt% polyvinyl alcohol solution were added, followed by stirring for one hour to prepare a resist composition.
  • Photopolymerization initiator 2.4 Parts by weight of 2-methyl-l-(4- methylthiophenyl)-2-morpholinopropan-l-one (D-2) 14.0 Parts by weight of ethylene glycol monobutyl ether and 13.8 parts by weight of propylene glycol monomethyl ether
  • E Polymerizable monomer 1.4 Parts by weight of an acrylic acid adduct of bisphenol F diglycidyl ether (manufactured by NIPPON KAYAKU CO., LTD.
  • the substrate was dried at 80 °C for 15 minutes to obtain a coated substrate comprising a resist composition coating film having a thickness of about 8 ⁇ m. After evaluation of storage stability (2), the resist composition was also dip-coated.
  • EGB Ethylene glycol monobutyl ether
  • PGM Propylene glycol monomethyl ether
  • Examples 2 to 19 In the same manner as in Example 1, except that those described in Table 1 were used as (D-l) and (D-2) in the amounts described in Table 1, resist compositions were produced and evaluated. The results are shown in Table 1. Comparative Example 1 In the same manner as in Example 1, except that ethyl lactate was not used and (D-2) EGB was used in the amount described in Table 1, a resist composition was produced and evaluated. The results are shown in Table 1.
  • Comparative Examples 2 to 4 In the same manner as in Example 1, except that acetylacetone, methyl acetoacetate and methyl salicylate described in Patent Document 2 (Japanese Examined Patent Publication (Kokoku) No. 6-44150) were used in place of (D-l) ethyl lactate, resist compositions were produced and evaluated. The results are shown in Table 1.
  • Example 20 In the same manner as in Example 1, except that all of (D-l) ethyl lactate, (D-2) ethylene glycol monobutyl ether and propylene glycol monomethyl ether were replaced by butyl lactate, a resist composition was produced and evaluated. The results are shown in Table 1.
  • Example 21 In the same manner as in Example 1, except that the total amount of (D-2) ethylene glycol monobutyl ether and propylene glycol monomethyl ether was replaced by water, a resist composition was produced and evaluated. The results are shown in Table 1. As is apparent from the results shown in Table 1, the resist compositions of the present invention do not cause deterioration of sensitivity, increase of viscosity and formation of precipitates due to copper ions eluted from a copper plate as compared with the resist compositions of the prior art.
  • the resist composition of the present invention can suppress a problem such as ion crosslinking due to copper ions eluted from a copper plate while maintaining sensitivity, especially in a dip coating method, and contributes to quality stabilization of printed circuit boards and improvement of productivity.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte à une composition de matière de réserve utilisée pour la production de cartes à circuits imprimés, qui comprend (A) un composant résine, (B) un amorceur de photopolymérisation, (C) de l'eau et (D) un solvant organique, ledit solvant organique (D) contenant: (D-1) au moins un solvant organique sélectionné dans le groupe constitué par un ester α-hydroxycarboxylate, un ester β-alcoxycarboxylate, un composé 1,3-diol et un dérivé de composé 1,3-diol, et (D-2) un solvant organique ayant un groupe hydroxyle autre que (D-1).
EP04747446A 2003-07-08 2004-07-06 Composition de matiere de reserve Withdrawn EP1644777A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2003193831 2003-07-08
US48949303P 2003-07-24 2003-07-24
PCT/JP2004/009980 WO2005003859A2 (fr) 2003-07-08 2004-07-06 Composition de matiere de reserve

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EP1644777A2 true EP1644777A2 (fr) 2006-04-12

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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3115462B2 (ja) * 1993-12-14 2000-12-04 富士写真フイルム株式会社 感光性組成物及び感光性平版印刷版
AU2002353536A1 (en) * 2001-12-03 2003-06-17 Showa Denko K. K. Photosensitive composition and production processes for photosensitive film and printed wiring board

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005003859A3 *

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