CN102396037A

CN102396037A - Composition for forming conductor layer, conductor substrate, and method for producing conductor substrate

Info

Publication number: CN102396037A
Application number: CN2010800168159A
Authority: CN
Inventors: 清水克也
Original assignee: Asahi Chemical Co Ltd
Current assignee: Asahi Chemical Co Ltd
Priority date: 2009-04-14
Filing date: 2010-04-05
Publication date: 2012-03-28
Anticipated expiration: 2030-04-05
Also published as: CN102396037B; TW201036944A; JPWO2010119787A1; KR20120008019A; WO2010119787A1

Abstract

Disclosed is a composition for forming a conductor layer, which is capable of forming a conductor layer that has excellent electrical conductivity. When a conductor layer is formed using the composition, the number of steps is reduced and no high-temperature treatment is required, thereby reducing the production cost of the conductor layer. Also disclosed are a conductor substrate using the composition for forming a conductor layer, and a method for producing the conductor substrate. The composition for forming a conductor layer contains a metal complex represented by formula (1).

Description

Conductor layer forms the manufacturing approach with composition and conductor substrate and conductor substrate

Technical field

The present invention relates to conductor layer and form manufacturing approach with composition and conductor substrate and conductor substrate.

Background technology

As the method for the conductor layer of the antenna of making IC tag, electromagnetic wave shield, flexible printing wiring board etc., extensively utilize photoetching process.

As the method that only forms conductive pattern through simple printing, the known method that the conductivity China ink that printing forms by the metal particle of silver etc. is arranged.When using metal particle,, make that closely to merge between particle be indispensable in order to obtain sufficient conductivity.In addition, need remove nonmetal compositions such as resin fully, under a lot of situation, under the high temperature more than 150 ℃, implement to burn till as the binding agent cooperation of metal particle.

Except photoetching process, the conductivity ink print, also known have an addition process (additive method).Photoetching process is the method (subtractive method, the method for residues) of removing unwanted conductor layer through etching, and is relative therewith, and addition process is the method that only forms conductor layer in the place of needs through chemical plating.In this method, through the catalyst layer of formation chemical platings such as print process, implement chemical plating at this place then usually.

For example disclose in the patent documentation 1 and printed the method that contains palladium, platinum, nickel, copper complex formazan China ink.Disclosing printing in the patent documentation 2 contains polymer and 1B and belongs to the method for implementing metal-plated behind the catalyst ink of compound, complex compound or colloid that metal or the 8th belongs to metal.

The prior art document

Patent documentation

Patent documentation 1: United States Patent (USP) the 4th, 368, No. 281 specifications

Patent documentation 2: the flat 6-508181 communique of the special table of Japan

Summary of the invention

The problem that invention will solve

Yet photoetching process needs many operations: the operation of painting photoresist on copper-clad laminate; By the exposure of photomask resist is carried out the operation that pattern is ablated through being situated between; Photoresist is developed and the operation of etching Copper Foil etc.

Because the conductivity ink print need burn till under the temperature more than 150 ℃, so there is unworkable problem in general-purpose plastics base materials such as PETG aspect stable on heating.

About addition process; For example the China ink of patent documentation 1 also contains bonding agent as necessary composition owing to not only contain solvent, so not only need make the operation of solvent seasoning, also need after printing, be used to the heat treatment step that makes bonding agent crosslinked; Therefore, there is the many and numerous and diverse problem of operation quantity.In the method for patent documentation 2, the drying process after printing, in order to make catalyst activation, need under 160～500 ℃ of such high temperature, heat-treat, existence can't be avoided the rotten problem of resin film of base material.

In addition, the composition that cooperates in the China ink of patent documentation 1 and patent documentation 2 is limited to the palladium based compound in fact.Therefore, existence can't be avoided because of using the disadvantageous problem of the cost aspect that expensive palladium produces.

For for the existing China ink of above-mentioned Mo Wei representative, many except the operation quantity that is used to form conductor layer, need processing etc. high temperature under the problem, also there is the very expensive problem of black composition, expect to develop the technology that addresses this is that.

The present invention In view of the foregoing carries out; Purpose is to provide a kind of conductor layer to form with composition, the conductor substrate that uses it and manufacturing approach thereof; Said conductor layer forms the conductor layer that can process excellent electric conductivity with composition; And when forming conductor layer, operation quantity is few and need not the processing under the high temperature, low cost of manufacture.

The scheme that is used to deal with problems

The inventor furthers investigate in order to solve above-mentioned problem; The result finds; The metal complex that has ad hoc structure through use forms as conductor layer and uses composition, thereby can on base material, form the conductor layer of excellent electric conductivity, and operation quantity is few and need not the processing under the high temperature; Cost is low, thereby has accomplished the present invention.

That is, the present invention is described below.

[1] a kind of conductor layer forms and uses composition, and it comprises the metal complex shown in the following formula (1).

(in the formula (1), R ¹, R ², R ³, R ⁴And R ⁵Represent hydrogen atom, carboxyl, alkoxy carbonyl, cyanic acid, formoxyl, acyl group, nitro, nitroso, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxyl, sulfydryl, alkylthio group, alkoxyl, halogen atom or amino independently of one another.For R ¹, R ², R ³, R ⁴And R ⁵, can be in them at least 2 bondings and form saturated rings or unsaturated ring each other, also can have independently of one another from the compound shown in the formula (1) and break away from 1 valency group that 1 hydrogen atom forms as substituting group.M representes to be selected from the metal more than in the group of being made up of Cu, A g, Au, Ni, Pd, Co, Rh, Fe, In and Sn any.N representes 1～6 integer.)

[2] use composition according to the conductor layer formation of [1], wherein, aforementioned R ¹, R ², R ³, R ⁴And R ⁵Represent hydrogen atom or isopropyl independently of one another.

[3] use composition according to the conductor layer formation of [1] or [2], wherein, aforementioned M representes Cu.

[4] a kind of conductor substrate, it comprises base material, and

Through being formed, each conductor layer in [1]～[3] reduces the conductor layer that forms after being applied on the aforementioned substrates with composition.

[5] a kind of manufacturing approach of conductor substrate, it comprises following operation: the conductor layer that will comprise the metal complex shown in the following formula (1) forms and is applied on the base material with composition, reduces then.

(in the formula (1), R ¹, R ², R ³, R ⁴And R ⁵Represent hydrogen atom, carboxyl, alkoxy carbonyl, cyanic acid, formoxyl, acyl group, nitro, nitroso, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxyl, sulfydryl, alkylthio group, alkoxyl, halogen atom or amino independently of one another.For R ¹, R ², R ³, R ⁴And R ⁵, can be in them at least 2 bondings and form saturated rings or unsaturated ring each other, also can have independently of one another from the compound shown in the formula (1) and break away from 1 valency group that 1 hydrogen atom forms as substituting group.M representes to be selected from the metal more than in the group of being made up of Cu, Ag, Au, Ni, Pd, Co, Rh, Fe, In and Sn any.N representes 1～6 integer.)

[6] manufacturing approach of the conductor substrate of basis [5], wherein, aforementioned reduction uses sodium borohydride to carry out.

[7] manufacturing approach of the conductor substrate of basis [5] or [6] wherein, after carrying out aforementioned reduction, also comprises the operation of aforementioned conductor layer being implemented plating.

[8] manufacturing approach of the conductor substrate of basis [7], wherein, plated is a chemical plating.

[9] manufacturing approach of the conductor substrate of basis [8], wherein, aforementioned chemical plating is an electroless copper.

[10] according to the manufacturing approach of each conductor substrate in [5]～[9], wherein, aforementioned conductor layer is formed the method that is applied on the base material with composition carry out through flexible printing or intaglio printing.

The effect of invention

According to the present invention; Can provide a kind of conductor layer to form with composition, the conductor substrate that uses it and manufacturing approach thereof; Said conductor layer forms the conductor layer that can process excellent electric conductivity with composition; And when forming conductor layer, operation quantity is few and need not the processing under the high temperature, low cost of manufacture.

Embodiment

Below to embodiment (below be called " this execution mode ".) be elaborated.In addition, the present invention is not limited to this execution mode and explains, in the scope of its purport, can suitably be out of shape and implements.

[metal complex]

The conductor layer of this execution mode forms and comprises the metal complex shown in the following formula (1) with composition.Even forming, the conductor layer of this execution mode do not use bonding agent can on base material, form conductor layer securely with composition yet.And, burn till owing to when forming conductor layer, also can not heat, thus base material etc. can be prevented because of heat takes place to go bad, and need not to consider the thermal endurance of base material etc., so material chosen scopes such as base material are wide.In the past, when forming conductor layer, for employed material is processed solution and had to use in a large number the situation of the high halogen series solvent of solvability also a lot.In this case, producing the halogen series solvent is penetrated in the base material, makes problems such as base material is rotten.The conductor layer of this execution mode forms with composition because the solvent of broad variety is had excellent dissolubility, thus can also suppress the rotten of said base material etc., to environment also close friend.

In the formula (1), R ¹～R ⁵Represent hydrogen atom, carboxyl, alkoxy carbonyl, cyanic acid, formoxyl, acyl group, nitro, nitroso, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxyl, sulfydryl, alkylthio group, alkoxyl, halogen atom or amino independently of one another.

As alkoxy carbonyl, for example can enumerate out methoxycarbonyl, ethoxy carbonyl, hydroxyl-oxethyl carbonyl.In the middle of these, from the viewpoint of the easy property made, preferred methoxycarbonyl.

As acyl group, from the viewpoint of the easy property made, preferred acetyl group.

As alkyl, for example can enumerate out methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group.In the middle of these, from the easy property of raw material acquisition, the viewpoint of performance, preferable methyl, isopropyl.During for methyl, isopropyl,,, consequently, can more effectively form conductor layer so can modulate the China ink that contains metal with higher concentration because the dissolubility of the metal complex shown in the formula (1) in organic solvent improves.

As alkenyl, for example can enumerate out acrylic, isopropenyl, cyclobutenyl, isobutenyl.

As cycloalkyl, for example can enumerate out cyclohexyl.

As aralkyl, for example can enumerate out benzyl.

As alkylthio group, for example can enumerate out methyl sulfane base, ethyl sulfane base, propylthio alkyl, 2-methyl sulphur ethyl, 3-methyl thiopropyl.

As aryl, from the viewpoint of the easy property made, preferred phenyl.

As alkoxyl, for example can enumerate out methoxyl group, ethyoxyl, propoxyl group.In the middle of these, from the viewpoint of the easy property made, preferred methoxyl group.

As halogen atom, from the viewpoint of the easy property made, preferred chlorine atom or bromine atoms.

Amino can not have replacement or replacement is arranged.As single substituted-amino, for example can enumerate out that methylamino, ethylamino, propyl group are amino, isopropyl is amino, butyl is amino, isobutylamino, cyclohexyl amino, benzylamino, phenyl amino.In the middle of these, the viewpoint of the easy property that obtains from raw material, preferable methyl is amino.As disubstituted amido, for example can enumerate out that dimethylamino, diethylamino, diisopropylaminoethyl, dibutylamino, diisobutyl are amino, dicyclohexyl is amino, dibenzyl amino, diphenyl amino, pyrrolidinyl, piperidyl, morpholinyl.In the middle of these, the viewpoint of the easy property that obtains from raw material, preferred dimethylamino.

In the formula (1), R ¹～R ⁵In at least 2 bondings and form saturated rings or unsaturated ring each other.As this saturated rings, unsaturated ring, for example can enumerate out phenyl ring, pyrazoles ring 、 isoxazole ring, isothiazole ring, imidazole ring 、 oxazole ring, thiazole ring, triazole ring, the such azoles ring of tetrazole ring.In addition, R ¹～R ⁵Also can have independently of one another from the compound shown in the above-mentioned formula (1) and break away from 1 valency group that 1 hydrogen atom forms as substituting group.

In the formula (1), R ¹～R ⁵It can be the combination in any of above-mentioned group.R ¹～R ⁵Combination unqualified, preferably be hydrogen atom, alkyl, alkenyl, cycloalkyl, aralkyl or aryl, more preferably hydrogen atom or isopropyl independently of one another.The dissolubility of such compound in various organic solvents is more excellent, so preferred.In addition, from the viewpoint of the easy property made, R ¹～R ⁵Be preferably hydrogen atom, cyanic acid, alkyl, alkenyl, halogen atom or amino independently of one another.

In the formula (1), M representes to be selected from the metal more than in the group of being made up of Cu, Ag, Au, Ni, Pd, Co, Rh, Fe, In and Sn any.In view of the high meaning of self-catalysis ability from conductivity the high and chemical plating, be preferably selected from the metal more than in the group of forming by Cu, Ag, Au, Ni and Co any.From the viewpoint of cost-effectiveness (cost-effectiveness), more preferably be selected from the metal more than in the group of forming by Cu, Ni and Co any, in the middle of these, from the viewpoint of the easy property made, more preferably Cu.Owing to have the complex structure of this execution mode, thereby the dissolubility in organic solvent becomes very high, can access the high China ink of metal containing ratio.Thus, the operation that can carry out more well thereafter is a chemical plating.

In the formula (1), n is the valence mumber of metal ion, the integer of expression 1～6.

The conductor layer of this execution mode forms can contain a kind in the compound shown in the formula (1) separately with composition, also can contain more than 2 kinds.In this execution mode, the metal complex shown in the formula (1) also can be taked the structure of equal value with formula (1) such shown in the following formula (2).Compound shown in compound shown in the formula (2) and the formula (1) is of equal value.

The conductor layer of this execution mode does not form with the content of the above-mentioned metal complex in the composition is special and limits, and is preferably 0.01～100 quality %, more preferably 0.1～90 quality %.Be set at above-mentioned scope through content, thereby can make conductor layer effectively metal complex.

[manufacturing approach of metal complex]

Metal complex shown in the formula (1) can be made through known method.For example can enumerate out the method that the Tropolones as part is mixed in organic solvent with slaine, obtains with the mode of solution; Method of in the aqueous solution of the alkali metal salt of tropolone, adding slaine, obtaining with sedimentary mode etc., the method that more preferably obtains with the mode of solution.

[manufacturing approach of Tropolones]

Tropolones as the part of the metal complex shown in the formula (1) can synthesize through the method for application of known.If for example use the method for record in " big organic chemistry, the 13rd volume, non-benzene series aromatic ring compound " (little bamboo do not have two male prisons are repaiied, bookstore's (strain) distribution, nineteen sixty), then can use various Tropoloneses towards the storehouse.

[organic solvent]

The conductor layer of this execution mode forms with in the composition, preferably except that the aforementioned metal complex compound, also comprises organic solvent.Through comprising organic solvent, can further improve the coating on base material.The conductor layer of this execution mode forms with metal complex contained in the composition owing to the solvent to broad variety has excellent dissolubility, so the wide range that solvent is selected.In the past, processed solution and had to use the situation of the high halogen series solvent of solvability a lot of for the material that will form conductor layer.A large amount of when using the halogen series solvent, the halogen series solvent is penetrated in the base material, cause that rotten and so on problem takes place for base material etc.Yet the conductor layer of this execution mode forms with composition and nonessential employing halogen series solvent, thus can suppress the rotten of said base material etc., also friendly to environment.But the organic solvent that uses in this execution mode is not limited to non-halogen series solvent, in the scope of the effect of this execution mode, no matter halogen system also is non-halogen series solvent, all can suitably use known organic solvent.

As organic solvent, not special the qualification for example can be enumerated out ethers such as ether, oxolane 、 diox, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, propane diols dimethyl ether, propane diols Anaesthetie Ether; Glycol monoethers (so-called cellosolve class and carbitol class) such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propane diols list ethylether, diethylene glycol monomethyl ether, TC; Ketones such as MEK, acetone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone; Ester classes such as the acetate of ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, aforementioned glycol monoether (for example methyl glycol acetate, ethyl cellosolve acetate), acetic acid methoxy-propyl ester, acetic acid ethoxycarbonyl propyl ester, dimethyl oxalate, methyl lactate, ethyl lactate; Alcohols such as methyl alcohol, ethanol, isopropyl alcohol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerine, terpinol; Carrene, 1, halogenated hydrocarbons such as 1-dichloroethanes, 1,2-dichloroethene, n-propyl chloride, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorohenzene, m-dichlorobenzene; N, dinethylformamide, N, amide-types such as N-dimethylacetylamide; Pyrrolidinone compounds such as N-methyl pyrrolidone; Lactone such as gamma-butyrolacton; Sulfoxide classes such as dimethyl sulfoxide (DMSO); Chain or cyclic saturated hydrocarbons such as hexane, cyclohexane, heptane; Other organic polar solvent class.And then, as organic solvent, also can enumerate out aromatic hydrocarbon based and other organic non-polar solven class such as benzene,toluene,xylene.These organic solvents can use a kind or make up more than 2 kinds and to use separately.In the middle of these, from the viewpoint of fail safe, preferred ethers, ester class, alcohols, more preferably ethers, alcohols.

The content of organic solvent is not special to be limited, and the viewpoint from coating, system film property with respect to 100 mass parts metal complexs, is preferably 10～100000 mass parts, more preferably 50～10000 mass parts.

[inorganic filler]

The conductor layer of this execution mode forms can contain known inorganic fillers such as barium sulfate, barium titanate, silica powder, micro mist shape silica, amorphous silica, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica powder as required with composition.Thus, can improve the various characteristicses such as adaptation of conductor layer and base material.

The content of inorganic filler is not special to be limited, and the viewpoint from coating, system film property with respect to 100 mass parts metal complexs, is preferably 0～100 mass parts, more preferably 0～50 mass parts.

[resinous principle]

The conductor layer of this execution mode forms can contain polyester based resins such as PETG, polybutylene terephthalate (PBT), poly terephthalic acid tetramethylene ester, PEN with composition; Polyimides such as condensed type polyimides, addition polyimide, high temperature addition polyimide are resin; Epoxy resin resins such as bisphenol A-type (BA type) epoxy resin, Bisphenol F type (BF type) epoxy resin, phenoxy resin; Phenolic aldehyde such as linear phenol-aldehyde resin, cresol novolac resin, poly hydroxy styrenes are resin; Polyethylene, polypropylene, polystyrene, gather polyolefin-based resins such as cycloolefin; Nylon 6,6, nylon 6, nylon 6, polyamide-based resins such as T, nylon 4,6, nylon 12, nylon 6,12 etc.; And polyurethane series resin, polycarbonate-based resin, polyacetals be resin, polyphenylene oxide be resin, gather (methyl) acrylic ester resin, acrylonitrile-butadiene-styrene copolymer is that resin, polyphenylene sulfide are that resin, polyether-ether-ketone are that resin, PEI are that resin, polyether sulfone are that resin, polybenzoxazole are general resins such as resin.Thus, can improve the various characteristicses such as adaptation of conductor layer and base material.In the middle of these,, preferred polyester system, polyurethane series, gather the resin of (methyl) acrylic ester from the viewpoint of cost-effectiveness.

The content of resinous principle is not special to be limited, and the viewpoint from coating, system film property with respect to 100 mass parts metal complexs, is preferably 0～1000 mass parts, more preferably 0～500 mass parts.

[other additive]

And then the conductor layer of this execution mode forms and can suitably contain as required with composition: colouring agents such as phthalocyanine blue, phthalocyanine green, iodine are green, dual-azo yellow, crystal violet, titanium oxide, carbon black, naphthalene are deceived; Polymerization inhibitors such as quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine; Thickeners such as asbestos, ORBEN, bentonite (bentone), imvite; Antifoaming agents such as silicone-based, fluorine system, macromolecular; The additive kind of adaptation imparting agents such as levelling agent, imidazoles system, thiazole system, triazole system, silane coupler etc. and so on; Oxidation inhibitor, the hindered amine of hindered phenol system are that light stabilizer (HALS) waits other additive.

The content of colouring agent is not special to be limited, and the viewpoint from coating, system film property with respect to 100 mass parts metal complexs, is preferably 0～100 mass parts, more preferably 0～50 mass parts.

The conductor layer of this execution mode forms also can be through containing photocurable compound and Photoepolymerizationinitiater initiater is processed Photocurable composition with composition.Photocurable compound is not special to be limited, and can use known photocurable compound.For example can enumerate out compound with polymerism unsaturated group.Here so-called " polymerism unsaturated group " is meant the unsaturated group of participating in radical polymerization or polyaddition reaction.As the polymerism unsaturated group of participating in Raolical polymerizable, for example can enumerate out acryloyl group, methacryl, as the polymerism unsaturated group of participating in polyaddition reaction, for example can enumerate out epoxy radicals, oxetanyl, vinyl ether group.

As compound, can enumerate out olefines such as ethene, propylene, styrene, divinylbenzene with the unsaturated group of participating in Raolical polymerizable; (methyl) acrylic acid and derivative thereof; The haloalkene hydro carbons; Unsaturated nitriles such as acrylonitrile; (methyl) acrylamide and derivative thereof; Allyl compounds such as allyl alcohol, pi-allyl isocyanates; Unsaturated dicarboxylic and derivatives thereof such as maleic anhydride, maleic acid, fumaric acid; The vinylacetate class; The N-vinyl pyrrolidone; N-VCz etc.In the middle of these, preferred (methyl) acrylic acid or derivatives thereof.Compound with the unsaturated group of participating in Raolical polymerizable can use a kind or and with the compound more than 2 kinds according to purpose.

As (methyl) acrylic acid derivative, for example can enumerate out following compound and (methyl) acrylic acid carboxylate etc. with alcohol hydroxyl group.

As the above-mentioned compound with alcohol hydroxyl group, can enumerate out that cycloalkyl alcohol, bicyclic alkyl alcohol, cycloalkenyl group are pure, bicyclic alkenyl alcohol etc. has the compound of the skeleton of ester ring type; Benzyl alcohol, phenol, fluorenol etc. have the compound of aromatic skeleton; Alkylol, haloalkyl alcohol, polyalcohols such as alkoxyalkyl is pure, phenoxyalkyl is pure, hydroxy alkyl is pure, aminoalkyl is pure, tetrahydrofurfuryl is pure, allyl alcohol, glycidol, aklylene glycol, polyether polyols, (alkyl/pi-allyl oxygen) PAG, trimethylolpropane etc.

As the concrete example of (methyl) acrylic acid derivative, can enumerate out (methyl) acrylic acid phenoxy ethyl, (methyl) Hydroxyethyl Acrylate, diethylene glycol butyl ether (methyl) acrylic acid ester, ethylene glycol phenyl ether (methyl) acrylic acid ester, trimethylolpropane (methyl) acrylic acid ester, (methyl) lauryl acrylate etc.

(methyl) acrylic acid derivative also can be and contains the carboxylate as heteroatomic heteroaromatic compound such as nitrogen, sulphur for the compound of the ester of the compound with aromatic skeleton the time.

As the compound of the unsaturated group of participating in polyaddition reaction, can enumerate out the compound with epoxy radicals that can carry out the ring opening polyaddition reaction.As the compound with epoxy radicals that can carry out opening, can enumerate out: make polyol reaction such as epoxychloropropane and various dihydroxylic alcohols or trihydroxy alcohol and the compound that obtains, make the ethylene linkage reaction in peracid and the molecule and the epoxy compounds that obtains etc.Particularly; Can enumerate out ethylene glycol diglycidylether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, TEG diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1; Diglycidyl ether, the polytetramethylene glycol diglycidyl ether of 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol S expoxy propane diglycidyl ether (bisphenol S propylene oxide diglycidyl ether), hydrogenated bisphenol A diglycidyl ether, addition of ethylene oxide or expoxy propane form on bisphenol-A compound, gather (propane diols adipate ester) glycol diglycidyl ether, gather (glycol adipate) glycol diglycidyl ether, gather (caprolactone) glycol diglycidyl ether, 3; 4-epoxy radicals cyclohexyl methyl-3 '; 4 '-epoxy radicals cyclohexane carboxylic acid ester, 1-methyl-3; 4-epoxy radicals cyclohexyl methyl-1 '-methyl-3 '; Two [1-methyl-3,4-epoxy radicals cyclohexyl] ester, the VCH diepoxides of 4 '-epoxy radicals cyclohexane carboxylic acid ester, adipic acid, polydiene such as peracetic acid and polybutadiene or polyisoprene are reacted and obtain gather epoxy compounds, epoxidised soybean oil etc.

Compound with the unsaturated group of participating in polyaddition reaction can use a kind or and with the compound more than 2 kinds according to purpose.

The content of photocurable compound is not special to be limited, and the viewpoint from coating, system film property with respect to the above-mentioned metal complex of 100 mass parts, is preferably 0～1000 mass parts, more preferably 0～500 mass parts.

The conductor layer of this execution mode forms can also contain Photoepolymerizationinitiater initiater with composition.Photoepolymerizationinitiater initiater can suitably be selected from known material.As Photoepolymerizationinitiater initiater, for example can enumerate out benzoin alkylether classes such as benzoin, benzoin ethylether; 2-hydroxy-2-methyl propiophenone, 4 '-isopropyl-2-hydroxy-2-methyl propiophenone, 2, acetophenones such as 2-dimethoxy-2-phenyl acetophenone, diethoxy acetophenone; Radical polymerization light triggers such as 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholinyl-propane-1-ketone, phenyl glyoxalic acid methylester, benzophenone, benzil, biacetyl, diphenylsulfide, eosin, thionine, anthraquinone class; Absorbing light and cationic polymerization light triggers such as acidic aromatic series diazol, aromatic series salt compounded of iodine, aromatic series sulfonium salt; Absorbing light and produce anionic polymerization light trigger of alkali etc.As the anionic polymerization light trigger, it is useful that light alkali produces agent, for example can enumerate out in No. 2008/072651 communique of International Publication disclosed compound etc.

The content of Photoepolymerizationinitiater initiater is not special to be limited, and the viewpoint from coating, system film property with respect to 100 mass parts metal complexs, is preferably 0～100 mass parts, more preferably 0～50 mass parts.

[conductor substrate]

Can the conductor layer of this execution mode be formed and process base material, that is, in this execution mode, can process and comprise base material and reduce the conductor substrate of the conductor layer that forms after being applied on the aforementioned substrates with composition through above-mentioned conductor layer is formed with composition.For example, composition is used in the conductor layer formation that comprises the metal complex shown in the formula (1) through reduction on base material, can on base material, form conductive pattern.And then, can also pass through plated conductor pattern after reduction, thereby process the conductor substrate of excellent electric conductivity.

[base material]

The conductor layer that is coated with this execution mode does not form with the base material of composition is special and limits.As its concrete example, can enumerate out polyester such as PETG, polybutylene terephthalate (PBT), poly terephthalic acid tetramethylene ester, PEN is base material; Polyimides such as condensed type polyimides, addition polyimide, high temperature addition polyimide are base material; Epoxy resin base materials such as BA type epoxy resin, BF type epoxy resin, phenoxy resin; Phenolic resins such as linear phenol-aldehyde resin, cresol novolac resin, polycarboxylated styrene are base material; Polyethylene, polypropylene, polystyrene, gather polyolefin base materials such as cycloolefin; Nylon 6; 6, nylon 6, nylon 6; T, nylon 4; 6, polyamide-based base material such as nylon 12, nylon 6,12 etc. and polyurethane series base material, polycarbonate-based base material, polyacetals are that base material, polyphenylene oxide are base material, to gather (methyl) acrylic ester base material, acrylonitrile-butadiene-styrene copolymer be that base material, polyphenylene sulfide are that base material, polyether-ether-ketone are that base material, PEI are that base material, polyether sulfone are that metals such as base material, polybenzoxazole are base material, the resin base material strengthened through glass fiber etc., Cu, Ag, Au, Ni, Pd, Co, Rh, Fe, In, Sn are base material etc.Because the formation of the conductor layer of this execution mode need not carrying out sintering more than 150 ℃ when on base material, forming conductor layer with composition, so the thermal endurance of base material etc. are unrestricted.Therefore, can use above-mentioned various resin.

The coated conductor layer forms with the not special restriction of the form of the base material of composition.As its concrete example, can enumerate out film like, sheet, band shape, microgranular, laminated sheet, three-dimensional moulding article, metals such as Cu, Ag, Au, Ni, Pd, Co, Rh, Fe, In, Sn are carried out printed wiring board or film, the band etc. that patterning forms.Therefore; Used also not special qualification of form of conductor substrate of this execution mode of said base material; Can suitably select according to use etc., can process film like, sheet, band shape, microgranular, laminated sheet, three-dimensional moulding article, metals such as Cu, A g, Au, Ni, Pd, Co, Rh, Fe, In, Sn are carried out printed wiring board or film, the band etc. that patterning forms.

In this execution mode, can also possess resin bed on the surface of above-mentioned conductor layer one side of being formed with of base material.Particularly when on the base material of asperitiesization, forming conductor layer, through on the face of asperitiesization, forming the resin bed that refractive index and base material are similar to, thereby can improve the transparency of conductor substrate.Consequently, can produce: be applicable to that also plasma scope requires the conductor substrate of the purposes of high transparent with electromagnetic shielded film etc.

Be formed at not special qualification of kind of the resin bed on the substrate surface, for example can enumerate out epoxy resin such as bisphenol A type epoxy resin or bisphenol f type epoxy resin, four hydroxyphenyl methane type epoxy resin, phenolic resin varnish type epoxy resin, resorcinol type epoxy resin, polyalcohol/many diol types epoxy resin, polyolefin-type epoxy resin, ester ring type or halogenated bisphenol; Natural rubber, polyisoprene, gather 1,2-butadiene, polyisobutene, polybutene, gather-2-heptyl-1,3-butadiene, gather-the 2-tert-butyl group-1,3-butadiene, gather-(two) alkene classes such as 1,3-butadiene; Polyethers such as polyoxyethylene, polyoxypropylene, polyvinyl ethylether, polyvinyl hexyl ether, polyvinyl butyl ether; Polyesters such as polyvinylacetate, polyethylene propionic ester; Polyurethane, ethyl cellulose, polyvinyl chloride, polyacrylonitrile, polystyrene, polymethacrylonitrile, polysulfones, polythiaether, phenoxy resin, polyethyl acrylate, butyl polyacrylate, polyacrylic acid 2-Octyl Nitrite, the polyacrylic acid tert-butyl ester, polyacrylic acid 3-ethyoxyl propyl ester, polyoxy carbonyl tetramethyl acrylic acid ester, PMA, polyisopropyl methacrylate, polymethylacrylic acid dodecyl ester, polymethylacrylic acid myristyl ester, poly-n-propyl methacrylate, polymethylacrylic acid 3; 3; 5-3-methyl cyclohexanol ester, polyethyl methacrylate, polymethylacrylic acid 2-nitro-2-methyl propyl ester, gather four carbonyl methacrylates, polymethylacrylic acid 1,1-diethyl propyl ester, polymethyl methacrylate etc. gather copolymer resinses such as (methyl) acrylic acid ester, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate etc.In the middle of these, from the viewpoint of cementability, preferred epoxy acrylate, polyether acrylate.

As epoxy acrylate; Not special the qualification; For example can enumerate out 1, (methyl) acrylic acid addition products such as 6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinolformaldehyde resin, adipic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester, polyethyleneglycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, T 55, pentaerythrite four glycidol ethers, D-sorbite four glycidol ethers etc.

As polyether acrylate, not special the qualification for example can be enumerated out polyethylene glycol acrylate, polypropylene glycol acrylic acid ester etc.

Above resin can also can blend use copolymerization more than 2 kinds more than 2 kinds.

[manufacturing approach of conductor substrate]

The manufacturing approach of the conductor substrate of this execution mode comprises following operation: the conductor layer that will comprise the metal complex shown in the formula (1) forms and is applied on the base material with composition, reduces thereafter.Use composition through using above-mentioned conductor layer to form, can under the condition of gentleness, make conductor layer with the high pattern of fineness.

[painting process]

In the manufacturing approach of the conductor substrate of this execution mode, the conductor layer that will comprise the metal complex shown in the formula (1) forms and is applied on the base material with composition.The conductor layer formation of this execution mode is applied to not special qualification of method on the base material with composition.As its concrete example, for example can enumerate out known method such as flexible printing method, woodburytype, hectographic printing method, gravure processes, silk screen print method, ink-jet method, spray-on process, spin-coating method, rolling method, electrostatic spraying method, curtain formula rubbing method.In the middle of these, preferred flexible print process and woodburytype.Be applied on the base material with composition through utilizing these print processes that conductor layer is formed, can form the conductor layer of the thickness that is suitable for implementing chemical plating with the high position precision.

In the past, adopted the method for example use etching method etc. on base material, to form conductor layer always, processed the shape etc. of the antenna of IC tag for the conductor layer that will be formed at substrate surface, and must remove unwanted conductor layer part through etching.But, in the manufacturing approach of this execution mode, owing to can only optionally form conductor layer through painting process in the place of needs, so do not need this numerous and diverse operation.

[reduction operation]

In the manufacturing approach of the conductor substrate of this execution mode, with conductor layer form be applied on the base material with composition after, the conductor layer that reduction is coated with forms uses composition.Under the effect that reduction is handled, the structure of the metal complex of formula (1) changes.Handle through reduction, the metal ion of the n valency of the metal complex of formula (1) is reduced into metal ion or the metal below (n-1) valency.Accompany therewith, dissociate out from metal ion, become free Tropolones or free tropolonate ion as the anion (tropolonate ion, tropolonate ion) of the Tropolones of part.Like this, conductor layer forms and is reduced with composition, thereby the metal ion of the n valency in the formula of making (1) becomes the metal of 0 valency.

The method of reduction is not special to be limited, as long as adopt known method.Method in the solution that for example can enumerate out the method that contacts with reducibility gas such as hydrogen, impregnated in reducing agent etc., if consider simplicity, the efficient of equipment, the then preferred latter.Because the conductor layer of this execution mode forms with composition and handles the metal that makes the metal ion of the n valency in the formula (1) become 0 valency through reduction, so the platings of stating after can further carrying out such as chemical plating.

The dissolubility of metal complex shown in the formula (1) in organic solvent etc. is excellent, so can modulate the solution of high concentration.Therefore, use composition, then can consequently, can form the highdensity conductor layer of excellent electric conductivity through reduction with the metal complex of high density cloth of coating-type (1) on base material if use it to form as conductor.In addition, the dissolubility of the metal complex of this execution mode in the organic solvent of wide scope is high, is organic solvent so needn't specially use the strong halogen of dissolving power.Because halogen is that the power of impregnation of organic solvent in base material is strong; So except base material takes place the rotten problem easily; Also and deposit the problem high to the harmfulness of human body, if use the metal complex of this execution mode, then can avoid such halogen is the problem of organic solvent.

The kind of reducing agent is not special to be limited, and for example can enumerate out inorganic salts such as sodium hypophosphite, potassium hypophosphite, titanium chloride, boron compounds such as dimethyamine borane, sodium borohydride, potassium borohydride, reproducibility organic compounds such as formaldehyde, hydrazine etc.Wherein, from need not high-temperature process and can suppressing the rotten viewpoint of base material, boron compounds such as preferred dimethyamine borane, sodium borohydride, potassium borohydride, hydrazine.And then, reactivity high aspect, preferred boron compound, from the viewpoint of fail safe and cost-effectiveness, preferred especially sodium borohydride (NaBH ₄).Impregnated in the method in the solution of reducing agent, solvent types is not special to be limited, if consider fail safe, preferably makes water or ethanol, more preferably water.The dissolubility of above-mentioned metal complex in organic solvent is excellent, and on the other hand, the dissolubility in water is low.According to these, even used the method for reducing of water, the metal complex that is applied on the base material can stripping in water yet, can keep the state that is coated with, so can on base material, carry out plating.In addition, because above-mentioned metal complex is excellent to the adaptation of base material, so need not to cooperate bonding agent etc. to be used to guarantee the resinous principle with the adaptation of base material.Cooperating under the situation of resinous principle, need be used for the high-temperature process of crosslinked this composition, consequently, the situation that base material rotten becomes problem is a lot, yet owing to do not need above-mentioned high-temperature process, so can prevent the rotten of base material.And employed base material may not be high for thermal endurance, so the Material Selection scope of base material is wide.

[plating operation]

In the manufacturing approach of the conductor substrate of this execution mode, can implement plating to the conductor layer of making through reduction.The method of plating is not special to be limited; As long as implement plating such as copper facing, nickel plating, chromium plating, zinc-plated, zinc-plated and ashbury metal, gold-plated, silver-plated, platinum plating family through known method, perhaps chemical platings such as chemical nickel plating, electroless copper, chemical palladium-plating, chemical gilding, self-catalysis type chemical gilding, electroless cobalt plating get final product; But never need set out preferred chemical plating with electrode engagement and easy viewpoint.In the middle of these, form the viewpoint of conductor layer, more preferably electroless copper or chemical nickel plating, further preferred electroless copper with high conductivity from using cheap material.

When using the conductor layer of this execution mode to form on base material, to make conductor layer with composition; Have the following advantages etc.: (1) because as long as at least on substrate surface the coated conductor layer form and to reduce with composition, so operation quantity few (for example etch processes etc. not necessarily); (2) can as lithographic printing, not produce the development waste liquid, etching waste liquor etc. of photoresist; (3) since high-temperature process such as high temperature sintering not necessarily, so the material chosen restriction of base material is obtained relaxing; (4) owing to also can not use expensive black composition such as palladium, so cost is low.Like this, the manufacturing approach of this execution mode can be easy and makes conductor substrate with low cost.

The conductor layer of this execution mode forms and can be applied to composition and conductor substrate: RFID is with the antenna circuit of IC tag, the circuit of printed wiring boards such as flexibility, rigidity, rigid-flexible, and electromagnetic wave shielding is used fine wiring; Semi-conductive wiring, transistorized wiring, the wiring of capacitor; The wiring of resistor, the wiring of battery, electrode, the wiring in the OLED display, electrode; Wiring, electrode in the inorganic EL display, the wiring in the digital signage, electrode, the wiring in the Electronic Paper, electrode; Wiring in the LCD, electrode, the wiring of plasma scope, electrode, purposes such as the wiring of face luminous lightings such as organic EL, electrode.

In above-mentioned,, can enumerate out IC tag antenna circuit substrate, flexible printed circuit board as the optimal way of the conductor substrate of this execution mode.In these substrates, need on resin film, form high-precision conductor layer.But, be background with low price tendency in recent years, how can be very important with low-cost production.In the manufacturing of the conductor substrate of this execution mode, owing to do not need burning till high temperature under, thus can on resin film, form conductor layer with high accuracy, and owing to not needing etching work procedure, so can also form conductor layer with high efficiency.Therefore, the conductor substrate of this execution mode is suitable as IC tag antenna circuit substrate, flexible printed circuit board.

Because it is few in restriction suffered aspect the material of the substrate that forms conductor layer etc. that the conductor layer of this execution mode forms with composition and conductor substrate, so various characteristicses such as desired thermal endurance, dimensional stability, insulating properties are adjusted its composition in can the purposes according to them.

Embodiment

Below, the present invention will be described in more detail through embodiment, but the present invention is not limited to these embodiment.

[embodiment 1]

< synthesizing of metal complex solution >

1.8g (11mmol) 4-isopropyl tropolone (Asahi Kasei Finechem Co., Ltd. system, chamenol) is dissolved in the 20g ethanol under 25 ℃.In this solution, add 1.0g (5mmol) Schweinfurt green monohydrate, stirred 1 hour down, obtain the copper complex formazan solution of 4-isopropyl tropolone at 50 ℃.The copper complex formazan affirmation of 4-isopropyl tropolone is carried out through elementary analysis (device name: Perkin-Elmer Corporation system, CHNS).

< coating >

The flexible printing plate of the straight-line pattern of protuberance live width 1mm is carved with in use, and the aforementioned metal complex solution is applied on the PETG made membrane (be split into industry (strain) system, " サ Application De マ Star ト processing PET Off イ Le system (sand pad processing PET film) ", surface roughness: Ra=0.641 μ m, Rmax=7.732 μ m) of thickness 100 μ m with linearity.In addition, as printing machine, the IGT printability testing machine Model F1 that uses IGT Testing Systems to make printed with print speed printing speed 18m/ minute.

< reduction >

Under 25 ℃ at 5 quality %NaBH ₄The aforementioned PETG made membrane that will be coated with metal complex in the aqueous solution flooded 2 minutes, thereby reduced this metal complex, on the PETG made membrane, formed the metallic copper pattern of linearity.

< chemical plating >

Bathe in (50 ℃) at the electroless copper of forming by 3.0g copper sulfate pentahydrate, 7.0g Calcium Disodium Versenate dihydrate, 18.7g 37 quality % formalins, 100mL 1M NaOH; The aforementioned PETG made membrane that is formed with the metallic copper pattern was from the teeth outwards flooded 10 minutes, thereby on the PETG made membrane, form the conductive pattern of linearity.The conductivity of resulting conductive pattern is 53 * 10 ⁶S/m shows very good electrical conductivity.The mensuration of the conductivity of conductive pattern is carried out through the three Multitester CP-7D that make with electric gauge Co., Ltd..

In addition, the conductivity reaches through following formula (a) and (b) obtains.

σ[S/cm]＝1/ρv (a)

ρv＝R×w×t/L (b)

ρ v: specific insulation [Ω cm]

R: conductor layer resistance value [Ω]

W: conductor layer width [cm]

T: conductor layer thickness [cm]

L: conductor layer length [cm]

[embodiment 2]

< synthesizing of metal complex solution >

Except using ethyl cellosolve to replace the ethanol, likewise obtain the copper complex formazan solution of 4-isopropyl tropolone with embodiment 1.

< coating >

With the same condition of embodiment 1 under implement, with linearity coating metal complex solution on substrate.

< reduction >

With the same condition of embodiment 1 under implement, on substrate, form the metallic copper pattern.

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 54 * 10 ⁶S/m shows very good electrical conductivity.

[embodiment 3]

< synthesizing of metal complex solution >

Under 25 ℃, 1.8g (11mmol) 4-isopropyl tropolone (Asahi Kasei Finechem Co., Ltd. system, chamenol) is dissolved in the 20g ethanol.In this solution, add 1.3g (5mmol) nickel sulfate hexahydrate compound, stirred 1 hour down, obtain the solution of 4-isopropyl tropolone nickel complex at 50 ℃.

< coating >

< reduction >

With the same condition of embodiment 1 under implement, on substrate, form the metallic nickel pattern.

< chemical plating >

At the electroless nickel bath (pH=9 that forms by 20g/L nickel sulfate hexahydrate compound, 15g/L sodium hypophosphite monohydrate, 30g/L Triammonium citrate; 50 ℃) in; The aforementioned PETG made membrane of the pattern that is formed with metallic nickel was from the teeth outwards flooded 10 minutes, thereby on the PETG made membrane, form the conductive pattern of linearity.The conductivity of resulting conductive pattern is 2 * 10 ⁶S/m shows good electrical conductivity.

[embodiment 4]

< synthesizing of metal complex solution >

Under 25 ℃, 1.78g (11mmol) is dissolved in the 20g terpinol through the synthetic 3-isopropenyl tropolone of known method (" new experimental chemistry lecture ", ball kind (strain), distribution in 1977, p.914).In this solution, add 1.0g (5mmol) Schweinfurt green monohydrate, stirred 1 hour down, obtain the copper complex formazan solution of 3-isopropenyl tropolone at 50 ℃.The copper complex formazan affirmation of 3-isopropenyl tropolone is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 53 * 10 ⁶S/m shows very good electrical conductivity.

[embodiment 5]

< synthesizing of metal complex solution >

Under 25 ℃, 1.5g (11mmol) is dissolved in the 30g ethanol through the synthetic 4-methyl tropolone of known method (" new experimental chemistry lecture ", ball kind (strain), distribution in 1977, p.913).In this solution, add 1.0g (5mmol) Schweinfurt green monohydrate, stirred 1 hour down, obtain the copper complex formazan solution of 4-methyl tropolone at 50 ℃.The copper complex formazan affirmation of 4-methyl tropolone is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 50 * 10 ⁶S/m shows very good electrical conductivity.

[embodiment 6]

< synthesizing of metal complex solution >

Under 25 ℃, 1.34g (11mmol) tropolone (Tokyo changes into industry (strain) system) is dissolved in the 40g ethanol.In this solution, add 1.0g (5mmol) Schweinfurt green monohydrate, stirred 1 hour down, obtain the copper complex formazan solution of tropolone at 50 ℃.The copper complex formazan affirmation of tropolone is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

[embodiment 7]

< synthesizing of metal complex solution >

1.51g (11mmol) is mixed through the synthetic amino tropolone of 5-, 40g ethanol and 1.0g (5mmol) the Schweinfurt green monohydrate of known method (" new experimental chemistry lecture ", ball kind (strain), distribution in 1977, p.919); Stirred 1 hour down at 50 ℃, obtain the copper complex formazan solution of the amino tropolone of 5-.The copper complex formazan affirmation of the amino tropolone of 5-is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 45 * 10 ⁶S/m shows very good electrical conductivity.

[embodiment 8]

< synthesizing of metal complex solution >

2.21g (11mmol) is mixed through synthetic 5-bromine tropolone, 40g ethanol and 1.0g (5mmol) the Schweinfurt green monohydrate of known method (" new experimental chemistry lecture ", ball kind (strain), distribution in 1977, p.920); Stirred 1 hour down at 50 ℃, obtain the copper complex formazan solution of 5-bromine tropolone.The copper complex formazan affirmation of 5-bromine tropolone is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 47 * 10 ⁶S/m shows very good electrical conductivity.

[embodiment 9]

< synthesizing of metal complex solution >

1.62g (11mmol) is mixed through synthetic 5-cyanic acid tropolone, 40g ethanol and 1.0g (5mmol) the Schweinfurt green monohydrate of known method (" big organic chemistry the 13rd volume non-benzene series aromatic cycle compound ", (strain) towards the storehouse bookstore, nineteen sixty distribution, p.375); Stirred 1 hour down at 50 ℃, obtain the copper complex formazan solution of 5-cyanic acid tropolone.The copper complex formazan affirmation of 5-cyanic acid tropolone is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 48 * 10 ⁶S/m shows very good electrical conductivity.

[embodiment 10]

< synthesizing of metal complex solution >

With 1.9g (11mmol) through known method (" new experimental chemistry lecture ", ball kind (strain), distribution in 1977, p.909) synthetic 4; 5-benzo tropolone, 40g ethanol and 1.0g (5mmol) Schweinfurt green monohydrate mix; Stirred 1 hour down at 50 ℃; Obtain 4, the copper complex formazan solution of 5-benzo tropolone.4, the copper complex formazan affirmation of 5-benzo tropolone is carried out through elementary analysis.

< coating >

< reduction >

< chemical plating >

With the same condition of embodiment 1 under implement, on substrate, form conductive pattern.The conductivity of resulting conductive pattern is 46 * 10 ⁶S/m shows very good electrical conductivity.

[comparative example 1]

< synthesizing of metal complex solution >

1.3g (5mmol) acetylacetone copper (II) (Tokyo changes into industry (strain) system) and 20g ethanol are mixed, stirred 1 hour down at 50 ℃, but insoluble matter is more, becomes suspended state.Filter out insoluble composition, obtain acetylacetone copper (II) solution.

< coating >

< reduction >

Though with the same condition of embodiment 1 under implement, do not see separating out of metallic copper pattern.

< chemical plating >

Though with the same condition of embodiment 1 under implement, do not see the formation of conductive pattern.

[comparative example 2]

< synthesizing of metal complex solution >

Under 25 ℃ with 2.5g (11mmol) 1,3-diphenyl-1,3-propanedione (Tokyo change into industry (strain) system) is dissolved in the 20g toluene.In this solution, add Schweinfurt green monohydrate 1.0g (5mmol), stirred 1 hour down at 50 ℃, but insoluble matter is more, becomes suspended state.Filter out insoluble composition, obtain 1,3-diphenyl-1,3-propanedione copper (II) complex solution.

< coating >

< reduction >

< chemical plating >

According to above content check, the conductor layer of embodiment 1～10 forms all can form metal pattern with composition on substrate, can process the conductor substrate of excellent electric conductivity through plating.Confirm that on the other hand comparative example 1 and 2 conductor layer form and all can't on substrate, form metal pattern with composition, also can't on substrate, form conductor through plating.

The application is based on the Japanese patent application (Japan special hope 2009-097902) of on April 14th, 2009 to the application of the japanese Room, with fitting into this in it as reference.

Utilizability on the industry

Conductor layer of the present invention forms with composition, uses the manufacturing approach of its conductor substrate and conductor substrate, as the technology of the conductor layer of the antenna of manufacturing IC tag, electromagnetic wave shield, flexible printing wiring board etc., can in extensive fields, utilize.

Claims

1. a conductor layer forms and uses composition, and it comprises the metal complex shown in the following formula (1),

In the formula (1), R ¹, R ², R ³, R ⁴And R ⁵Represent hydrogen atom, carboxyl, alkoxy carbonyl, cyanic acid, formoxyl, acyl group, nitro, nitroso, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxyl, sulfydryl, alkylthio group, alkoxyl, halogen atom or amino independently of one another; For R ¹, R ², R ³, R ⁴And R ⁵, can be in them at least 2 bondings and form saturated rings or unsaturated ring each other, also can have independently of one another from the compound shown in the formula (1) and break away from 1 valency group that 1 hydrogen atom forms as substituting group; M representes to be selected from the metal more than in the group of being made up of Cu, Ag, Au, Ni, Pd, Co, Rh, Fe, In and Sn any; N representes 1～6 integer.

2. conductor layer according to claim 1 forms and uses composition, wherein, and said R ¹, R ², R ³, R ⁴And R ⁵Represent hydrogen atom or isopropyl independently of one another.

3. conductor layer according to claim 1 and 2 forms and uses composition, and wherein, said M representes Cu.

4. conductor substrate, it comprises base material, and

Through being formed, each described conductor layer in the claim 1～3 reduces the conductor layer that forms after being applied on the said base material with composition.

5. the manufacturing approach of a conductor substrate, it comprises following operation: the conductor layer that will comprise the metal complex shown in the following formula (1) forms and is applied on the base material with composition, reduce then,

In the formula (1), R ¹, R ², R ³, R ⁴And R ⁵Represent hydrogen atom, carboxyl, alkoxy carbonyl, cyanic acid, formoxyl, acyl group, nitro, nitroso, alkyl, alkenyl, cycloalkyl, aralkyl, aryl, hydroxyl, sulfydryl, alkylthio group, alkoxyl, halogen atom or amino independently of one another; For R ¹, R ², R ³, R ⁴And R ⁵, can be in them at least 2 bondings and form saturated rings or unsaturated ring each other, also can have independently of one another from the compound shown in the formula (1) and break away from 1 valency group that 1 hydrogen atom forms as substituting group; M representes to be selected from the metal more than in the group of being made up of Cu, A g, Au, Ni, Pd, Co, Rh, F e, In and Sn any; N representes 1～6 integer.

6. the manufacturing approach of conductor substrate according to claim 5, wherein, said reduction uses sodium borohydride to carry out.

7. according to the manufacturing approach of claim 5 or 6 described conductor substrates, wherein, after carrying out said reduction, also comprise the operation of said conductor layer being implemented plating.

8. the manufacturing approach of conductor substrate according to claim 7, wherein, said plating is a chemical plating.

9. the manufacturing approach of conductor substrate according to claim 8, wherein, said chemical plating is an electroless copper.

10. according to the manufacturing approach of each described conductor substrate in the claim 5～9, wherein, said conductor layer is formed the method that is applied on the base material with composition carry out through flexible printing or intaglio printing.