TW200920873A - Method of forming a conductor layer, method of manufacturing a circuit board, method of manufacturing conductive fine particles, and composition for forming a conductor layer - Google Patents

Abstract

A method of forming a conductor layer includes: a coating film formation step (S1) of forming a coating film by applying a coating liquid containing a polyimide precursor resin onto the surface of an insulating substrate and drying the same; an impregnation step (S2) of treating the coating film with a metallic compound solution and thereby impregnating the surface layer of the coating film with metal ions present in the solution; a metal coating formation step (S3) of forming a metal coating as the conductor layer by subjecting the metal ions impregnated into the surface layer of the coating film to a reduction treatment; and an imidization step (S5) of imidizing the polyimide precursor resin in the coating film to thereby form a polyimide resin layer. The metallic compound solution contains: a metallic compound including a metal having a normal electrode potential of -0.25 to + 1.55; and a nitrogen-containing compound having an equilibrium constant of 6 or lower for a complex-forming reaction with the metal ions, and has a pH of 9 to 12.

Description

200920873 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Fields of the Invention] A method for manufacturing a circuit wire, for example, a method for forming a conductor layer of a wiring or the like in an electronic component, and a method for forming a conductor layer

And a conductive fine particle floc; a raw material, a t B &method' and a conductor layer forming composition used for forming a conductor layer. [Prior Art] In recent years, the miniaturization of electronic components and the speed of signal transmission are required. High-density wiring is required for circuit boards such as printed substrates. What is indispensable for real-thickness density fabrics is that the conductor layer formed with the ® case is finely processed (10)'. The right-handed conductor layer is finely processed, and the close contact with the substrate is reduced. Therefore, in order to achieve an increase in the reliability and productivity of the electronic component, it is important to improve the adhesion between the conductor layer and the substrate, so that it can be finely processed. ^ is a method for forming a fine pattern on a circuit board and having excellent adhesion to a substrate. The method described below is described in the following: _ uniform in a thermosetting resin composition containing an organic W A conductive metal f obtained by dispersing fine metal particles having a fine average particle diameter. In the search for this patent document, the printing method of the ink method is applied to the substrate by the electroless metal paste, and the coating film is heated to 15 (rc~21 (the temperature of rc. The heating system is such that It is carried out for the purpose of curing the coating film and curing the thermosetting resin. However, in the method of Patent Document 1, if the gold 97134815 4 200920873 is not successfully carried out, it is a cerium particle. In the case of sintering, the conduction of the conductor layer is not achieved, and the reliability of the electronic component may be lowered. Further, as a method of forming a conductor layer that does not use metal fine particles, Patent Document 2 describes the following method: A polyamidene precursor resin solution containing a palladium ion-containing compound and a polyimine precursor resin. In the method of Patent Document 2, the above-mentioned polyamidene precursor resin solution is applied to a polymer by a bar coater. After brewing the imine substrate, the coating film is dried to form a polyimine precursor metal complex layer. Eight people, in the presence of a hydrogen donor, the polyimine precursor metal complex layer Irradiation service 'outside line' forms ore matrix nucleus Thereafter, the metal layer of the mineralized matrix is formed by electroless plating treatment. Further, after the plating layer is formed by plating on the metal layer of the keying matrix, or the like, the polyimine precursor resin is heated and imidized. The polyimine resin layer is formed. The technique described in Patent Document 2 does not use a conductive metal paste containing metal fine particles, and therefore has an advantage that the conductor layer can be formed without being affected by the sintered state of the metal fine particles. In the method of Patent Document 2, the reduction of the metal ions is carried out by ultraviolet irradiation, and the efficiency of suppressing the metal ions is insufficient. Therefore, there is a problem that the step of electroless plating is required. In the method of the layer, it is known that after introducing a cation exchange group into a resin substrate, the metal ion is chemically adsorbed to the cation exchange group by a metal ion-containing liquid, and then a reduction treatment is performed. However, when the metal ion adsorbed to the cation exchange group is reduced by the reduction ▲ liquid, the metal precipitates as an island on the surface of the resin. There is a problem that it is difficult to form a metal film having no defects. In order to improve this problem, for example, JP-A 97314815 200920873 discloses a technique in which a metal ion is adsorbed to a cation exchange group to reduce the imine resin. In the reducing agent solution of pHi~6, 're-electroless mineralization is carried out. However, in the method of Patent Document 3, it is necessary to have a step of introducing a cation exchange group into the sulphuric lion and an electroless plating step. Therefore, there is a disadvantage that the number of steps is increased. Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-324966 (Patent Document No. JP-A-2005-154880) (Patent Document No. 2002-266075) [Summary of the Invention] • (The problem to be solved by the invention) The method of feeding and dispensing 3 is to form a conductor layer having high adhesion to the polyimide resin, and is included in the polyacid A step of reducing the metal ions to precipitate a metal on the surface of the amine resin or the polyanilin precursor resin. However, if the reduction efficiency is low or the amount of adsorption of the metal ions to the resin is insufficient, the defects occurring on the metal film after the reduction treatment become large, and the conduction cannot be achieved depending on the state, and as a result, the plating core (species) cannot be used. Therefore, in the methods of Patent Document 2 and Patent Document 3, it is necessary to carry out the step of electroless plating of the deposited metal film. However, electroless ore has the management of the plating solution or the waste of the night treatment, and must also consider the impact on the environment. Therefore, it is strongly desired to develop an "alternative technique" of "layer" which is required to perform electroless plating and which is excellent in adhesion to the surface of the substrate. Μ The object of the present invention is to provide a reduction treatment by metal ions. Further, a method of forming a conductor layer having excellent adhesion strength to a polyimide resin and having few defects is formed on the surface of the imine resin. The method for forming the first observation conductor layer of the present invention is The method of forming a conductor layer on the surface of the hetero-imide tree substrate or the wake-up imine resin film is characterized in that the step of impregnation is carried out by containing a standard electrode potential of _Q. a metal compound solution having a metal compound in a range of a ruthenium and a nitrogen-containing compound having an equilibrium constant of 6 or less and a pH of 9 to 12, and belonging to the sub The substrate or film formed of the precursor of the amine resin = the resin or the film, and the ions of the above metal are impregnated into the surface layer of the substrate or film formed of the above-mentioned polyimide resin The step of forming a metal film as the conductor layer is carried out by reducing the ions of the metal impregnated in the surface layer of the substrate or the film formed of the imine precursor resin. In the method for forming a conductor layer according to the first aspect, the metal having a standard electrode potential of 25 to +1. 55 may be selected from the group consisting of a crime, a %, a rib, an Ag, a Pt, and an Au. Further, in the above method of the conductor layer of the first aspect, the nitriding person may be ammonia or a first- or second-order amine. σ In addition to the method for forming a conductor layer of the above i-th aspect, The conductor layer may be a patterned conductor layer. 曰97134815 200920873 In the method for forming a conductor layer according to the first aspect, the polyimide film may be formed on a surface of a spherical insulating substrate. In the method of forming a conductor layer according to the first aspect of the invention, the method of producing a circuit board of the second aspect of the present invention is to provide an insulating base. Material and formation A method of manufacturing a circuit board of a conductor layer on an insulating substrate, comprising the step of forming the conductor layer on the insulating substrate, wherein the step of forming a coating film includes a step of forming a coating film a coating liquid of an amine precursor resin is applied onto the surface of the insulating substrate and dried to form a coating film; and the impregnation step is performed by treating the coating film with a metal compound solution to make the solution The metal ion is impregnated into the surface layer of the coating film _; and the metal film forming step is to reduce the metal ions impregnated into the surface layer of the coating film to form a metal film as the conductor layer; a metal compound containing a metal having a standard electrode potential in the range of -0.25 to +1.55, and a nitrogen-containing compound having an equilibrium constant of 6 or less with a mismatch reaction with the ion of the above metal, and having a pH of 9 to A solution in the range of 12. The method for producing conductive fine particles according to the third aspect of the present invention is characterized in that the spherical insulating substrate and the conductive fine particles covering the conductive layer of the spherical insulating substrate are characterized in that they are provided in the spherical insulating layer. a step of forming the conductor layer on the surface of the substrate, the step comprising: 97134815 8 200920873 a film forming step of applying a coating liquid containing an imine precursor resin onto the surface of the spherical insulating substrate, and applying Drying to form a resin film covering the spherical insulating substrate; ... the impregnation step' is to treat the resin film by a metal compound solution, so that metal ions in the solution are impregnated into the surface layer of the resin film, and the metal is In the step of forming, the metal ions impregnated into the surface layer of the resin film are subjected to (iv) original treatment, and (4) the ore is a metal film of the upper body layer; (the above metal compound solution contains a standard electrode potential of _0 25 to +1. a metal compound having a metal of 55 and a nitrogen-containing compound having an equilibrium constant of 6 or less in a misalignment reaction with an ion of the above metal, and The method of producing the conductive fine particles according to the fourth aspect of the present invention is characterized in that the spherical polyimide-based resin substrate and the conductive layer covering the spherical hetero-imide resin substrate are electrically conductive. And a method for producing the fine particles, comprising the step of forming the conductor layer on the surface of the spherical particles of the polyimine precursor resin which is subjected to the imidization of the spherical polyimide resin substrate The step includes: impregnating the step of treating the surface of the above-mentioned heteroparticles with a metal compound solution, thereby impregnating the metal ions in the solution into the surface layer of the spherical particles; and forming the impregnation with the base metal film forming step The metal ions in the surface layer of the spherical particles are treated as (4) as the conductive metal film; the metal compound solution contains a metal containing a metal having a standard electrode potential in the range of _〇25 to 97138815 9 200920873 +1.55 a nitrogen-containing compound having an equilibrium constant of a compound and a complex reaction with an ion of the above metal, and having a pH of from 9 to 12 The composition for forming a conductor layer according to the fifth aspect of the present invention is for impregnating a metal ion to a polyimine resin for forming a conductor layer on a polyimide or a semiconductor layer. a metal substrate containing a metal having a standard electrode potential in a range of from -0.25 to +1_55, and a treatment in a substrate or a film formed of a precursor of a polyimide-based precursor resin The nitrogen-containing compound having a balance constant of the metal ion is 6 or less and has a pH of 9 to 12. Further, the "conductor layer" in the present invention uses the following two meanings: The meaning of the metal film formed on the surface of the polyimide resin by the reduction of ions; and the meaning of the plating film including the above metal film and the upper layer formed thereon. Further, the conductor layer may have any layer other than the metal film or the plating layer. (Effect of the Invention) The method for forming a conductor layer of the present invention is to use a metal compound containing a metal having a standard electrode potential of from -0.25 to 1.55, and an equilibrium constant of a mismatch reaction with the above metal. A metal compound solution having a nitrogen-containing compound of 6 or less and having a pH of 9 to 12. By using this metal compound solution, a sufficient amount of metal ions can be impregnated into the polyamidene precursor resin when the metal film is formed, and high reduction efficiency can be obtained in the reduction treatment. Further, according to the method for forming a conductor layer of the present invention, by subjecting a sufficient amount of metal ions to impregnate the state of 9713815 10 200920873 to the polyimine precursor resin, it is not necessary to carry out the step of selfless plating. The ground forms a dense and dense metal film with the polyimide resin. Further, according to the method of manufacturing a circuit board using the method for forming a conductor layer of the present invention, an insulating substrate and a polyimide film layer, a polyimide resin layer, and a conductor layer as a wiring can be produced at a high yield. Excellent electronic components with high adhesion and reliability. ° (In addition, according to the method for producing conductive fine particles using the method for forming a conductor layer of the present invention, it is possible to produce a conductive material having excellent adhesion between the polyimide film substrate or the polyimide layer and the ν layer; The fine particles are used in the production process of various electronic components, and can be used for, for example, solder balls, conductive pastes, conductive adhesives, etc. Further, the conductor layer forming composition of the present invention, A nitrogen-containing compound having a balance constant of 6 or less and a pH of 9 to a metal compound containing a metal having a standard electrode in the range of 〇·25 to +1.55 and a mismatch reaction with an ion of the above metal In the range of 12, when used in the polyimine precursor resin, the metal ions in the 6-well composition can be largely impregnated into the surface layer of the polyimide precursor resin. Further, by using the present invention The conductor layer forming composition can provide high reduction efficiency in the reduction treatment. Therefore, by using the conductor layer forming composition 'of the present invention, the electroless plating step can be easily formed, and the polysiloxane can be easily formed. The composition for forming a bulk layer of the present invention is excellent in the use of the surface layer forming conductor layer of the polyimide layer to form a conductor layer 9713815 11 200920873. Other objects of the present invention [Embodiment] [Embodiment] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Fig. 表示 shows a conductor layer of this embodiment. FIG. 2 is an enlarged explanatory view showing a cross section of a main part of the circuit board of FIG. 1. First, a circuit to which the embodiment of the present invention is applied will be described with reference to FIGS. 1 and 2. The circuit board 1 includes an insulating base material 3 and a patterned conductor layer 5 which is a wiring on the insulating base material 3. As the insulating base material 3, an inorganic substrate such as a glass substrate, a tantalum substrate, or a ceramic substrate can be used. Or a synthetic resin substrate such as polyimine resin or polyethylene terephthalate (PET). (J patterned conductor layer 5 is as shown in Fig. 2 3 having a via in the insulating substrate

The metal film 9 formed by the polyimide resin layer 7 and the plating layer 11 formed to cover the metal film 9 are formed. The polyimide film 7 and the metal film 9 and the plating layer 11 are patterned into a predetermined shape. Further, the plating layer η may not be provided. In the present embodiment, only the metal film 9, or the metal film 9 and the plating layer U are regarded as "patterned conductor layer 5". Further, the patterned conductor layer 5 may have any layer other than the above layers. The polyimine resin layer 7 is mainly composed of a polyamidene resin which is heated by a polyamide amine 97138815 12 200920873 acid which is a poly-bromide precursor resin and subjected to dehydration/cyclization reaction. By. The polyimide resin is more suitable for use as a thermosetting resin such as an epoxy resin, a phenol resin or an acrylic resin than the other resins because of its excellent heat resistance and dimensional stability. The polyimide resin layer 7 in the present embodiment is obtained by pattern-coating a coating liquid containing a polyimide pigment precursor resin on an insulating base material 3, and then polymerizing the polyimide polyimide precursor. Formed by the formation. Therefore, the polyimide film 7 has high adhesion to the insulating base material 3. Such a polyimide resin layer 7 is interposed between the insulating base material 3 and the metal film 9, and functions as a binder. The metal film 9 is a film made of a metal which is precipitated by a metal ion which is impregnated with a polyimide resin (the yttrium imide resin layer 7) The metal on the surface of the imine resin. The metal constituting the metal film 9 is a metal having a standard electrode potential of from 〇25 to +1.55 as described later. . The plating layer 11 is a metal film mainly composed of, for example, Cu, Au, Ni'Co, Sn, Pd, Sn-Cu or the like. Among these metals, Cu, Au, etc. can be used particularly. Further, it is preferable that the metal constituting the electric clock layer 11 is made of a metal species W different from the metal constituting the metal film 9 because high adhesion can be obtained between the coating film 9 and the plating layer u. On the circuit board 1 , the gold film 9 is formed by impregnating metal ions with a polyimide resin and then reducing it. Therefore, there is a high adhesion between the polyimide film 7 and the metal film 9 by the erroneous effect caused by the impregnation, and the metal layer 11 is formed by the metal layer of the metal layer. The film 9 is firmly fixed to the polyimide film 7 . Further, the polyimine resin layer 7 is formed by coating the imide first on the insulating base material 3, and then the imide is imidized, so that the insulating base material 3 has high adhesion. For the reason described above, the circuit board i to which the method for forming a conductor layer of the present embodiment is applied is less likely to cause peeling even if the pattern is made fine, and has high reliability. Next, a method of forming a conductor layer according to a third embodiment of the present invention will be described with reference to Figs. 3 to 9 . The conductor layer formed in this embodiment is a patterned conductor layer. Fig. 3 is a flow chart showing an outline of main steps in a method of forming a conductor layer according to the embodiment. 4 to 9 are explanatory views for explaining main steps of a method of forming a conductor layer according to the embodiment. As shown in Fig. 3, the method of forming the conductor layer of the present embodiment includes steps S1 to S5 as main steps. In the step si, the coating liquid containing the polyimine precursor resin is applied to the insulating substrate 3 in a predetermined pattern as shown in FIG. The coating film 4Q is formed (coating film forming step). Further, reference numeral 40a in Fig. 4 denotes a coating film before drying. The coating film formed in the step & the cross-sectional shape of the transfer film 4 () formed on the insulating substrate 3 is shown in Fig. 5. In the present embodiment, as the coating liquid 20, a polyimine precursor resin before the imidization is used. The polyimine precursor resin has a property of easily impregnating metal ions contained in a metal compound solution described later. The polyimine precursor resin used in the coating liquid is used as a polyacrylamide resin obtained by using the same monomer component as the polyimine resin or containing a photosensitive group in the molecule (for example, Polyethylenic acid of the ethylenically unsaturated hydrocarbon group. Such a polyiminoimine precursor resin can be produced by reacting a known diamine compound with an acid anhydride in the presence of a solvent. Here, as the diamine compound used in the production of the polyimine precursor resin, for example, 4,4-monoaminodiphenyl, 2,-methoxy-diaminophenylanilide may be mentioned. , 1,4-bis(4-aminophenoxy)benzene, anthracene, 3-bis(4-aminophenoxy)benzene, 2, 2'-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2,-dimethyl-4,4'-diaminobiphenyl, 3,3, monodihydroxy-4,4,diaminobiphenyl, 4,4' - Diaminobenzimidil and the like. Further, as the diamine compound other than the above, for example, 2,2-bis-[4-(3-aminophenyloxy)phenyl]propane, bis[4_(4-aminophenoxy) can be used. Phenyl] stone, bis[4-(3-amine basic oxy)phenyl]; 5 wind, bis[4_(4-aminophenoxy)] phenyl, bis[4-(3-amino) Phenoxy)]biphenyl, bis[丨_(4-aminophenoxy)], phenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4_(4-amine) Phenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4- (3-Aminophenoxy)phenyl]ether, bis[4-(4-aminophenyloxy)]diphenyl ketone, bis[4-(3-aminophenoxy)]diphenyl ketone , bis[4,4'-(4-aminophenoxy)]benzamide, bis[4,4,-(3-aminophenoxy)]benzamide, 9, 9-double [4-(4-Aminophenoxy)phenyl]anthracene, 9,9-bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 97134815 15 200920873 4, 4'-methylenedi- O-aniline, 4, 4'-arylene-2,6- Diphenylaniline, 4,4'-indenyl-2,6-diethylaminoamine, 4,4,-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4 , 4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylnonane, 3,3,-diaminodi Phenyl decane, 4, 4'-diaminodiphenyl sulfide, 3,3,-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3, 3, _Diaminodiphenyl milling, 4, 4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl ether, 3,4,-diamine C 1 -diphenyl ether, Benzidine, 3,3'-diaminobiphenyl, 3,3,-dimercapto-4,4-aminobiphenyl, 3,3'-dimethoxyoxybenzidine, 4, 4'' -Diamine-based two '3,3-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine, 2,diaminopyridinium, 1,4-bis(4-aminophenoxyl) Benzene, [,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylphenylbis(1-indenylethylene)]diphenylamine, 4, 4-[1,3-phenylenebis(1-fluorenylethylene)]diphenylamine, bis(p-aminocyclohexyl)methyl, double ( -dot-amino-t-butylphenyl)ether, bis(p-monomethylamido-5-aminopentyl)benzene, p-bis(2-indolyl-4-aminopentyl)benzene , p-bis(indenyl, fluorenyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(/5-amino-- Tributyl)toluene, 2,4-diaminoindenylbenzene, m-diphenylbenzene-2,diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-diphenylene diamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-anthracene, parnor, and the like. Examples of the acid anhydride used in the production of the polyimine precursor resin include pyromellitic anhydride 3,3,4,4-diphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenyl. 97134815 16 200920873 Two needles of ruthenium tetracarboxylic acid, 4,4,-oxyl sulphur. Further, as the acid anhydride other than the above, for example, 2, 2, 3, 3, -, 2, 3, 3, 4, or 3, 3, 4 4, diphenyl ketone tetraphthalic acid dianhydride may be mentioned. , 2,3',3,4,-biphenyltetracarboxylic dianhydride, 2'2',3'3,-biphenyltetracarboxylic dianhydride, 2,3,,3,4, _diphenyl Ether tetraruthenic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, and the like. Also, it is also possible to use 3;3,,^4^4,,^2^3, needle 2, 2 bis(2,3- or 3, 4-carboxyphenyl)-propanone two-needle, double (2 3 a 3,4-monodecylphenyl) fluorene two-needle, bis(2,3_ or 3,4-didecylphenyl) hard: anhydride, 1,1-bis (2, 3- or 3) , 4-dicarboxyphenyl)ethane dianhydride, l 2, 7, 8_, I 2' 6' 7- or hydrazine, 2, 9, 10 phenanthrene-tetracarboxylic dianhydride, 2, 3, 6, 7 _蒽tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 2, 3, 5, 6-cyclohexane dianhydride, 2, 3, 6, 7- Naphthalene tetraphthalic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1' 4,5, 8-naphthalenetetracarboxylic dianhydride, 4,8-dimercapto 2, 3, 5, 6, 7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-u 4,5,8-tetradecanoic acid dianhydride, 2, 3, 6 , 7-(or 1,4, 5, 8-) tetrachloronaphthalene-i,4, 5, 8_(or 2, 3, 6, 7_) tetradecanoic dianhydride, 2,3,8,9-, 3,4,9,10-,4,5,10,ll- or perylenetetracarboxylic dianhydride, cyclopentane-1, 2,3,4-tetracarboxylic dianhydride, pyrex-2, 3, 5, 6-tetradecanoic acid dianhydride, pyrrolidine-2, 3, 4, 5-tetradecanoic acid dianhydride, thiophene-2, 3, 4, 5_ tetracarboxylic acid diif, 4, 4'-double (2, 3-dioxaphenoxy)diphenyl sulfonium dihydrogen and the like. The diamine compound and the acid anhydride may be used alone or in combination of two or more. Further, a diamine 97134815 17 200920873 compound or _ other than the above may be used in combination with the above diamine compound and acid anhydride. At this time, other than the above: the use ratio of the amine compound or the material is further less than 9 〇 mol%, preferably 50 mol%. When the system is used to find the bismuth resin, the enthalpy of the yoke is used to eliminate the rider's axis: the molar ratio of the oxime compound to the anhydride, the thermal expansion, the adhesion, and the glass transition point (Tg). Wait. Further, the reaction of the diamine compound with the acid anhydride is preferably carried out in an organic solvent. The organic solvent is not limited, and specific examples thereof include dimethyl hydrazine, N'N-methyl methamine, N, N dimethyl ethanoamine, and methyl 2- fluorenone. /, methyl amide, benzene, a, 7 _ butyl, etc., these can be used alone or in combination. X is not particularly limited as the amount of the mixed medium medium. The concentration of the heteroimine precursor obtained by the polymerization reaction is preferably adjusted to a range of about 5 to 3 G% by weight. use. The thus-regulated > trough liquid can be directly used as a coating liquid. The polyimine precursor resin is preferably selected in the form of a polyimine resin layer 7A having a thermoplasticity. By using the thermoplastic polyimide resin, the polyimide-imided resin layer 7 can be used as an adhesive layer which improves the adhesion between the insulating base material 3 and the metal film 9. The viscosity of the coating liquid 20 is preferably set to a viscosity in the range of 丨〇 10 〇 〇〇〇 cps. When the viscosity of the coating liquid 20 is less than i 〇 cps, it is difficult to control the target line width when coating with the dispenser 3 虞. When the viscosity of the coating liquid 2 exceeds 100, OOOcps, the coating liquid 20 blocks the nozzle of the dispenser 3 and cannot be applied to the insulating substrate 3. Further, the viscosity of the coating liquid 20 can be adjusted according to the line width of the coating film 4, 97134815 18 200920873. For example, when the line width L of the coating film 40 is in the range of l〇em or more and 100/zm or less, the viscosity of the coating liquid 2 is preferably in the range of 10 to 100 cps. When the line width l of the coating film 40 is set to be in the range of more than 100 and 200 " m or less, the viscosity of the coating liquid 2 is preferably in the range of 100 to 500 cps. When the line width of the coating film 40 is set to be more than 200/zm and 300 "in or less, the viscosity of the coating liquid 2 is preferably in the range of 500 to 50, OOOcps. When the line width l of the coating film 40 is in the range of more than 300 / / m and 400 / / m or less, the viscosity of the coating liquid 2 is preferably in the range of 50,000 to 70,000. When the line width l of the coating film 4 is in the range of more than 400 μm and 500//m or less, the viscosity of the coating liquid 2 is preferably in the range of 70,000 to 90,000. When the line width L of the coating film 4 is set to be more than 500 // m and 600 / zm or less, the viscosity of the coating liquid 2 is preferably in the range of 90,000 to 100,000. The viscosity of the polyimine precursor resin as the coating liquid 20 can be adjusted by controlling the molecular weight of the polyimine precursor resin or the solid content concentration of the polyimide precursor resin solution. Further, in the present embodiment, since the coating liquid 2 contains a metal compound (metal ion), it is not necessary to prepare a viscosity adjusting agent in the coating liquid 20. Therefore, even if the wet reduction method is employed, the problem that the polyiminoimine precursor resin is eluted by the action of the viscosity modifier and the reduction efficiency is lowered does not occur, and an efficient reduction treatment can be performed. In addition, the weight average molecular weight of the polyamidene precursor resin is preferably in the range of 10,000 to 300,000, more preferably in the range of 1,500 to 250,000, and 97134815 19 200920873 and more preferably 30,000 〜 200, within the scope of 〇〇〇. When the average molecular weight of the polyimine precursor resin is less than 10,000, the polyimine resin formed by subsequent imidization of the hydrazine becomes brittle. On the other hand, if the weight average molecular weight of the polyimine precursor resin exceeds 300,000, the viscosity of the polyimine precursor of the coating liquid is too high and it is difficult to handle. Further, the solid content concentration of the polyimine precursor resin solution is preferably in the range of 5 to 30% by weight. In the coating liquid 20, for example, a leveling agent, an antifoaming agent, an adhesion imparting agent, a crosslinking agent, or the like can be added as an optional component other than the above-mentioned essential components. The coating liquid 20 can be prepared, for example, by mixing a polyimine precursor resin and any of the above components in any solvent (for example, a pyridine solvent or an imidazole solution). Further, in the present embodiment, a polyamic acid varnish containing polyamic acid can be used as the coating liquid 2 (polyimine precursor resin solution). As a polyamic acid varnish, it can be paste (4) Days of age, limited shares, read plasticity, polyimine varnish SPI-200N (trade name), ibid. SPI_3〇〇N (trade name), ibid. SPI-l〇 〇〇G (trade name), TORAYNEACE #3000 (trade name) manufactured by Toray Industries, Inc., etc. In the coating film forming step of the step si, as the dispenser 30 for discharging the coating liquid 2, a known constituent can be used. For the commercial product, for example, (10) remuneration product ^Sonic Co., Ltd.) can be used. By using a dispenser 3, even a three-dimensional surface such as a concave-convex surface or a curved surface can be directly coated with a predetermined coating.

Cloth coating solution 20. Therefore, not only the conventional two-dimensional (planar) circuit formation but also a three-dimensional (stereo) circuit can be formed. V 97134815 20 200920873 When the coating film 40 is formed, the line width L of the pattern-like coating film 4 is preferably in the range of l〇~400//m, more preferably in the range of 15~2〇〇//111. Inside. Further, the line width L· of the coating film 40 formed by the dispensing machine is adjusted by the viscosity of the solution of the polyimide resin, the nozzle (discharge) diameter, and the discharge pressure. Control, depiction of speed control or a combination of these, and the target size can be adjusted. In the present embodiment, as described above, by setting the viscosity of the coating liquid 20 to 1 〇 to 1 〇〇, within the range of 〇〇〇cps, clogging of the discharge nozzle 30a of the dispenser 30 can be prevented, and In the coating film forming step of the step S1, the coating liquid 2 is discharged onto the insulating base material 3, and then dried to form a coating film 4〇. The coating liquid 20 discharged to the insulating substrate 3 is preferably in the range of 5 (M50 ° C, more preferably 80 to 140) (in the range of (wherein, more preferably i〇〇~i2 (Tc), The heating is carried out for a period of about 3 to 1 minute. At this time, if the heating temperature exceeds 150 〇c, the immersion step of the polyimide-based precursor resin proceeds, followed by the impregnation step (step 〇S2). It is difficult to impregnate the metal ions, and it is preferable to dry at a temperature within the above range. Next, the insulating substrate 3 having the coating film 40 is subjected to a solution containing a metal compound (hereinafter referred to as "metal compound" in the step S2. The solution") is treated to impregnate the metal ions in the metal compound in the coating film ( In the impregnation step of step S2, as shown in FIG. 6, an impregnation layer 41 is formed which impregnates metal ions from the surface of the coating film 40 to a certain depth portion. In the impregnation step, As the metal compound, an equilibrium constant of a metal compound containing a metal having a range of 971 971 25 25 to + 丨 55 in a range of 971 348 971 25 至 至 至 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 6 6 6 6 6 6 6 In the present embodiment, the reason for using the conductor layer forming composition is the same as the composition for forming a conductor layer in the range of 9 to 12 in the present embodiment.

*Reducing by metal ions 1^ Forming a metal material on the surface of the polyimine precursor resin. If the shapeable material has a certain reduction or more (4) metal film, it may be a slightly electroless plating step. Therefore, it is important to sufficiently increase the amount of metal ions impregnated in the resin (especially in the vicinity) and to increase the reduction efficiency of the ions in the reduction treatment as much as possible. Further, by increasing the amount of metal ions impregnated on the surface of the polyimide precursor resin, the impurity between the polyimide layer I and the conductor layer can be improved by the effect. Under the increase in the impregnation amount of the metal ion-polyimine precursor resin and the reduction efficiency, the above-mentioned composition for forming a conductor layer can exert a superior effect. In the formation of the conductor layer of the metal compound solution, the metal having a standard electrode potential of from -25 to +1.55 may, for example, be Ni, Sn, Pb, cu, h A§ Pt, Au or the like. When the standard electrode potential of the metal is less than 〇 25, it is difficult to carry out the method of forming the metal film after the (four) wet reduction method. In addition, the standard electrode and the stored Nernest formula are obtained from the standard margin of 25. Among the above-mentioned genus types, in the plating step described later (in the case of step, it is particularly preferable to have Ni and Sn which are excellent properties as a core). As a metal compound containing the above metal species, the metal can be used as a metal compound. Salt or 97113815 22 200920873 organic group-based complex, etc. Examples of the metal salt include sulfur (tetra), acetate, oxalic acid, and citrate. When the metal is Cu or Ni, it is preferable to use a metal. Preferred examples of such a metal compound include Ni (CH3COO) 2 > Cu(CH3C00) 2 ^ NiS〇4 ^ CuS〇4, NlC〇3. ^ ^ NiCl2 ^ CuCh, NiBr2, CuBr2 , Ni(N〇3)2, NiC2〇4, _^^^ η

Cul ^ Cu(N〇3) 2 ^ Ni(CH3C0CH2C0CH3)2 .  Cu(CH3C0CH2C0CH3)2# 〇和' as an organic silk compound which forms the above-mentioned metal and a ruthenium-based complex, and examples thereof include diterpenoids such as propylene, benzophenone, and benzophenone. A ketone carboxylate such as ethyl acetate or the like. Further, in the formation of the conductor layer as the metal compound solution, the equilibrium constant of the mismatch reaction with the ions of the metal is less than G, and the yttrium-containing sigma' is a metal ion from the metal compound and the amine is wrong. Compound. Since the amine complex thus formed has a property that the metal ion has a ligand which is easily freed in the subsequent step, it is considered that the reduction reaction of the metal ion can be smoothly performed to promote the formation of a uniform metal film. Further, the nitrogen-containing compound can exert a sputum adjustment action (buffering action). In the present embodiment, it is more preferable that the equilibrium constant of the ion-coincidence reaction with the metal is 4 or less. 3 gas. As the nitrogen-containing compound, it is preferably ammonia or! Grade or grade 2 amine. More preferably, it may be an aliphatic amine of 1, 1, and or 2. Specific examples of such an aliphatic amine include, for example, ethanolamine, diethanolamine, ethylenediamine, diethylamine, and the like. Among these, ammonia is easy to handle and has excellent transferability. Here, the "balanced reaction 97134815 23 200920873 balance # number" means that the equilibrium constant of the mismatch reaction of the coordination number 1 defined by the following formula can be obtained, for example, as a value in the pit salt aqueous solution. Reaction formula M+il~MLi Equilibrium constant @1=[ML] · [μ]-1 · [L]-1 (wherein, Μ is a metal ion 'L is a ligand, and [] represents a molar concentration m.卜 L-1) 吏 /, the equilibrium constant of the mismatch reaction between the ions of the above metals exceeds 6 = when the 3 IUt compound is formed, the metal ions of the composition layer for forming the conductor layer and the S-nitride S are formed. The nitrogen-containing compound belonging to the ligand becomes difficult to dissociate after the mismatched ion 'advances between the terminal sulfhydryl groups of the polyimine precursors to form a miscellaneous ion. As a result, it was expected that the reduction of the metal ions on the surface of the heteroimine precursor was relatively reduced. Therefore, in the metal film forming step to be described later, the metal film as the conductor layer is not formed or is insufficient. The pH of the composition for forming a conductor layer is in the range of pH 9 to 12. When the pH is out of the above range, it is not preferable because it affects the chemical structure of the polyaminic acid precursor polyamine. The pH of the conductor layer-forming composition can be adjusted by the above nitrogen-containing compound. The metal species and the nitrogen-containing compound in the conductor layer-forming composition are preferably, for example, a combination of Ni and ammonia, Ni and diethanolamine, Sn and ammonia, Sn and diethanolamine, Ag and ammonia, Ag and diethanolamine. Among these, the combination of Ni and ammonia is the best. In the conductor layer-forming composition used in the impregnation step, it is preferred to formulate a metal compound in a concentration range of from 1 mM to 500 mM. Metal compound blending 97138815 24 200920873 When it is less than 1 mM, it is too expensive to impregnate metal ions to the surface of coating film 40, which is not good. When it exceeds the ceremony, it consists of polyimine precursor resin. The surface of the formed coating film 4G is dissolved (dissolved), which causes deterioration of the patterned conductor layer 5, which is not preferable. Further, it is preferable that the molar ratio (nitrogen-containing compound/metal compound) of the nitrogen-containing compound and the metalized opening of the above-mentioned metal layer for the formation of the body layer is in the range of 2 to 12, and the above molar ratio is less than 2 Or more than 12, it is difficult to adjust the pH of the metal ruthenium compound solution, and there is a case where the metal ion is insufficient in the impregnation amount in the polyimide resin precursor resin. In the step of the present invention, the method of treating the polyimide film of the coating film 40 by the metal compound is not limited, and for example, a method of impregnating the polyether amine precursor resin in the mixture solution can be mentioned. A method of applying the solution to a polyimide precursor resin or the like. In the present embodiment, it is particularly preferable to adjust the metal compound solution having the above concentration to a temperature in the range of 20 to 40 C, and to impregnate the insulating base substrate 3 on which the coating film 4 is formed. In this case, the impregnation time may be such that the metal ions in the metal compound solution are impregnated into the surface layer portion of the coating film 4 to form the impregnation layer 41, preferably, for example, 5 minutes to 5 hours, more preferably 5 Minutes ~ 2 hours. When reddish between the immersion/bechazine for 5 minutes, the impregnation of the metal ion to the coating film 4〇 was insufficient, and the anchoring effect described later could not be sufficiently obtained. On the other hand, even if the impregnation time exceeds an hour, the degree of impregnation of the coating film 4 is exceeded by the metal ions, so that the above effects cannot be expected to be improved. In the case of the person S, in the step S3, the metal in the impregnation layer 41 of the coating film 4 is removed from the metal film by a metallurgical process. In this step, the method of the S3 metal is also not limited to the method of the Qing Dynasty. The wet reduction method, the hydrogen reduction method, the ultraviolet irradiation reduction method, the electron beam irradiation method, the heating reduction method, and the electricity are not used. Method such as sexual reduction method. The wet reduction method is a method in which the coating film 40 on which the impregnation layer 41 is formed is immersed in a solution containing a solution (a solution) to make a gold. The material reduction method is a method in which the coating film (4) (4) of the impregnation layer 41 is formed and the metal ions are regenerated. The hydrogen reduction method is a method in which a coating 4b having an impregnation layer 41 is formed in a nitrogen atmosphere to reduce metal ions. In the reduction treatment method, it is preferable to use a wet reduction method in which the metal coating film 9 in the metal film forming step has a small unevenness in precipitation and can form a uniform metal film in a short period of time. In addition, as described in the above-mentioned Patent Document 2 (Japanese Patent Laid-Open No. -15 No. 5), in the poly-branched imine tree saponin containing the precursor and the poly-bromide precursor resin, Yu Zizi A three-dimensional cross-linking reaction occurs between the splits of the poly-aracine which belongs to the polyimine precursor resin. Therefore, over time, the polyamidene first resin solution is viscosified, _, _ (four) cloth silk amine substrate. 2 In order to prevent such gelation, in the technique of Patent Document 2, a low: sub-organic compound of B-propene or Ethylacetate is added to the polyaniline precursor resin solution as a viscosity. stabilizer. However, since the low molecular organic compound has a dissolution effect on the polyimine precursor resin, there is a problem that the reduction efficiency of the polyimide in the wet reduction step is lowered. Therefore, in the method of Patent Document 2, which is formulated with a polymethyleneimine precursor of a low molecular organic compound, 9713815 26 200920873, a secret solution > a liquid solution, a metal ion can be used by ultraviolet irradiation. Restore. On the other hand, in the method for forming a conductor layer of the present embodiment, since the coating liquid 20 (polyimine precursor resin solution) does not contain a metal compound, it is not necessary to add a low molecular organic compound, and wet reduction can be employed. . The reducing agent used in the wet reduction method for the optimum reduction method is preferably a boron compound such as sodium borohydride, potassium borohydride or dinonylamine borane. The boron compound such as () can be used as a solution (reducing agent solution) such as sodium phosphite, furfural or hydrazine. The concentration of the boron compound in the reducing agent solution is preferably, for example, 〇.  005~0·5mol/L. Better for you.  01~〇 lm〇1/L. When the concentration of the boron compound in the reducing agent solution is less than 〇5m〇1/L, the reduction of the metal ions contained in the impregnation layer 41 of the coating film 40 becomes insufficient, and if it exceeds O. In the case of lmol/L·, the polyiminoimine precursor resin in the coating film 4 is dissolved by the action of the boron compound. Further, the 'reduction type treatment towel' is a reducing agent solution in which the insulating substrate 3' of the coating film 40 is formed at a temperature in the range of 1 Torr to 9 (the range of TC, preferably 5 Torr to 7 Torr). In the middle, the immersion is 20 seconds to 30 minutes, preferably 3 seconds, minutes, and more preferably 1 minute to 5 minutes. By the above metal film forming step, the metal ions on the surface of the coating film 4 are reduced to precipitate metal. As shown in Fig. 7, a metal film 9 covering the coating film 40 is formed. This metal film 9 can serve as a core for subsequent plating, or can be directly used as the patterned conductor layer 5. 97134815 27 200920873 For the formation method of the body layer of the &, the step % immersion step and the metal immersion of the step S3 may be repeated for a plurality of times, for example, 2 to 10 times, preferably 2 to 5 times, as needed. The film 9 can be made into a denser thick film. In the subsequent plating step, sufficient conduction can be ensured. / In the step S4, the metal film 9 is plated as a core to form a plating layer 11 (electroplating step). By means of electric money, as shown in FIG. 8, it is formed in such a manner as to cover the metal film 9. Further, the step of the step S4 is an arbitrary step. The electric ore system may be, for example, a sulfuric acid, a copper sulfate, a hydrochloric acid or a gloss agent [for example, a MacuSpec (trade name) manufactured by MacDennid, Japan, which is commercially available, etc. In the plating liquid towel of the composition, the metal film g of the insulating base material 3 is used as a cathode, and a metal such as Cu is used as an anode. The current density at the time of plating is preferably in the range of, for example, 3·5Α/ώη2. Further, as the anode for electroplating, for example, a metal such as Ni or Co may be used in addition to Cu. Next, in step S5, the polyimine precursor resin in the coating film 40 is imidized (imine) For example, the polyamine acid in the coating film is subjected to dehydration and cyclization by heat treatment to carry out hydrazine imidization, whereby a polymer having excellent adhesion to the insulating substrate 3 is formed as shown in FIG. The imine resin layer 7. The heat treatment by the heat treatment is carried out by using a heat treatment apparatus which can heat the coating film 40 to a desired temperature. Preferably, it can be carried out in an inert gas atmosphere of nitrogen. The heat treatment can be, for example, 150~ 40 (temperature conditions within the range of TC for 60 minutes When the heat treatment temperature is less than 15 (TC, the yttrium imidation cannot be sufficiently performed, and when the heat treatment temperature exceeds 400 ° C, the thermal decomposition of the polyimide resin occurs. 97134815 28 200920873 As described above, it can be produced as described above. A circuit board 1 which is a patterned conductor layer 5 of a metal wiring is formed on the surface of the insulating base 3. The circuit board 1 is suitable for use in a rigid printed circuit board, a flexible printed circuit board, and a TABCTape Automated Bonding material. Or a CSP (Chip Size Package) material, a COG (Chip on Glass) material, or the like. In the present embodiment, a configuration is adopted in which a coating film forming step (step si) in which a coating film 40 is formed without using a metal compound (the coating liquid 40 is formed); and the coating film 40 is insulated. The substrate 3 is treated by a metal compound solution to form an impregnation step of the impregnation layer 41 on the surface of the coating film 40 (step S2); and the metal film formed by reducing the metal ions contained in the impregnation amount 41 to form the metal film 9 is formed. In the step (S3), the use of the coating liquid 20 containing no metal compound does not cause a problem of an increase in the viscosity of the coating liquid 2, so that the operation of the coating liquid 2 is easy. In the coating liquid used, since ruthenium does not contain a metal compound, the problem of viscosity-increasing gelation due to crosslinking of metal ions and poly-proline is not caused. Thus, even in the coating liquid 20 When the dispenser 30 is used for coating, the clogging of the nozzle is less likely to occur, and the coating is easy. Further, since the viscosity adjusting agent is not required to be disposed in the coating liquid 20, the wet reduction method using a metal ion reduction treatment is excellent. No need to bear The problem of elution of the imine precursor resin caused by the viscosity adjusting agent of the heart. In addition, the polyimine precursor resin constituting the coating film 40 has a content containing a metal ion in addition to the property of easily impregnating the metal ion. The electrode potential is 97138815 29 200920873 ί -0.  25 to +1.  A metal compound solution (conductor layer forming composition) having a metal compound in a range of 55 and a nitrogen-containing compound having an equilibrium constant of 6 or less in a mismatch reaction with the ion of the metal, and having a pΗ of 9 to 12 As the metal compound solution used in the impregnation step, the amount of metal ion impregnation with respect to the coating film 40 can be greatly increased. Therefore, it is extremely easy to form the metal film 9. In other words, after the coating film 40 is formed on the insulating base material 3, the metal compound solution is treated (impregnation treatment or the like) and the reduction treatment, whereby the surface of the coating film 40 can be easily formed into a dense thickness with a sufficient thickness. The metal film 9 can sufficiently achieve electrical conduction even without electroless plating or introduction of a cation exchange group. This metal film 9 can serve as a core for electroplating which is subsequently performed, or can be directly used as the patterned conductor layer 5. Therefore, in the method of forming the patterned conductor layer of the present embodiment, the electroless plating step necessary in the prior art can be eliminated, and the problem of plating solution management or waste liquid treatment does not occur, and the patterned conductor layer & In addition, the present invention is prepared by applying a coating liquid 20 containing a polyimide precursor resin to an insulating substrate 3 to form a coating film 4, followed by being subjected to amination. Since the polyimide film 7 is formed, high adhesion is obtained between the insulating base material 3 and the polyimide resin layer 7. Further, in the coating film 40 formed of the polyimine precursor, the metal ion is impregnated for 4 days, and then the metal film 9 is formed, which has a staggering effect on the polyimide layer 7 . By the anchoring effect of the straw, the adhesion between the layer 7 and the metal film 9 can be improved. Moreover, by using the above-mentioned derivative as the metal compound solution used in the impregnation step, the impregnation amount of the metal ion to the coating film 4 大幅 can be greatly increased, and the above-mentioned effect can be further increased by 9713 135 30 200920873 The imide resin layer 7 is more strongly cut with the metal. Further, the polyimine resin used in the present embodiment can easily control the molecular alignment under other synthetic resins, so that the thermal linear expansion coefficient of the polyimide resin layer 7 can be suppressed to be lower. The coefficient of thermal linear expansion of the metal constituting the metal film 9 and the plating layer 11 as wirings is made close. From the above facts, in the present embodiment, the patterned conductor layer 5 excellent in adhesion to the insulating base material 3 can be formed. Further, in the present embodiment, by directly applying the coating liquid 20 to the insulating base material 3 by using the dispenser 3 in accordance with a predetermined pattern, the photolithography step or etching can be omitted during the formation of the patterned conductive layer 5. step. Further, by using the dispenser 30 during the application of the coating liquid 2, the patterned conductor layer 5 can be easily formed even for a three-dimensional surface such as an uneven surface or a curved surface of the insulating base material 3. Therefore, in the present embodiment, the circuit board 1 having a flat plate or a three-dimensional shape can be manufactured with a small number of steps. According to the method of manufacturing a circuit board using the method for forming a conductor layer of the present embodiment, an electronic component having high adhesion between the insulating base material 3 and the patterned conductor layer 5 and excellent reliability can be manufactured with high yield. Further, in the present embodiment, since the conductive metal paste containing the conductive metal fine particles is not used, the conduction failure of the patterned conductor layer 5 is less likely to occur without the need for the sintering step. [Second Embodiment] Next, a second embodiment of the present invention will be described with reference to Fig. 10 . Fig. 10 is a flow chart showing the outline of the procedure of the method of forming the conductor layer of the embodiment. The method for forming the body layer of the genus 97134815 31 200920873 is provided with the steps shown in FIG. In the present embodiment, the surface treatment step of the step S11 of performing the surface modification of the insulating base material 3 is performed before the coating film forming step of the step S12 corresponding to the coating film forming step of the step S1 of the second embodiment. . Further, the steps S12 to S16 of the present embodiment are the same as the steps of the step S5 of the i-th embodiment, and therefore the description thereof is omitted. In the present embodiment, in the surface treatment step of step S11, it is preferable to mix (the content of the material of the insulating base material 3 is selected to be modified. The insulating base material 3 is made of an inorganic material such as a glass substrate or a ceramic substrate. In the case of the structure, it is preferable to surface-treat the surface of the insulating base material 3 with a Wei coupling agent. In this case, the surface treatment can be carried out, for example, by impregnating the insulating base material 3 in the solution of the sulphur coupling agent. The surface treatment of the smouldering agent can hydrophobize the surface of the insulating substrate 3 of the inorganic material, suppress the liquid flow after the application of the coating liquid 20, and suppress the line width expansion. Further, by using the stone smelting coupling agent The surface treatment can also improve the adhesion between the coating film 4 and the insulating substrate. Therefore, the pattern precision formed by the coating film 4 can be maintained, and the patterned conductor layer 5 can be reduced from the insulating base. The surface of the insulating substrate 3 is preferably treated with a contact angle with water of, for example, 2 G to 11 (in the range of Γ, more preferably 3 (M (9)). At this time, the contact angle with water is less than 2 〇. When the flow of the liquid after the application of the coating liquid 2 is suppressed, and when it exceeds n 〇, the adhesion between the coating film and the insulating base material 3 is lowered. As the Wei coupling agent used for the surface treatment, For example: 3 aminopropyl 97138815 32 200920873 triethoxy decane, 3-aminopropyl trimethoxy decane, 3-(2-aminoethyl) aminopropyl triethoxy decane, 3 -(2_Aminoethyl)aminopropyltrimethoxy oxime, 3-(2-aminoethyl)aminopropyl decyl diethoxy decane, 3-(2-amino B Aminopropyl decyl decyloxydecane, 3-triethoxydecyl-N-(l,3-dimercapto-butylene)propylamine, N-phenyl-3-amino The hydrochloride salt of propyl tridecyl oxide, N-(vinylbenzyl)-2-aminoethyl-3-ylaminopropyltrimethoxy decane, 3-ureidopropyltriethoxy Decane, 3-mercaptopropyl decyl decyl oxalate, 3-M propyl propyl decyloxy decane, 3-isocyanate propyl triethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, 2_(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3_epoxypropyl Oxypropyl propyl trimethoxy decane, 3-glycidoxy triethoxy decane, p-styryl trimethoxy oxime, 3-methyl propyloxypropyl f-group tri-f-oxy, 3 _Methylpropoxypropylmethyldiethoxywei, 3-methylpropoxypropyltrimethoxy zeoxime, 3-methylpropoxypropyltriethoxywei, 3-propylene In the case where the insulating base material 3 is made of a synthetic resin material, such as a polyamidide substrate or a pET (poly(ethylene terephthalate) substrate, etc., the oxypropyl triethoxy decane is used. Preferably, the surface of the insulating substrate 3 is surface-treated by a plasma, whereby the surface of the substrate 3 can be roughened by the surface treatment of the electrode, or the chemical structure of the surface can be changed. Therefore, the surface measurement of the swarf wire 3 can be improved, and the affinity of the cloth (4) can be improved. 1. The surface of the wire is stably held to maintain the coating liquid 2 依 according to the predetermined shape. Therefore, the pattern precision formed by the coating film 40 can be maintained. 97134815 33 200920873 As the plasma side, if using a field pressure treatment device, the mice, milk, nitrogen or a mixture of these gases are generated in a vacuum. The pressure at this time is preferably in the range of _~2_〇Pa, the processing temperature is in the range of i〇'°c, and the high-frequency (or microwave) output is in the range of 5〇. Further, when the material of the insulating base material 3 is a polyimide resin, as a means for improving the adhesion between the insulating base material 40 and the insulating base material 3, it is effective to subject the surface of the insulating base material 3 to aggregation. The imine resin is subjected to hydrolysis. Here, as the test f, for example, U 〇 H, K OH, and the like metal hydroxide, etc., it is preferable to use one or more selected from the group consisting of Κ0Η or NaOH. As described above, by performing the surface treatment step of the step S11, the flow of the liquid after the application of the coating liquid 20 can be suppressed, and the expansion of the line width can be suppressed. Further, by the surface treatment, the adhesion between the coating film 4 and the insulating base material 3 can be improved. Therefore, the pattern accuracy of the patterned conductor layer 5 can be maintained, and the occurrence of defects in the peeling of the patterned conductor layer 5 due to the decrease in the adhesion between the insulating base material 3 and the polyimide layer 7 can be reduced. The other actions and effects of the embodiment are the same as those of the first embodiment. [Third Embodiment] Next, a third embodiment of the present invention will be described with reference to Figs. 11, 12A and 12B. Fig. 11 is a flow chart showing an outline of a procedure for forming a conductor layer according to the embodiment. The method of forming the conductor layer of the present embodiment includes the steps S21 to S25 shown in Fig. 11. In the coating film forming step of the step S1 of the first embodiment, the coating liquid 20 is applied by the dispenser 30, but in the embodiment, in the coating film forming step of the step S21, in the embodiment of the invention. A droplet discharge device 50 that discharges minute droplets is used. The steps S22 to S25 of the present embodiment are the same as the steps % to S5 of the first embodiment, and the description thereof is omitted. In the present embodiment, as shown in Fig. 12A, the coating liquid 20 is applied onto the insulating base material 3 in a predetermined pattern by using a liquid droplet ejection. The droplet discharge device 5 includes droplets that can relatively move in the χγ direction with respect to the insulating base material 3 (the discharge nozzle 52 is provided. The droplet discharge nozzle 52 is provided with a discharge mechanism using an inkjet printing technique. (not shown), as shown in FIG. 12A, the coating liquid 2 is discharged to the insulating base material 3 by fine droplets. That is, the "droplet discharge head 52" includes, for example, a plurality of fine nozzle holes 52a; The nozzle hole 52a is connected to each other, and is configured to be capable of increasing or decreasing the internal volume by a contraction or elongation of a pressure element (piezo-element) (not shown), and is configured to use electricity from a control unit (not shown). The driving signal drives the pressure element to change the volume of the pressure generating chamber, and the coating liquid 20 is made into a small number of droplets of several microliters to several microliters from each nozzle hole 52a by the internal pressure rise occurring at this time. The liquid droplet ejection head 52 may be used as the liquid droplet ejection head 52. Instead of the above-described pressure method, a heat method may be used. As the coating liquid 20', the coating liquid of the first embodiment may be used. Almost the same composition In particular, the viscosity of the coating liquid 2 when the droplet discharge device 5 is used is preferably in the range of 10 to 20 cps. When the viscosity of the coating liquid 20 is less than i〇cps, it is difficult to control the target line width. Further, if the viscosity of the coating liquid 2超过 exceeds 97138815 35 200920873 20cps ', the coating liquid 20 is clogged in the nozzle hole 52a, and the coating liquid 20 cannot be coated. The polyimine precursor resin as the coating liquid 20 The viscosity of the solution is the same as that of the i-th embodiment. It can be adjusted by controlling the molecular weight of the polyimine precursor resin or the solid content concentration of the polyamidene precursor resin solution. The polyacid used in the present embodiment. The molecular weight of the imine precursor resin, the solid content concentration of the polyimide precursor resin solution, the preparation method, and the like are the same as in the first embodiment. When the coating film 40 is formed by the droplet discharge device 50, the pattern coating is applied. The line width L of the film stack 40 is preferably in the range of 10 to 400 / zm, more preferably in the range of 15 to 2 〇〇 / / m. Further, the droplet discharge nozzle 52 of the droplet discharge device 50 is used. The line width L of the formed coating film 40 is obtained by a polyimide resin precursor resin solution. The adjustment of the nozzle, the control of the nozzle (discharge) diameter, the control of the discharge pressure, the control of the stroke speed, or the like, can be adjusted to the target size. In the present embodiment, the coating liquid 20 is used as described above. The viscosity is set to be in the range of 10 to 20 cps, which prevents the liquid droplet ejection device 5 from being discharged from the internal pressure generating chamber (not shown) or the nozzle hole 52a. The line width is formed into a fine pattern. The coating liquid 20 is discharged from the liquid droplet discharging head 52 onto the insulating base material 3, and then dried. The drying can be carried out under the same conditions as in the step S1 of the first embodiment. The coating film 4 is formed on the insulating substrate 3 in a predetermined pattern. The other actions and effects of the embodiment are the same as those of the first embodiment. Further, in the present embodiment in which the droplet discharge device 50 is used, it is the same as in the second embodiment. It is also possible to provide a surface treatment step before the coating film forming step. [Fourth Embodiment] Next, a method of forming a conductor layer according to a fourth embodiment of the present invention will be described with reference to Figs. 13 to 18 . First, Fig. 13 is a cross-sectional view showing the internal structure of the conductive fine particles 10 应用 Q applied to the method for forming a conductor layer according to the embodiment of the present invention. Fig. 14 is a flow chart showing the main steps of a method of forming a conductor layer according to the embodiment. Figs. 15 to 17 are explanatory views for explaining main steps of the conductor layer forming method of the embodiment. Fig. 18 is a cross-sectional view showing the internal structure of another conductive fine particle 2〇〇 applied to the method for forming a conductor layer according to the present embodiment. The method of forming the conductor layer of the present embodiment is applied to the production process of conductive fine particles. The conductive fine particles 1 shown in Fig. 13 are suitably used for, for example, a bad ball or the like. Further, the conductive fine particles 2 shown in Fig. 18 are suitably used, for example, as a conductive paste or a conductive adhesive for bonding an electrode of an electronic component or a wiring board or the like. As shown in Fig. 13, the conductive fine particles have a spherical insulating base material (10) having an average particle diameter of, for example, about 5/zm to 1〇〇〇7, and a wake-up of the spherical solid material 1〇3. The polyimide film of the imide resin film 105 and the conductor layer of the coated polyimide resin layer 1G5. In addition, as a whole particle having the conductive fine particles 1GG of the polymerized layer 1G5 and the conductor layer 107, the particle size of the spherical insulating substrate 103 which is a core is arbitrary, and therefore, it can be used freely for use. set up. As the spherical insulating base material 103, for example, no fine particles of 97134815 37 200920873, or synthetic resin fine particles such as polyimine resin or polyethylene terephthalate (pET) can be used. . The polyimine resin layer 105 is mainly composed of a polyamidene resin obtained by heating and dehydrating and cyclizing a polyphosphonic acid which is a polyimine precursor resin. The polyimine resin layer 105 of the present embodiment is coated on a spherical insulating substrate 103 by coating a resin solution containing a polyimide precursor resin, and then iodizing the polyimine precursor resin. Former. Therefore, the polyimide layer Ο 105 has high adhesion to the spherical insulating substrate 103. The polyimide resin layer 105 is interposed between the spherical insulating substrate 103 and the metal film 1〇9 to exhibit a binder effect. The polyimine resin layer 105 is obtained from the viewpoint of ensuring high adhesion to the spherical insulating substrate 1〇3 and ensuring the thickness of the polyimide intermediate precursor resin required for sufficiently impregnating metal ions. The thickness is preferably, for example, about #5#m~50/ζιη. The conductor layer 107 has a metal film 1〇9 of the first conductor layer ti adjacent to the polyimide resin layer 1〇5, and an electric ore layer 111 covering the second conductor layer of the metal film 1〇9. Further, the plating layer 1Π may not be provided. In the present embodiment, only the metal film 109 or the metal film 109 and the plating layer m are regarded as "conductor layer 107". Further, the conductor layer 107 may have any layer in addition to the above layers. The thickness of the conductor layer i is preferably 50 nm or more, more preferably about 50 nm to 100/zm, from the viewpoint of ensuring sufficient conductivity of the conductor layer. The metal film 109 is precipitated to the polyimine precursor resin by reduction of the metal ion impregnated with the polyimide precursor resin (i-imidized into a polyfluorene 97138815 38 200920873 imine resin layer 105) The film formed by the metal on the surface. The metal constituting the metal film 109 is the same as the metal film 9 of the second embodiment, and the standard electrode potential is -0. 25 to + 1. Metal within the range of 55. - The metal species constituting the plating layer 丨丨1 is the same metal species as the plating layer 11 of the first embodiment. In the conductive fine particles, the metal film 1〇9 is formed by impregnating a metal ion with a polyimine precursor resin and then reducing it. Therefore, there is a close adhesion between the polyimide film 105 and the metal film 109 due to the anchoring effect of the impregnation. Further, the plating layer 11 is firmly fixed to the polyimide film layer 105 by interposing the metal film 1〇9 of the metal layer between the polyimide layer 1〇5 and the polyimide. In the resin layer, a resin solution containing a polyhimemine precursor resin is applied onto the surface of the spherical insulating substrate 1〇3, and then formed by hydrazine imidization, so that the spherical insulating substrate 103 has high adhesion. Sex. From the above facts, the conductive fine particles used in the method of forming the conductor layer are less likely to cause peeling of the conductor layer 107, and have high reliability. Next, a method of forming the conductor layer of the present embodiment will be described. As shown in Fig. 14, the method of forming the conductor layer of the present embodiment includes the steps of steps S31 to S35 as main steps. In the step S31, a resin solution containing a polyimine precursor resin is applied onto the surface of the spherical insulating substrate 103 and dried to form a resin film 12 (the resin film forming step). The cross-sectional shape of the spherical insulating base material 103 covered with the resin film 12A is shown in Fig. 15. As the resin used in the present embodiment, 97134815 39 200920873 can be used in the same manner as in the first embodiment. The method of applying the resin solution to the spherical insulating substrate 103 i is not limited, and for example, a method of impregnating the spherical insulating substrate 103 with a resin sheet, a method for the spherical insulating substrate 1G3 resin solution, or the like can be employed. Further, the drying of the resin solution is carried out in the same manner as in the step S1 of the first embodiment. Then, in step S32, the spherical insulating substrate 103 having the resin film 12 is treated with a metal compound solution to impregnate the metal ions in the metal compound solution into the resin film 12 (the impregnation step). In the impregnation step of this step, as shown in Fig. 16, a surface layer portion formed on the surface of the resin layer 12Q to a certain depth is impregnated with a metal ion impregnated layer ΐ2ι. Here, the impregnation step towel can be used as a metal compound solution for the conductor layer forming composition of the third embodiment. Further, the method of impregnating the metal film in the metal compound solution with the resin film 12 can be carried out in the same manner as in the third embodiment. Then, in step S33, the metal ions in the impregnation layer 121 of the resin film 12 are subjected to reduction treatment to form a metal film 丨〇9 (metal film formation + step). In this step, the metal ions on the surface of the resin film 12 are reduced to precipitate a metal, and as shown in Fig. 17, a metal film 109 covering the resin film 120 is formed. The reduction treatment in the metal film forming step of this step S33 can be carried out in the same manner as in the first embodiment. This metal film 1〇9 can be used as a core for subsequent plating, or can be directly used as the conductor layer 107. In the method for forming the conductor layer of the present embodiment, the step of forming the metal film in step S32 and the step of forming the metal film in step S33 may be repeated a plurality of times (for example, about 2 10 people, preferably 2 to 5 times). about). Thereby, the 'metal film 1 〇 9 can be made into a denser thick film' in the latter stage to ensure sufficient conduction. Although the steps are not shown in the drawings, if necessary, in the step coffee, the metal film is used as a core to carry out the electricity money, and the electric ore layer 111 is formed (the electric shovel step). Further, in the step S35, the polyimine resin layer 105 as a polyanilin resin film can be subjected to amination of the polyaniline precursor resin of the resin film 12Q (1 imidization step). . The steps of the electroplating step and the step of the imidization step of the above step S34 can be carried out in the same manner as in the first embodiment. Further, the electrowinning step of the step S34 and the hydrazine imidization step of the step S35 are arbitrary steps. As described above, the conductive fine particles in which the conductor layer 1G7 is formed on the surface of the hetero-imide resin layer 1G5 covering the spherical insulating substrate (10) can be produced (see Fig. 13). As the conductive fine particles, conductive particles for use as an example solderable ball, an anisotropic conductive film, or an anisotropic conductive paste are suitably used. In the present embodiment, the poly-amine precursor resin constituting the resin film 120 has a property of impregnating a metal ion material, and the composition for forming a conductor layer is used as an impregnation step metal compound solution. ^ The impregnation amount of the genus ion pair fine _ 12G is greatly increased. Therefore, the resin film 120 is formed, and after the metal compound solution is treated (the impregnation step) and the metal film forming step, the surface of the resin film 12 can be divided into a thickness to form a metal (10), which can sufficiently reach f. Sexual conduction. The metal film 1G9 formed by the dense formation of the city can be used as the core for subsequent electroplating, or the straight layer 97138815 41 200920873 is connected as the conductor layer 107'. In the method for forming the conductor layer of the present embodiment, the prior art is not required. The electroless plating step does not cause problems with ore deposits, management or waste disposal. - In the case of the present embodiment, a resin film containing a polyimide resin precursor resin is formed on the spherical insulating substrate 1〇3, and then a ruthenium is formed to form a polyimine. Since the resin layer is 1〇5, high adhesion 4 is obtained between the spherical insulating substrate 1〇3 and the polyimide resin layer 1G5, so that the metal ions are impregnated with the poly(imine) precursor resin. The metal film 109' obtained by the reduction has an anchoring effect on the polyimide layer ι〇5. By this anchoring effect, the adhesion between the polyimide film layer 105 and the metal film 1〇9 can be improved. Further, by using the above-described composition for forming a conductor layer as the metal compound solution used in the impregnation step, the impregnation amount of the metal ion to the resin film 120 can be greatly increased, and the above anchoring effect can be further increased to make the polyimine The adhesion between the resin layer 105 and the metal film 1〇9 is more secure. Further, the method for forming the conductor layer of the present embodiment can be applied to the spherical polyimide film base material 103a formed of the polyimide resin as the conductor layer 1 to 7 as shown in Fig. 18, for example. The conductive fine particles of the coated structure are manufactured. At this time, in Fig. 14, the conductor layer 107 may be formed in the same order as the step S32 to the step S35 except that the resin film forming step of the step S31 is not required. In other words, spheroidal polyimide precursor resin particles (not shown) which are to be formed into a spherical polyimine resin base material 103a are prepared, and the surface thereof is directly treated with a metal compound solution to form an impregnation layer. , the reduction treatment, electroplating, 97138815 42 200920873, yttrium imidization treatment, etc. can be. Further, the above spherical spheroidal polyimide precursor resin particles, for example, will contain

The acid liver such as PMDA is combined with a diamine such as 0M, and is stored at a reaction temperature of about 4 ° C and subjected to ultrasonic irradiation, whereby it can be easily formed. The spherical polyimine precursor resin particles thus formed have fine particles having an average particle diameter of 5 Å and less than 5 Å. X, the thickness of the conductor layer 107 is preferably, for example, about 3 〜 to 2_. Therefore, the conductive fine particles 200' obtained by using the spherical polyimine precursor resin particles are ultrafine particles having an average particle diameter of i 〇〇 nm or more and can be suitably used for, for example, a conductive paste or a conductive adhesive. Uses such as a solvent or a conductive ink for inkjet. The other actions and effects of the embodiment are the same as those of the i-th embodiment. Further, in the present embodiment, the spherical insulating substrate 3 may be provided with a surface treatment step similar to the step su of the second embodiment before the step of forming the resin film in the step S31. Next, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto. Further, in the following examples and comparative examples, the measurement of the standard electrode potential and the measurement of the equilibrium constant of the mismatch reaction were carried out by the following methods, without particular limitation. [Measurement of Standard Electrode Potential] A standard hydrogen electrode and a nickel electrode were combined, and an aqueous solution of 1 M nickel sulfate (1)) was used as an electrolyte to prepare an electrochemical cell. (The potential difference between the two poles is measured. The nickel values described in the following examples and comparative examples are the values calculated by the above-mentioned measurement method, 97138815 43 200920873. Further, the values of copper and silver are used in the basics of the chemical handbook. (Revised 3rd edition, Maruzen Press). The 'any-value is set to the standard electrode-position in the 25ΐ aqueous solution. Feeding-[Measurement of the equilibrium constant of the mismatch reaction] The standard electrode potential used in the measurement of the previous item is used. The electrolyte of the electrochemical cell is used as an aqueous solution of ammonium nitrate, and the potential difference E〇c between the two electrodes is measured at 25 °. The following formula is derived from the Naraest formula and the standard electrode current (the position E °c and the presence of the wrong ion) The relational constant of the equilibrium constant of the mismatch reaction / 3. The equilibrium constant of the erroneous reaction is calculated from the measured value of the potential difference using the following formula: E °c = E ° - RT / nF InySi

In^ ι=( E° — E°c)nF/RT E°c : Standard electrode potential E when there is a mismatched ion: Standard electrode potential (measured value of the previous item) F: Faraday constant L) R : gas constant τ : Absolute temperature η: valence of metal ions Stone 1: equilibrium constant of the mismatch reaction • (Reaction formula: M+1L-ML·, /^[ΜΙ^ΜΠΓ) Here's '金属: metal ion' l : coordination Base, [] represents the molar concentration m〇i · Li. Further, the values described in the following examples and comparative examples are the usual logarithmic values of the equilibrium constant of the mismatch reaction of the coordination number 1 calculated as described above, and the value of ammonia is determined by the measurement method described in 97138815 44 200920873. Calculate the value. In addition, the values of ethanolamine, diethanolamine, ethylenediamine and diethylamine are quoted from the Basics of Chemical Handbook (Revised 3rd Edition, Maruzen Press) and STABILITY CONSTANTS OF METAL-ION. c〇MPLEXES (published by 1964 BURLINGTON HOUSE) . Further, when the measurement conditions are different from those described above (in a 1 M aqueous ammonium nitrate solution at 25 ° C), the measurement conditions are added to the numerical values. [Production Example 1] (in the case of N,N-dimercapto-acetamide (hereinafter abbreviated as "DMAc") 170 ml, pyromellitic dianhydride (hereinafter abbreviated as "PMDA") 7.123g and 4, 4,-Diaminodiphenyl ether (hereinafter abbreviated as "〇DA") 7.877g, stirred at room temperature for 6 hours to prepare a polyamidamine precursor varnish A. The viscosity of this solution is E The viscosity was measured and found to be 13926 cps. The polyamidene precursor varnish A was diluted with DMAc to a volume ratio of 2 times to prepare a polyimide varnish a. [Production Example 2] 〇SN1 In 70 ml of decyl-2-pyrrolidone (hereinafter abbreviated as "NMP"), 5.45 g of PMDA and 5.0 g of 0DA were added, and the mixture was mixed at room temperature for 4 hours to prepare a styrene precursor varnish B. The viscosity of the solution was measured by an E-type viscosity meter, and the result was 665 cps ° [Production Example 3] In __, 3, 3, 4, 4 was added, and the second stupid base of tetracarboxylic acid was referred to as "hidden". ) 7.36g and bis-[4_(4-aminophenyloxy)phenyl]propanone (hereinafter referred to as "Cong") 10.26g, at room temperature for 4 hours, made 97138815 45 200920873 Imine precursor Paint C. The viscosity of this solution was measured by a £-type viscosity meter and found to be 15 cps. [Production Example 4] - Nickel acetate (11) tetrahydrate NKCHsCOO) 2 · 4IM) was dissolved in pure water to prepare a 100 mM aqueous solution of nickel (π) acetate. To a 10 mM aqueous solution of nickel acetate (11), a 30% by weight aqueous ammonia solution was stirred and a molar ratio of ammonia to nickel of 6 equivalents was adjusted to prepare a metal compound solution D. 5。 The metal compound solution D of Qi 0 is 10.35. 5。 The standard electrode potential of nickel is _ 〇 228, the equilibrium constant of ammonia for the mismatch reaction is 2. 36. [Production Example 5] Acetic acid (11) tetrahydrate Ni (CH3 2 • Glycol was dissolved in pure water to prepare a 100 mM nickel acetate (hydrazine) aqueous solution. In a 1 〇〇-nickel acetate aqueous solution, diethanolamine was added thereto with stirring. The molar ratio of the amine to the nickel was made into 6 amounts, and the metal compound solution E was prepared. The metal compound solution E was 犯9. (Also, diethanolamine (Mt, 0.43 M ethanolamine nitrate aqueous solution) for the ion The equilibrium constant of the mismatch reaction was 3.31. [Production Example 6] Nickel acetate (11) tetrahydrate Ni (CH3 2 • was dissolved in pure water to prepare a 100 mM aqueous solution of nickel acetate (11). In the aqueous solution of nickel acetate (丨I), the molar ratio of the amine to the molar ratio of nickel is 6 equivalents, and the metal compound solution F is prepared. The oil of the metal compound solution F is a crime. Further, ethanolamine (25t) 'Ion strength 〇. 1M) 9713415 46 200920873 for the misalignment reaction of Ni ions The equilibrium constant was 2.98. [Production Example 7] Nickel (II) acetate tetrahydrate Ni(CH3C00)2 · 4H2 〇 as pure water Dissolved, adjusted - made into a 100 mM aqueous solution of nickel (II) acetate. And a solution of the metal compound solution G is 11.30. Further, two of the aluminum compound solution (G) is added to the aqueous solution of the nickel acetate (11), and the molar ratio of the amine to the nickel is 6 equivalents. The equilibrium constant of the misc reaction of ethylamine (25 ° C, 2 M aqueous solution of ammonium nitrate) with respect to Ni ion f was 2.78. [Production Example 8] Nickel (II) acetate tetrahydrate NUCMXX)) 2 · 4 仏0 is dissolved in pure water to prepare a 100 mM aqueous solution of nickel (II) acetate. In an aqueous solution of i〇QmM nickel acetate (丨I), ethylenediamine is added with stirring to make the molar ratio of amine to nickel 6 equivalent. The metal compound solution solution H. The metal compound solution 11 is 1 〇 89. The equilibrium constant of the 'ethylene diamine (25 ° C 'ion strength 〇 · 1M) for the Ni ion mismatch reaction is 7. 35 (25 °C, ionic strength: 0.1 M) [Production Example 9] A copper (II) acetate-hydrate coffee (10) was dissolved in pure water to prepare an aqueous copper acetate (1) solution. In the 1 〇〇m liquid stomach, the addition of (four) gauge water is applied to prepare the metal compound solution ί relative to the amount of steel. The solution of the metal compound solution is 10·25. Further, the standard electrode potential of copper is 〇· 337, ammonia (10), (4) chloric acid recorded aqueous solution) to avoid the ion balance of the counter-contact equilibrium of 4. 27. 97134815 47 200920873 [Production example ίο] Dissolve copper (II) acetate monohydrate (CH3COO) 2Cu · mo in pure water, and adjust f " into a 100-secret copper (II) acetate aqueous solution. In a 1 〇〇 acetic acid steel (II) aqueous solution, diethanolamine was added with stirring to make the molar ratio of the amine to copper 4, and the metal compound solution J was obtained. The equilibrium constant of the miscible reaction of the diamine (25 ° C, 0.43 M ethanolamine nitrate aqueous solution) for the U ion is 4.75. (Production Example 11) Copper (II) acetate-hydrate (CH3COO) 2Cu · Η 2 溶解 was dissolved in pure water to prepare a 100 mM aqueous solution of copper (II) acetate. Ethylenediamine was added to an aqueous solution of 1 mM mM copper acetate (1)) to make the molar ratio of the amine to copper 4 equivalent, and the metal compound solution κ was prepared. The oil of this metal compound solution is 丨〇68. Further, the equilibrium constant of the ethylene-amine (25 ° C 'ion strength 〇.1 M) for the Cu ion mismatch reaction was 10.54. "{j [Production Example 12] Dissolve light silver scales in pure water to form a dirty aqueous solution of silver. In the dirty water of silver (4), Sheng Yang 3Q heavy duty water ammonia relative to the ear ratio into 4 2 #量' modulation into a metal compound solution L. The metallization of the 5 solution is 10.02. In addition, the standard electrode of silver, ammonia (10), infinite dilution solution) has an equilibrium constant for Ag separation of 3.315. [Production Example 13] 97134815 48 200920873 The silver nitrate AgN 3 was dissolved in pure water to prepare a mM silver nitrate aqueous solution. In a 100 mM silver nitrate aqueous solution, diethanolamine was added thereto to make the amine molar ratio of the amine to 2 equivalents to prepare a metal compound solution Μ. The metal compound-solution Μ is 9.35. Further, the standard electrode potential of silver is 0.7991, and the equilibrium constant of the diethanolamine (25 ° C '0.4 M lithium nitrate aqueous solution) for the Ag ion is 3. 48. [Production Example 14] ") Silver ruthenate Α Ν〇 3 was dissolved in pure water to prepare a 100 mM aqueous solution of silver nitrate. In an aqueous solution of 100 mM acid silver, ethylenediamine was added with stirring to make the amine relative to silver. Moerby becomes 2 equivalents 'modulated into -7。 The compound compound solution N. The pH of the metal compound Loose N is 1 〇 22. Further, the equilibrium constant of the ethylene diamine (2 〇〇 c, ionic strength 〇. 1M) for the Ag ion mismatch reaction is 4. 7 [Example 1] A test piece of an alkali-free glass (AN_1〇〇, manufactured by Asahi Glass Co., Ltd.) (I2·5 cm×12. 5 cm (thickness: 0·7 mm) was subjected to a 5 N sodium hydroxide aqueous solution at 50°C. After the treatment, the glass substrate of the test piece was washed with pure water, and dried, and then dried in a weight of 1% by weight of 3-aminopropyltrimethoxy decane (hereinafter referred to as "γ APS"). In the aqueous solution, the glass substrate was taken out from the γ aqueous solution, dried, and heated at 15 ° C for 5 minutes. The polyacrylonitrile precursor varnish A was applied to the glass substrate using a spin coater at 100 rpm. After spin coating for 1 second, it was dried at 130 t for 30 minutes. The thickness of the resin coating film formed by spin coating and drying was about 3. 5 # m. 97134815 49 200920873 Next, the above polyimine precursor resin was coated. The film was immersed in the above metal compound solution D at 25 ° C for 10 minutes to impregnate the metal ions to the polyimide precursor. In the fat, the polyimine precursor resin coating film is pulled up from the metal compound solution, washed with water, and dried. The polyimide film is coated with a polyimide film by a derivative-based plasma luminescence analysis method (Icp_AES). The nickel contained therein was quantified, and the result was llOOnmol/cm 2 per unit area. The above-mentioned polyimide ion impregnated with a metal ion was coated with a film of 3 Å. The crucible was immersed in a 10 mM sodium borohydride aqueous solution for 1 minute. A wet reduction treatment is performed to form a metal thin film on the surface of the resin coating film. Observation of the surface and cross section of the metal thin film by an electron microscope (SEM and TEM) confirmed that the metal thin film was dense and uniform and had a film thickness of 100 nm or more. Further, the metal film was firmly adhered to the polyimide film of the polyimide precursor, and it was confirmed that it had sufficient properties as a seed layer for electroplating in the subsequent step. [Example 2] A polyimide film of a polyimide film was formed as in Example 1. The polyimide film was coated in the above-mentioned metal compound solution E at 25 ° C for 10 minutes to impregnate metal ions into the polyaniline precursor resin. Thereafter, the polyimide-based resin coating film was pulled up from the metal compound solution, washed with water, and dried. The nickel contained in the polyimide film of the polyimide precursor was quantitatively determined by a combination of plasma-infrared spectroscopy (ICP-AES), and the result was l050 nm 〇 1 /cm 2 per unit area. The above-mentioned polyimine imide resin impregnated with a metal ion was coated with a film of 3 Å. The wet reduction treatment was carried out by immersing in a 10 mM aqueous solution of hydrogenated sodium hydride for 1 minute, and 97134815 50 200920873 formed a glossy metal film on the surface of the resin coating film. The surface and the cross section of the metal thin film were observed by an electron microscope (SEM and TEM), and it was confirmed that the metal thin film was dense and uniform and had a film thickness of 5 Å or more. Further, the metal film was firmly adhered to the polyimide film of the polyimide film, and it was confirmed that it had sufficient properties as a seed layer of the electric ore which is a later step. [Example 3] A polyimide film of a polyimide film was formed as in Example 1. This polyimide film was coated in the above-mentioned metal compound solution F at 25 ° C for 10 minutes to impregnate metal ions into the polyimide precursor resin. Thereafter, the polyimide film of the polyimide precursor was pulled up from the metal compound solution, washed with water, and dried. The nickel contained in the polyimide film of the polyimine precursor was quantified by derivatization combined with plasma luminescence analysis (ICP-AES), and the result was 765 nm 〇 1 /cm 2 per unit area. The above-mentioned polyimine imide resin impregnated with a metal ion was coated with a film of 30 Å. 〇 文 文 文 于 于 于 于 于 于 于 于 于 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 This metal film was firmly adhered to the polyimide film of the polyimide film, and it was confirmed that it had sufficient properties as a seed layer for the subsequent step. [Example 4] A polyimide film of a polyimide film was formed as in Example 1. The polyimide film was coated in the above-mentioned metal compound solution G at 25 ° C for 10 minutes to cause the metal ions to be contained in the polyaniline precursor resin. Thereafter, the polyimide-based resin coating film was pulled up from the metal compound solution, washed with water, and dried. 97134815 51 200920873 The above-mentioned polyimide ion impregnated metal ion precursor tree was coated with a film of 3 (rc was immersed in a 10 mM sodium borohydride aqueous solution for 1 minute for wet reduction treatment on the surface of the resin coating film. A glossy metallic thin enamel is formed. This metal film is firmly bonded to the polyimide-based precursor resin coating film, and it is confirmed that it has sufficient properties as a seed layer for electroplating in the subsequent step. [Example 5] Example 1 was formed by coating a polyimine precursor resin. The polyimide film was coated in a metal compound solution I at 25 ° C for 1 minute to impregnate the metal ions into the polyimide. In the amine precursor resin, the polyaniline precursor resin coating film is pulled up from the metal compound solution, and washed with water and dried. The above-mentioned polyimine imide precursor wax coating film impregnated with metal ions is used. Wet reduction treatment was carried out by dipping in a 10 mM sodium borohydride aqueous solution for 1 minute to form a metal thin film on the surface of the resin coating film. The metal film was firmly bonded to the polyimide film. Membrane on the membrane that confirms its subsequent steps The conduction y function can be applied as a seed layer. [Example 6] A polyimine precursor resin was coated as in Example 1. The polyimide film was coated in a metal compound solution J at 25 Å. 1 minute, the metal ions are impregnated into the polyimine precursor resin. Thereafter, the polyimide-based precursor resin coating film is pulled up from the metal compound solution, washed with water, and dried. The above is impregnated with metal ions. The polyimine precursor resin coating film was subjected to a reduction treatment by immersing in a hydrogenated aqueous solution of 1 GmM for 3 minutes, and a metal thin film was formed on the surface of the resin coating film. 97134815 52 200920873 The ground was adhered to the polyimide film of the polyimide precursor, and it was confirmed that it had the conduction function of the plating in the subsequent step, and it could be applied as a seed layer. [Example 7] A polyimine precursor resin was formed as in Example 1. Coating film: The polyimide resin precursor resin coating film is immersed in the metal compound solution L at 25 ° C for 1 minute to impregnate the metal ions into the polyimide pigment precursor resin. Imine precursor resin coating film from metallization The solution solution is pulled up, washed with water, and dried. The above-mentioned polyimine-imide resin impregnated with metal ions is coated with a film, and wet-reduced by 3 (rc is immersed in a 10 mM sodium borohydride aqueous solution for 1 minute, A glossy metallic thin enamel is formed on the surface of the resin coating film. The metal thin film is firmly adhered to the polyimide precursor resin coating film, and it is confirmed that it has sufficient properties as a seed layer for the subsequent step. Example 8] A polyimide-based precursor resin coating film was formed as in Example 1. The polyimide film was coated with a polyimide film in a metal compound solution at 25 ° C for 10 minutes to impregnate metal ions to In the polyimine precursor resin, the polyimine precursor resin coating film is pulled up from the metal compound solution, washed with water, and dried. The above-mentioned polyimide-impregnated precursor resin coated with a metal ion was immersed in a 10 mM smear aqueous solution for 1 minute at 3 〇〇c to carry out a wet reduction treatment, and was formed on the surface of the resin coating film. The shiny metal is thin. This metal film was firmly adhered to the polyimide film of the polyimide film, and it was confirmed that it had sufficient properties as the plating layer of the subsequent step 97134815 53 200920873. [Example 9] A polyimide film of a polyimide film was formed as in Example 1. This polyimide precursor resin coating film was immersed in the metal compound solution N at 25 ° C for 10 minutes to impregnate the metal ions into the polyimide precursor resin. Thereafter, the polyimine precursor resin coating film was pulled up from the metal compound solution, washed with water, and dried. The above-mentioned polyimine imide resin impregnated with a metal ion was coated with a film of 30 Å. (: A wet metal film was formed by immersing in a 10 mM hydrogenated shed aqueous solution for 1 minute to form a glossy metal film on the surface of the resin coating film. The metal film was firmly adhered to the polyimide film. On the film, it was confirmed that it had sufficient performance as a seed layer of the electric ore which is a later step. [Comparative Example 1] A polyimide film was formed as in Example 1. The polyimine was first.

The resin coating film was immersed in a 100 mM aqueous solution of nickel (II) acetate (pH 7.22) at 25 ° C for 10 minutes to impregnate metal ions into the polyimide precursor resin. Thereafter, the coating film of the 赆 lie precursor resin was pulled up from the metal compound solution, washed with water, and dried. The nickel contained in the polyimide film of the polyimide film was quantified by the derivative combined electron luminescence analysis method (ICp_aes), and the result was 120 nmol/cm 2 per unit area. The above-mentioned polyimine imide resin impregnated with a metal ion was coated with a film of 3 Å.浸 Dip in lGmM hydrogenated aqueous solution! Wet reduction treatment was carried out in minutes. As a result, the recorded microparticles were precipitated, but it was also observed that the fine particles of the brocade were dissolved in the aqueous solution of the reducing agent of 97134815 54 200920873. The surface and the cross section of the polyimide film coated with the polyimide film were observed by an electron microscope (SEM and TEM). As a result, it was confirmed that the fine particles of nickel were distributed on the surface of the resin coating film. The layer of the metal fine particles is not continuous, and although it can be used as a core for electroless plating, it is not sufficient as a seed layer for electroplating. [Comparative Example 2] A polyimide film of a polyimide film was formed as in Example 1. The polyimine precursor resin coating film is immersed in the above metal compound solution H at 25 ° C for 1 minute, (metal ions are impregnated into the polyimine precursor resin. Thereafter, the poly The amine precursor resin coating film is pulled up from the metal compound solution, washed with water, and dried. The nickel contained in the polyimide-based precursor resin coating film is quantified by derivatization combined with plasma luminescence analysis (ICP-AES). The unit area is 82 〇nm〇i/cm2. The above-mentioned metal ion imide precursor resin coated with metal ions is coated with a solution of 3 Torr. The solution is immersed in a 10 mM sodium borohydride aqueous solution for 1 minute for wet reduction. After the treatment, the metal film of nickel was not confirmed, and the surface of the resin coating film was only white turbid. (_ | [Comparative Example 3] A polyimide film was formed as in the first embodiment. The resin coating film is immersed in the metal compound solution K at 25 ° C for 1 minute to impregnate the metal ion into the polyphthalic acid resin. Thereafter, the polyaminic acid resin coating film is pulled up from the metal compound solution, and then Washed and dried. The above-mentioned polyimine impregnated with metal ions The resin coating film was subjected to wet reduction treatment by immersing in a 10 mM hydrogenated aqueous sodium solution at 30 ° C for 1 minute, but the copper metal film was not confirmed, and the dissolution of the resin coating film was confirmed. 97134815 55 200920873 From the above results, In the examples 丨 to 9 in which the conductor layer-forming composition (metal compound solution) of the present invention is used, it is formed to have a dense property capable of ensuring sufficient conduction, and has high adhesion between the polyimide-based precursor resins. Metallic film as a type of - bond (nuclear). In these examples, the metal species used is Ni or

In Examples 1 to 4 and 7 to 9 of the composition for forming a conductor layer of the metal compound of Ag and the nitrogen-containing compound, a glossy and dense metal thin film can be formed. In particular, in Examples and 2 in which a Ni compound and ammonia or diethanolamine are used, a uniform ('. and sufficient film-forming, absorbing metal film) can be obtained, and the result of maximizing the effects of the present invention is obtained. In the comparative example of using a metal compound solution containing no nitrogen-containing compound, it was confirmed that a discontinuous precipitation of metal particles was not observed, and a dense metal film could not be formed. Further, the equilibrium constant of the mismatch reaction with Νι ions exceeded 6 Comparative Example 2 of ethylenediamine or Comparative Example 3 using an ethylenediamine having an equilibrium constant of more than 6 in the miscombination reaction with Cu ions, a metal thin film could not be formed. Further, ij was compared with Examples 1 to 9 above. The results of Examples 1 to 3 are integrated in Table 1. 97134815 56 200920873 (Table 1) Evaluation of metal compound solution Metal standard electrode potential Nitrogen compound equilibrium constant pH Film state adhesion Example 1 Ni -0.228 Ammonia 2.36 10.35 Thick film • Very dense Good Example 2 Ni -0.228 Diethanolamine 3.31 9.82 Thick film • Compact very good Example 3 Ni -0. 228 Ethanolamine 2.98 10.52 Homogeneous continuous good implementation 4 Ni -0.228 Diethylamine 2. 78 11.30 Homogenization Continuous Good Example 5 Cu 0.337 Ammonia 4.27 10.25 Heterogeneous Continuous Good Example 6 Cu 0.337 Diethanolamine 4. 75 9. 75 Heterogeneous Continuous Good Example 7 Ag 0. 7991 Ammonia 3. 315 10.02 Homogeneous continuous good Example 8 Ag 0. 7991 Diethanolamine 3.48 9.35 Homogeneous continuous good Example 9 Ag 0.7991 Ethylenediamine 4. 70 10. 22 Homogeneous continuous good Comparative Example 1 Ni -0.228 — — 7.22 No Continuous - Comparative Example 2 Ni -0. 228 Ethylenediamine 7.35 10.89 Not formed - Comparative Example 3 Cu 0.337 Ethylenediamine 10.54 10. 68 Not formed - 97134815 57 200920873 [Example ίο] Prepared by Toray DuPont Co., Ltd. A test piece of 1QcmxlQan (thickness 25 (4) as a poly(imine) based on the polystyrene (4) "Kapt〇n ΕΝ" (trade name). A dispenser was used on the polyimide substrate (made by Sony Corporation) CASTPRO 11 (trade name)) After varnishing the polyimide precursor to a width of about Width, it was dried at 125 ° C for 1 G minutes. The thickness of the coating film formed by greening and drying was 2 / / m. Second, the above The imine is first coated with the above metal compound solution D to impregnate the metal ion in the polyurethane precursor with 25 (: 1). Thereafter, the polyamine precursor resin coating film is pulled from the surface compound solution to be washed with water and dried. The above-mentioned metal ion impregnated precursor resin coating film was impregnated with 1 G mM hydrogenated aqueous solution for 3 minutes, and subjected to wet reduction treatment to form a metal thin film on the surface of the sap . The surface and the cross section of the metal thin film were observed using an electron microscope (10) M and ◎ TEM), and it was confirmed that the metal thin film (4) was hooked to have a film thickness of 100 nm or more. Further, the metal film was firmly adhered to the polyimide film of the polyimide precursor, and it was confirmed that it had sufficient properties as a seed layer for electroplating in the subsequent step. Further, the nickel layer of the polyimide substrate was plated at a current density of 3.5 A/dm in a copper plating bath to form a copper wiring layer having a thick copper film thickness. The steel wire to be formed is formed into a polyimide substrate and heated to 300 ° C in a nitrogen atmosphere, and the polyimine precursor resin constituting the coating film is subjected to iminoation at a time of 5 minutes. Polyimine resin layer. Thereafter, the copper wiring is formed into a polyfluorene 97134815 58 200920873 sub-monthly female substrate in nitrogen%; the middle part of the cold to normal temperature. The copper wiring forms a polyimide-based substrate-based polyimine resin layer and the nickel layer is excellent in adhesion, and the copper wiring layer is firmly fixed to the polyimide substrate via the polyimide resin layer and the recording layer. on. In addition, the nickel layer and the bottom of the wire (4) are free from defects and have excellent conduction properties. [Example 11] A non-inspective glass (a test piece of AN__ manufactured by Asahi Glass Co., Ltd.) of 5Cmxl2·5em (thickness. 7mm) was treated with a 5N aqueous solution of sodium hydroxide for 5 minutes. Secondly, pure water was used. The surface substrate of the test piece was washed, dried, and then immersed in an i weight% r-APS aqueous solution. The glass substrate was taken out from the r-burning aqueous solution and then dried, and heated at 15 (rc for 5 minutes). The ink of the ink jet printer which is prepared in the market is filled with the above-mentioned polyimide varnish C as the droplet discharge device 5Q. Then, the ink jet printer discharges the polyimide on the glass substrate. An amine precursor varnish (:, a line of about 5 〇 #m width is drawn. Thereafter, the coating film on the glass substrate is dried at a temperature of 13{rc for 1 minute. The coating film formed by drawing and drying is formed. The thickness is 〇. 5#出. Next, the above-mentioned poly-labeled amine is first applied to the metal compound solution D at 25t: impregnation for 10 minutes to impregnate the metal ions in the polyimide precursor resin. After that, the polythene imine lion _ is pulled up from the metal compound solution, washed and dried. Applying the above-mentioned polyimine precursor precursor resin impregnated with metal ions to wet-reducting treatment with 3 (rc impregnated in 1 GmM aqueous solution of hydrogenated lysine for 1 minute, 59 97134815 200920873; surface of the coating of the tree A metal film is formed on the surface. The surface and cross section of the metal film are observed by an electron microscope (tank and TEM), and the film thickness of the metal film is dense and uniform, and the thickness of the film is more than U lGGnm. 4 capture, hinder $ to its full performance as a seed layer of Houbushe Electric Mine. Furthermore, the nickel layer of the glass substrate, in the copper electric mine bath, the current density of 2 5 A / dm2, A copper wiring layer having a copper film thickness and m is formed. The obtained copper wiring is formed into a glass substrate and heated in a nitrogen atmosphere to carry out the coating of the polyimide-coated precursor resin in the same manner for 5 minutes. Amination to form an ymine resin layer. Thereafter, the copper wiring is formed into a glass substrate and cooled to a normal temperature in a nitrogen atmosphere. The copper wiring forms a glass substrate, and the polyimide layer has a superior adhesion to the nickel layer. Through such a polyimide resin layer The nickel layer is used to firmly fix the copper wiring layer on the glass substrate. Further, the nickel layer and the copper wiring layer formed by using the same are free from defects and have excellent conduction performance. [Example 12] Test piece of 旭-100) manufactured by Asahi Glass Co., Ltd. 12. 5cmxl2. 5cm (thick Q. 7πιπι) was treated with 50 C of 5 Ν nitrogen oxide aqueous solution for 5 minutes. Secondly, the glass substrate of the test piece was washed with pure water. After drying, it was immersed in a 1% by weight aqueous solution of 7-APS. The glass substrate was taken out from the aqueous solution of 7-APS, and then dried and heated at 150 ° C for 5 minutes. The above-mentioned polyimide precursor varnish A was uniformly coated on the glass substrate, and dried at 130 ° C for 30 minutes. The thickness of the coating film formed by coating and drying was 2 #m. 97134815 60 200920873 Next, the above-mentioned Wei-imine precursor resin is used in the above-mentioned metal compound solution D in X 25 C / Å / Å for 1 minute to impregnate metal ions in the polyimide precursor resin. Thereafter, the polyimine precursor resin coating film was pulled from the metal compound solution and washed with water and dried. The above-mentioned metal ion imide precursor resin coating film is impregnated with 3 (rc / again: wet hydrogenation treatment in a lG mM hydrogenation aqueous solution for a minute to form a metal on the surface of the sap Thin film. Using electron microscope Na and TEM) to observe the surface and profile of the thin metal, it is true that the metal thin ship is dense and uniform and has a film thickness of more than 100 nm. Further, this metal ruthenium film was firmly adhered to the polyimide film of the polyimide precursor, and it was confirmed that it had sufficient properties as a seed layer for electroplating in the subsequent step. Further, the recording layer of the glass substrate was subjected to electric ore formation at a current density of 25 A/dm 2 in a copper coin bath to form a copper wiring layer having a copper film thickness of 2 G Am. The obtained copper wiring was formed into a glass substrate and heated to 3 G in a nitrogen atmosphere (TC), and the polyimine precursor resin constituting the coating film was subjected to hydrazine imidization to form a polyfluorene at a time of Q and 1 minute. The imide resin layer is formed, and then the copper wiring is formed into a glass substrate and cooled to a normal temperature in a nitrogen atmosphere. After the copper wire is laminated on the ore layer of the glass substrate, the dry film photoresist is laminated, and then exposed to ultraviolet light through the mask. Developing, forming a photoresist pattern with a wiring width/wiring interval (L/S)=20#m/30/zm丨 between 5〇_. The copper layer of the formed blank portion of the wiring is removed by rhyme, and then The polyimide resin is removed in the past to obtain a copper wiring to form a glass substrate. The copper wiring forms a glass substrate. The polyamido tree 97138815 61 200920873 The adhesion between the lipid layer and the nickel layer is excellent, and the copper wiring layer passes through the same. The polyimide layer and the recording layer are firmly fixed to the glass substrate. Further, the nickel layer and the copper wiring layer formed by using the same are free from defects and have excellent conduction performance. [Example 13] 〇g broken glass particles (M0RITEX company, Microspheres 424 (business Name) 'particle size distribution 5~50/zm) was dispersed in 50 N C 5N aqueous sodium hydroxide solution (500 mL) and stirred for 2 minutes. The glass fine particles were then filtered, washed with water, and dispersed in 1% by weight of T-APS aqueous solution ( After 500 mL), it was filtered, washed with water, and dried, and heated at 15 (TC for 5 minutes. The glass fine particles treated as described above were dispersed in 5 g of DMAc which made the polyimide varnish A diluted by 5 times by volume. In 10 ml of the solution, ethanol was added dropwise with stirring. After stirring for a while, the dispersion was filtered, washed with ethanol, dried, and heated at 13 μc for 1 minute to obtain glass fine particles M1 coated with the polyimide pigment precursor resin. Next, the above-mentioned polyimine-based resin-coated glass fine particles are dispersed in the metal compound solution D to be stirred at 25X for 1 minute. Thereafter, the dispersion is filtered, washed with water, and dried to obtain a coated impregnation. The glass microparticles of the polyimide ion-precursor resin having Ni ions are impregnated with the glass particles of the polyimidazolium precursor resin coated with the above-mentioned Ni ions, and dispersed in an aqueous solution of sodium borohydride of UhnM at a concentration of 3 Torr. 1 point Thereafter, the dispersion was dried, washed with water, and dried to obtain fine particles having a metal film of Mi. The microparticles having a metal thin film were observed by an optical microscope to confirm that they had a metallic luster. Further, electrons were observed by an electron microscope (SEM). Thin film particles 97138815 62 200920873 Subsurface, it was confirmed that the metal thin film was dense and continuous. [Example 14] As in Example 13, glass fine particles M2 coated with a polyimide pigment precursor resin were formed. Dispersion was carried out in a metal compound solution. In E, the mixture was stirred for 10 minutes at 25 ° C. Thereafter, the dispersion was filtered, washed with water, and dried to obtain glass fine particles coated with a polyimide ion impregnated resin impregnated with Ni ions. The above-mentioned Ni ions were impregnated with the glass microparticles coated with the polyamidene precursor resin, and dispersed in a 10 mM aqueous solution of sodium borohydride and stirred at 30 ° C for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles having a Ni metal thin film. The fine particles having a metal thin film were observed with an optical microscope to confirm that they had a metallic luster. [Example 15] As in Example 13, glass fine particles M3 coated with a polyimide pigment precursor resin were formed. This was dispersed in the metal compound solution F, and spoiled at 25 ° C for 1 minute. Thereafter, the dispersion was transferred, washed with water, and dried to obtain glass fine particles coated with a polyimide ion impregnated resin impregnated with Ni ions. The Ni ions were impregnated with the polyimide particles coated with the polyamidene precursor resin, dispersed in a 10 mM aqueous solution of sodium borohydride, and stirred at 3 (TC for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain Ni Microparticles of a metal thin film. Microparticles having a metal thin film were observed with an optical microscope, and it was confirmed that it had a metallic luster. [Example 16] 97134815 63 200920873 As in Example 13, glass microparticles M4 coated with a polyimide pigment precursor resin were formed. This was dispersed in the metal compound solution G, and stirred at 25 ° C for 10 minutes. - Thereafter, the dispersion was filtered, washed with water, and dried to obtain glass fine particles coated with a polyimide ion impregnated precursor resin impregnated with Ni ions. The Ni ions were impregnated with the polyimide particles coated with the polyamidene precursor resin, dispersed in a 10 mM aqueous solution of sodium borohydride, and stirred at 30 ° C for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain Fine particles of the Ni metal film f. The fine particles having the metal thin film were observed with an optical microscope, and it was confirmed that it had metallic luster. [Example 17] The glass fine particles M5 coated with the polyimine precursor resin were formed as in Example 13. This was dispersed in the metal compound solution I at 25. (: stirring for 10 minutes. Thereafter, the dispersion was filtered and washed with water, Drying, glass microparticles coated with a polyimide ion impregnated precursor resin impregnated with Cu ions are obtained. (j The above-mentioned Cu ions are impregnated with the polyimide particles coated with the polyamidene precursor resin, and dispersed in a 10 mM aqueous solution of sodium hydride hydride. The mixture was mixed with 3 (TC for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles having a Cu metal thin film. The fine particles having a metal thin film were observed by an optical microscope, and it was confirmed that the metal fineness was observed. [Example 18 The glass fine particles M6 coated with the polyimide precursor resin were formed as in Example 13 and dispersed in the metal compound solution j, and stirred at 25 ° C for 10 minutes. 97134815 64 200920873 Thereafter, the dispersion was filtered and It is washed with water and dried to obtain glass fine particles coated with a polyimine precursor resin impregnated with Cu ions. - The above-mentioned Cu ions are impregnated with a polyimide resin. The glass fine particles were dispersed in a 10 mM aqueous solution of sodium borohydride and stirred at 30 ° C for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles having a Cu metal film. The fine particles of ruthenium were confirmed to have a metallic luster. f [Example 19] Glass fine particles M7 coated with a polyimide pigment precursor resin were formed as in Example 13. This was dispersed in a metal compound solution L at 25. (: stirring for 10 minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain glass fine particles coated with a polyimine precursor precursor resin impregnated with Ag ions. The above Ag ions were impregnated with the polyimide particles coated with the polyamidene precursor resin, dispersed in a 10 mM aqueous solution of sodium borohydride, and stirred at 30 ° C for 1 minute. Thereafter, (_./, the dispersion was filtered, washed with water, and dried to obtain fine particles having a metal film of Ag. The fine particles having a metal thin film were observed with an optical microscope, and it was confirmed that the metal particles had a metallic luster. [Example 20] The glass fine particles M8 coated with the polyimine precursor resin were formed, and dispersed in a metal compound solution crucible 'stirred at 25 ° C for 10 minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain a coating. Glass microparticles impregnated with a poly(imine) precursor resin of Ag ions. 97134815 65 200920873 The above Ag ions are impregnated with a polyimide film coated with a polyamidene precursor resin, dispersed in a 10 mM aqueous solution of sodium borohydride and at a temperature of 3 〇. c. The mixture was stirred for 1 minute. Thereafter, the dispersion was dried, washed with water, and dried to obtain fine particles having a metal film of Ag. The fine particles having a metal thin film were observed with an optical microscope, and it was confirmed that it had metallic luster. [Example 21] In Example 13, a glass fine particle M9 coated with a polyimine precursor resin was formed, which was dispersed in a metal compound solution N and stirred at 25 ° C. After that, the dispersion was filtered, washed with water, and dried to obtain glass fine particles coated with a polyimine precursor precursor resin impregnated with Ag ions. The Ag ion was impregnated with a polyimide resin precursor resin. The glass fine particles were dispersed in a 10 mM aqueous solution of sodium borohydride and stirred for 3 minutes at 3 Torr. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles of a metal film of Ag. The film having a metal film was observed using an optical microscope. The fine particles were confirmed to have a metallic luster. [Comparative Example 4] Glass fine particles coated with a polyimide pigment precursor resin were formed as in Example 13. This was dispersed in a 100 mM aqueous solution of nickel acetate, and stirred at 25 ° C for 10 minutes. Thereafter, the dispersion is transferred, washed with water, and dried to obtain glass fine particles coated with a polyimide ion impregnated precursor resin impregnated with Ni ions. The Ni ions are impregnated with the glass fine particles coated with the polyimide polyimide precursor resin. Disperse in 10 mM hydrogenated shed aqueous solution and mix it for 3 minutes with 3 Torr. Thereafter, 97134815 66 200920873 The dispersion was filtered, washed with water and dried. Micro-black particles were obtained. Although observed by an optical microscope, no metal light was observed on the surface of the obtained fine particles. - [Comparative Example 5] As in Example 13, a glass coated with a polyimide pigment precursor resin was formed. The microparticles are dispersed in a metal compound solution crucible at 25° (:: 10 minutes of mixing. Thereafter, the dispersion is filtered, washed with water, and dried to obtain a coated impregnated ('Ni ion-based polyimine) The glass fine particles of the resin impregnated with the above-mentioned Ni ions are dispersed in a 10 mM aqueous solution of sodium borohydride and stirred at 3 (TC for 1 minute. Thereafter, the dispersion is filtered, Washed and dried to get white particles. At the time of the reduction treatment, there was no metal reduction on the surface of the fine particles, and even when observed by an optical microscope, the presence of the metal thin film was not confirmed on the surface of the obtained fine particles. [Comparative Example 6] C. As in Example 13, glass fine particles coated with a polyimide pigment precursor resin were formed. This was dispersed in a metal compound solution K and mixed at 25 ° C for 10 minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain glass fine particles coated with a polyimide ion impregnated resin impregnated with Cu ions. The Cu ions were impregnated with the polyimide particles coated with the polyamidene precursor resin, dispersed in a 10 mM aqueous solution of sodium borohydride, and stirred for 3 minutes at 3 (rc). Thereafter, the dispersion was filtered, washed with water, and dried to obtain a white color. In the case of the reduction treatment, there was no metal reduction on the surface of the fine particles, and even if observed by an optical microscope at 97138815 67 200920873, the presence of the metal thin film was not confirmed on the surface of the obtained fine particles. The above Examples 13 to 21 and Comparative Example 4 were The results of the integration of 6 are shown in Table 2.

I 97134815 68 200920873 (Table 2) Metal Compound Solution Cap Metal Standard Electrode Potential Nitrogen Compound Equilibrium Constant pH Film State Example 13 Ni -0. 228 Ammonia 2. 36 10. 35 Metallic Luster • Compact Example 14 Ni -0.228 Diethanolamine 3.31 9.82 Metallic luster Example 15 Ni -0. 228 Ethanolamine 2. 98 10.52 Metallic luster Example 16 Ni -0.228 Diethyl lunaran 2. 78 11.30 Metal luster Example 17 Cu 0.337 ammonia 4.27 10.25 Metal luster example 18 Cu 0. 337 Diethanolamine 4.75 9.75 Metallic gloss Example 19 Ag 0.7991 Ammonia 3.315 10.02 Metallic gloss Example 20 Ag 0. 7991 Diethanolamine 3.48 9.35 Metallic gloss Example 21 Ag 0.7991 Ethylenediamine 4. 70 10.22 Metallic gloss Comparative Example 4 Ni -0. 228 — — 7. 22 Matte ratio car exchange Example 5 Ni -0.228 Ethylenediamine 7.35 10.89 No formation of Comparative Example 6 Cu 0.337 Ethylenediamine 10.54 10. 68 Not formed ί. 97134815 69 200920873 [Examples 22] Disperse 10 g of glass fine particles (Molecular 424 (trade name) manufactured by M0RITEX Co., Ltd., particle size distribution 5 to 50 #m) in 5 (TC 5 N sodium hydroxide aqueous solution (500 mL) and The mixture was mixed for 2 minutes, and then the glass fine particles were filtered, washed with water, and dispersed in a 1% by weight aqueous solution of T-APS (500 mL), followed by filtration, washing with water, and drying, and heating at 150 ° C for 5 minutes. 5 g of microparticles were dispersed in a DMAc solution ΙΟιηΐ which was diluted with 5-fold by volume of the polyimide varnish A, and 100 ml of ethanol was added dropwise with stirring. After stirring for 1 minute, the dispersion was filtered. After washing, it is dried and heated at 130 ° C for 10 minutes to obtain glass fine particles coated with a polyimide pigment precursor resin. Next, the above-mentioned polyimide particles coated with the polyimide resin are dispersed in the metal compound solution D. The mixture was stirred at 25 t for 10 minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain glass fine particles coated with a polyimide ion impregnated precursor resin impregnated with Ni ions. The above Ni ion was impregnated with a polyimine precursor resin. The coated glass fine particles were dispersed in a 10 mM aqueous solution of sodium borohydride and stirred at 3 ° C for 1 minute. Thereafter, the dispersion was filtered and acid-treated with 1% by weight of an aqueous solution of oxalic acid. It was washed with water and dried to obtain fine particles having a Ni film. The fine particles of the above-mentioned Ni film were subjected to argonization at 30 (TC) for 5 minutes in a nitrogen atmosphere to obtain Ni-coated polyimide microparticles. On the surface of the above-mentioned Ni-coated polyimide microparticles, electroplating was used. The device (Shangsho 97138815 70 200920873 Industrial Co., Ltd., Flow-Through Platers RP-1 (trade name)) was electroplated at a current density of 1 A/dm 2 in a plating bath to form a solder (weight ratio:

Pb/Sn=60/40) plating thickness of 1 #m. [Example 23] As in Example 22, fine particles having a Ni film were obtained, which were imidized to obtain Ni-coated polyimine fine particles M11. This was dispersed in an electroless nickel bath (manufactured by Okuno Pharmaceutical Co., Ltd., TOP NIC0R0N T0M-S (trade name), 5 times diluted) (1000 mL), and mixed at 80 ° C for 5 minutes. Thereafter, the dispersion was passed through, washed with pure water, and dried to obtain Ni film fine particles M11. The above-mentioned Ni film fine particles M11' (10 §) were dispersed in a substitution gold plating solution (Melplate AU-601 (trade name) manufactured by Meltex) (1 〇〇〇 mL) to obtain 75. Stir for 5 minutes. Thereafter, the dispersion was filtered, washed with pure water, and dried to obtain metal film-coated polyimine fine particles. [Example 24] U A solution of 2 mml of 〇1 (436 mg) of pMDA dissolved in 25 ml of acetone and a solution of 2 mm 〇i (4 〇〇 mg) of 〇dA dissolved in 25 ml of acetone were respectively heated to 4 〇. C. This solution was mixed and irradiated with ultrasonic waves (ultrasonic washing machine, frequency 42 KHz) at 4 (rc, 1 minute) to form a suspension-like acetone solution in which poly-proline fine particles were precipitated in the solution. The mixture was washed with acetone to obtain 785 mg of polyacrylic acid microparticles M12. The obtained polyamic acid microparticles were spherical microparticles of 3 〇〇 to 6 〇〇 nm.

Next, the above polyamic acid microparticles M12 were dispersed in a metal compound solution D 97134815 71 200920873' and stirred at 25 C for 1 minute. Thereafter, the dispersion was dried, washed with water, and dried to obtain fine particles of lysine impregnated with Ni ions. The polyaminic acid microparticles impregnated with Ni ions were dispersed in an aqueous solution of sodium borohydride of i mM and were at 30. (: stirring for a few minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles having a Ni metal film. The fine particles were observed by a field emission scanning electron microscope (FE-SEM) at a magnification of 50,000 times. The result of the "evaluation of the deviation of the metal film" was confirmed to be non-deviation. The term "no deviation" as used herein means that when 20 fine particles are observed, all of the 20 fine particles form a continuous metal thin film. In the evaluation of the deviation of the film, the term "small variation in the metal film" means that there are 1 or 2 metal film discontinuous in the 20 fine particles, and the "large deviation of the metal film" means that the metal film is 20 pieces. There were three or more discontinuous ones. [Example 25] As in Example 24, polyamic acid microparticles M13 were formed. Disperse it in the metal compound solution E' at 251: followed by 1 G minutes. Thereafter, the dispersion was filtered. Washing and drying to obtain polyamic acid microparticles impregnated with Ni ions. Dispersing the above-mentioned polyaminic acid microparticles impregnated with Mi ions in an aqueous solution of sodium boron nitride After that, the dispersion was dried, washed with water, and dried to obtain fine particles having a Ni metal thin film. The fine particles were evaluated by field effect correction (electron microscopy (FE_SEM)), and the deviation of the metal thin film was evaluated. 97134815 72 200920873 [Example 26] Poly-proline fine particle M14 was formed as in Example 24. This was dispersed in the metal compound solution F, and spoiled at 25 t for 10 minutes. Thereafter, the dispersion was passed.遽, Washing, and drying' to obtain micro-islanded acid microparticles impregnated with Ni ions. The above-mentioned poly-proline microparticles impregnated with Ni ions are dispersed in a hydrogenation-removed water test of ΙΟπιΜ and scrambled at 3 ° C for 1 minute. Then, the dispersion was filtered, washed with water, and dried to obtain fine particles having a Ni metal thin film. The fine particles were observed by an electron microscope (FE-), and the deviation of the metal thin film was evaluated. [Example 27] As in Example 24, polyamic acid microparticles M15 were formed. Disperse it in metallization mouth cold liquid G, and stir it for 25 minutes at 25 Torr. Thereafter, the dispersion was passed. , washing with water, drying 'to obtain micronized phosphatic acid microparticles impregnated with Ni ions. The polyacrylic acid microparticles impregnated with Ni ions are dispersed in a fine hydrogenated G aqueous solution and stirred for 3 minutes at 3 Gt. Thereafter, The dispersion was filtered and washed with water to obtain fine particles having a Ni metal thin film. The fine particles were observed using a field emission-emission scanning electron microscope (FE_SEM), and the deviation of the metal thin film was evaluated. As a result, it was confirmed that the deviation was small. [Example 28] As in the case of the actual example 24' formation of polyamic acid microparticles, it was dispersed in the metal compound solution 1, and stirred for 10 minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain a concentration of impregnated with Cu ions. Amine _ particles. 97134815 73 200920873 The poly-prolyl microparticles impregnated with CU ions were dispersed in a 1 mM hydrogenated halogen water solution for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles having a Cu metal thin film. On the other hand, the fine particles were observed by a field emission type (four) sub-microscope (FE-SEM), and the deviation of the metal film was evaluated. As a result, it was confirmed that the deviation was small. [Example 29] As in Example 24, polyamic acid microparticles M17 were formed. This was dispersed in a metal ruthenium compound solution J, and stirred at 25 t for 1 Torr. Thereafter, the dispersion is filtered, washed with water, and contains 7 poly-proline microparticles having Qj ions. The 3 π poly-proline microparticles having Cu ions are dispersed in a 1 mM hydrogenated stone solution. The towel is 3 generations and wins 1 minute. Thereafter, the dispersion was dried and washed with water to obtain fine particles having a Cu metal film. The fine particles were observed by a blasting electron microscope using a sputum, and the deviation of the metal film was evaluated. As a result, it was confirmed that the deviation was small. Ο [Example 30] As in Example 24, polyamic acid microparticles M18 were formed. Disperse it in the metallization / Fen liquid L ' at 25. (: Mixing for 1 minute. Thereafter, the dispersion is filtered, washed with water, and dried to obtain fine particles of polyaminic acid impregnated with Ag ions. The poly-acid microparticles impregnated with Ag ions are dispersed in the nitriding of Li The aqueous solution of sodium borohydride was reddish 3 (rc·丨 min. Thereafter, the dispersion was filtered, washed with water and dried) to obtain fine particles having an Ag metal ruthenium film. The microparticles were observed using a field emission bounce electron microscope (FE_SEM). Evaluation of the deviation of the film of the thin metal 97138815 74 200920873, and it was confirmed that the deviation was small. [Example 31] Polyuric acid microparticles M19 were formed as in Example 24. This was dispersed in a metal compound solution crucible and stirred at 25 ° C. After 10 minutes, the dispersion was filtered, washed with water, and dried to obtain poly-proline microparticles impregnated with Ag ions. The poly-proline microparticles impregnated with Ag ions were dispersed in a hydrogenated aqueous solution of 1 〇 之The mixture was filtered for 3 days for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles having a metal film of Ag. The microparticles were observed using a field emission (IV) electron microscope (FE-SEM). When the deviation of the metal thin film was evaluated, it was confirmed that the deviation was small. [Example 32] Polyuric acid microparticles M20 were formed as in Example 24. This was dispersed in the metal compound solution N, and 25 c was stirred for 10 minutes. After that, the dispersion is filtered, washed with water and dried, and the phase is impregnated with Ag ions. The 3 x polyphosphonic acid microparticles with Ag ions are dispersed in a 10 mM hydrogenation aqueous solution ^ 3_mix 1 reading. Thereafter, The dispersion was subjected to hydrazine, water washing, and drying to obtain fine particles of Ag metal film. The microparticles were observed by an electron microscope (FE-SEM) to evaluate the deviation of the metal film. As a result, it was confirmed that [Comparative Example 7] was as in the example W w δ Μ鉾, city hetero-acid fine particles. Disperse it in 100 mM citric acid water, and stir for 10 minutes. Thereafter, it was dispersed. Liquid filtration, 97134815 75 200920873 Washed and dried to obtain poly-proline microparticles impregnated with Ni ions. The poly-proline microparticles impregnated with Ni ions were dispersed in a 1 mM hydrogenation aqueous solution and 30 〇. C is stirred for 1 minute. The dispersion was filtered, washed with water, and dried to obtain fine black particles. When observed by an electron microscope (FE_SEM), it was confirmed that the metal fine particles were distributed on the surface of the fine particles, and the metal layer was discontinuous. [Comparative Example 8] 24, forming poly-proline microparticles. Dispersing it in a metal compound solution ' 'mixed with 25 (10) for 1Q minutes. Thereafter, the dispersion is filtered, washed with water, and dried to obtain a poly-proline microparticle impregnated with ions. The polyaminic acid microparticles impregnated with Ni ions were dispersed in 1 mM hydrogenated aqueous solution 3G. (10) Mix for a minute. Thereafter, the dispersion was filtered, washed with water to give white fine particles. At the time of the reduction treatment, the fine particle dispersion did not change color. Even if it was observed by electron inspection (10), the presence of the metal thin film was not confirmed on the surface of the obtained fine particles. [Comparative Example 9] As in Example 24, polyamic acid microparticles were formed. This was dispersed in a metal compound solution K towel to stir for 1 G minutes. Thereafter, the dispersion was filtered, washed with water, and dried to obtain fine particles of polyaminic acid impregnated with Cu ions. The polyamic acid microparticles impregnated with CU ions were dispersed in a 1 mM sodium borohydride aqueous solution and stirred at 30 ° C for 1 minute. Thereafter, the dispersion was filtered, washed with water, and dried to obtain white fine particles. At the time of reduction treatment, fine particles were dispersed. 97134815 76 200920873 The liquid was not discolored, and even when observed by an electron microscope (FE-SEM), the presence of a metal thin film was not confirmed on the surface of the obtained fine particles. The results of the above Examples 24 to 32 and Comparative Examples 7 to 9 are shown in Table 3. (Table 3) Evaluation of metal compound solution Metal standard electrode potential Nitrogen compound equilibrium constant pH film discontinuity (in / 20) Example 24 Ni -0. 228 Ammonia 2. 36 10. 35 0 Example 25 Ni - 0. 228 Diethanolamine 3. 31 9. 82 0 Example 26 Ni -0. 228 Ethanolamine 2. 98 10. 52 0 Example 27 Ni -0.228 Diethylamine 2. 78 11. 30 1 Example 28 Cu 0 337 Ammonia 4. 27 10. 25 1 Example 29 Cu 0.337 Diethanolamine 4. 75 9. 75 2 Example 30 Ag 0. 7991 Ammonia 3. 315 10. 02 0 Example 31 Ag 0.7991 Diethanolamine 3.48 9. 35 0 Example 32 Ag 0. 7991 Ethylenediamine 4.70 10.22 2 Comparative Example 7 Ni -0. 228 — — 7. 22 20 Comparative Example 8 Ni -0.228 Ethylenediamine 7. 35 10.89 20 Comparative Example 9 Cu 0. 337 B Diamine 10.54 10.68 20

j 97134815 77 200920873 [Example 33] A solution of 2 mmol (436 mg) of PMDA dissolved in 25 ml of acetone was separately heated with a solution of 2 mm 〇 1 (4 〇〇 mg) of 〇DA in 25 ml of acetone. To °c. This solution was mixed and irradiated with ultrasonic waves (ultrasonic washing machine, frequency 42 KHz) at 4 (rc, 1 minute) to form an acetone solution in which a suspension of poly-proline fine particles was precipitated in the solution. And _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The mixture was stirred at 25 ° C for 10 minutes. The particles were impregnated with ionized polyamide microparticles, dispersed in a 10 mM aqueous solution of sodium borohydride and stirred at 3 Torr for 1 minute. Thereafter, the dispersion was filtered to The aqueous solution of oxalic acid in an amount of 1% by weight was subjected to an acid treatment, and then washed with water and dried to obtain fine particles having a Ni film. The fine particles having the above-mentioned film were placed in a nitrogen atmosphere at 3 Torr. (:: heating was carried out for 5 minutes, and 醯 was applied. The imidization of the film of the polyimine microparticles M21 is carried out on the surface of the above-mentioned Ni-coated polyimide microparticles using a plating apparatus (Flow-Through Platers RP-1 (trade name), manufactured by Uemura Kogyo Co., Ltd.). 1A in the plating bath The current density of /dm2 was electroplated to form a weld layer having a film thickness of 1/zm (weight ratio: Pb/Sn=60/40). [Example 34] As in Example 33, fine particles having a Ni film were obtained and carried out. The ruthenium is imidized to obtain Ni-coated polyimine fine particles M22, which is dispersed in electroless nickel plating 97138815 78 200920873 liquid (manufactured by Okuno Pharmaceutical Co., Ltd., TOP C0R0N ΤΟΜ-SC trade name), 5 times dilution) (1000 mL) 'The mixture was stirred at 80 ° C for 5 minutes. Thereafter, the dispersion was filtered, washed with pure water, and dried to obtain Ni film fine particles M22. The Ni film fine particles M22' (10 g) were dispersed in a substitution gold plating solution (Meltex system) Melplate AU-601C trade name), 1 〇 dilution) (l 〇〇〇 mL) in ' stirring at 75 ° C for 5 minutes. Thereafter, the dispersion was filtered, washed with pure water, and dried to obtain metal film-coated polyimine fine particles. Further, the present invention is not limited to the above embodiments, and various modifications can be made. For example, in the fourth embodiment described above, the ruthenium imidization step may be carried out after the electroplating step, but the ruthenium imidization step may be carried out before the electroplating step. Further, in the above-described first to fourth embodiments, after the impregnation step, a water washing step (washing step) performed by pure water or ion-exchanged water or the like may be provided. Further, in the third embodiment, in the coating film forming step, the coating liquid is applied to the insulating substrate in a predetermined pattern by using a dispenser or a droplet discharge device having a droplet discharge head. On top, a patterned coating film is formed. In the autumn, in the form of a coating film, the coating liquid (4) can be cut onto the entire surface of the coating to form a coating film (the "full coating" of the stomach). After the plating, a correction step and a chemical etching step are set. The conductor layer is processed into a predetermined pattern. (Industrial Applicability) The present invention can be suitably used for, for example, in the manufacture of a circuit board represented by a printed wiring board, or in the manufacture of conductive particles; The purpose of the metal film. Further, the present invention can be widely used for forming a conductor layer which is excellent in adhesion to a polyimide resin and has few defects, in addition to a circuit board or the like in the case of 97134815 79 200920873. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing the configuration of a circuit board to which a material for forming a (4) layer is formed. Fig. 2 is a cross-sectional view showing an enlarged main portion of the circuit board shown in Fig. 2; 3 is a flow chart showing the procedure of forming a conductor layer according to the first embodiment of the present invention. FIG. 4 is a view for explaining a step of forming a coating film in the method for forming a conductor layer according to the embodiment of the present invention. Fig. 5 is an explanatory view for explaining a state of a coating film after a coating film forming step, Fig. 6 is an explanatory view for explaining a state of a coating film after the impregnation step, and Fig. 7 is a view for explaining formation of a metal film. Explanation of the state of the patterned conductor layer after the step. L Head 8 is an explanatory diagram of the state of the patterned conductor layer after the lion face step. Fig. 9 is a view for explaining the state of the patterned conductor layer after the brewing imidization step Fig. 10 is a flow chart showing an outline of a procedure for forming a conductor layer according to a second embodiment of the present invention. Fig. 11 is a flow chart showing an outline of a procedure for forming a conductor layer according to a third embodiment of the present invention. Fig. 12A is an explanatory view for explaining a step of forming a coating of a conductive layer in a method of forming a conductor layer according to a third embodiment of the present invention. Fig. 12B is a view showing a shape of a conductor layer according to a third embodiment of the present invention. Fig. 13 is a cross-sectional view showing the internal structure of conductive fine particles applied to a method of forming a conductor layer according to an embodiment of the present invention. Fig. 14 is a view showing a conductor according to a fourth embodiment of the present invention. Fig. 15 is an explanatory view for explaining a state of the spherical insulating base material after the step of forming the resin film. Fig. 16 is a view for explaining the state of the spherical insulating base material after the impregnation step. Fig. 17 is an explanatory view for explaining a state of a spherical insulating base material after a metal film forming step. Fig. 18 is a view showing a conductive fine particle of another example of application of the green layer of the present invention. Cross-section of the structure. [Main component symbol description] I Circuit board 3 Insulation substrate 5 Patterned conductor layer 7 Polyimide resin layer 9 Metal film II Plating layer 97138815 200920873 20 Coating liquid 30 Dispenser 40 Coating film 41 Impregnated layer 50 Droplet discharge device 100 Conductive fine particles 103 Spherical insulating substrate 105 Polyimide resin layer 107 Conductor layer 109 Metal film 111 Electric Layer 120 layer 200 resin film 121 is impregnated with conductive fine particles 9713481582

Claims (1)

200920873 VII. Patent application scope: 1. The method for forming a kind of conductor layer is based on the surface of the polypyrene resin substrate or the polyimide resin film (4), which is characterized by the following steps: The impregnation step is a nitrogen-containing compound having an equilibrium constant of 6 or less by a metal compound containing a metal having a standard electrode potential in a range of -0.25 to +1 55, and a mismatch reaction with the gold ion. A solution of a metal compound having a pH in the range of 9 to Μ, which is subjected to the treatment of the first (four) polyanilin precursor tree belonging to the Wei-imine resin, and the ion impregnation of the above metal is impregnated to the above-mentioned polyfluorene The surface of the substrate or film formed by the resin; and the ruthenium/metal is immersed in the surface layer of the substrate or film which is opened by the above-mentioned polyimide resin precursor resin. The metal ions are subjected to a thorough treatment to form a metal film as the conductor layer.申》月专利|〗 〖The drum method of the conductor layer of the first item, wherein the above standard electrode potential is the metal of the iW, which is composed of Nl, Sn, b Cu ^^'^'(10)^ The method of forming a conductor layer, such as a grade or a grade 2 amine, is as described in the patent application. The above method for thin layer (10), wherein the V body layer is a patterned conductor layer. 5. The conductor layer cutting method of claim 1 (4), wherein 97134815 83 200920873 a polyimide film is formed on the surface of the spherical insulating substrate. 6. The method of forming a conductor layer according to the first aspect of the invention, wherein the poly-imine resin substrate is a spherical polyimide substrate. 7. A method of manufacturing a circuit board, comprising: a method of manufacturing a circuit board including an insulating base material and a conductor layer formed on the insulating base material, comprising the step of forming the conductor layer on the insulating base material; This step includes: a coating film forming step of applying a coating liquid containing a polyimide precursor resin (to the surface of the insulating substrate and drying to form a coating film; έ /文 step, The coating film is treated with a metal compound solution to impregnate metal ions in the δHeil bath into the surface layer of the coating film, and the metal film forming step is impregnated into the surface layer of the coating film. The metal ion is subjected to a reduction treatment to form a metal film as the conductor layer; and the metal compound solution contains a metal compound containing a metal having a standard electrode potential of _〇25 to +1.55, and an ion with the metal a nitrogen-containing compound having an equilibrium constant of 6 or less, and a solution having a pH in the range of 9 to 12. 8. A method for producing conductive fine particles, A method for producing a conductive fine particle comprising a spherical insulating substrate and a conductive layer covering the spherical insulating substrate, comprising the step of forming the conductive layer on a surface of the spherical insulating substrate, wherein the step comprises: In the film forming step, a coating liquid containing a polyimide precursor resin is applied onto the surface of the spherical insulating substrate, and dried to form a resin covering the spherical substrate 97112815 84 200920873 The film is impregnated by treating the resin film with a metal compound solution to impregnate the metal ions in the solution to the surface layer of the resin film; and the metal film forming step is performed by impregnating the surface of the resin film. The metal ion is subjected to a reduction treatment to form a metal film as the conductor layer; and the metal compound solution contains a metal compound containing a metal having a standard electrode potential of up to +1.55, and f' between the ion of the metal A nitrogen-containing compound having an equilibrium constant of 6 or less, and a solution having a pH in the range of 9 to 12. A method for producing conductive fine particles, which is a method for producing a conductive fine particle comprising a spherical-imine resin substrate and a conductor layer covering a 3 ichromeric polyimide resin substrate, and is characterized in that it is provided a step of forming the above-mentioned conductor layer on the surface of the spherical particles of the polyimine precursor resin which is imidized into the globular polyimide resin substrate, the step comprising: t containing the π step' The surface of the particle is treated by a metal ruthenium compound solution to impregnate the metal ions of the solution towel into the surface layer of the spherical particle; and the metal is immersed in the surface of the spherical particle The metal ion is also supplied to the county, and (4) is formed as a metal film of the upper body layer; the metal compound solution contains a metal compound containing a metal having a standard electrode potential of up to +1.55, and an ion with the metal The solution of the nitrogen-containing compound having an equilibrium constant of 6 or less is in the range of 9 97134815 85 200920873 to 12. 10. A composition for forming a conductor layer for impregnating metal ions into a polyimide resin layer for forming a conductor layer on a surface of a polyimide film or a polyimide film A metal substrate having a standard electrode potential of from -0.25 to +1.55, and a metal compound having a standard electrode potential of from -0.25 to +1.55, and a treatment in a substrate or a film formed of a precursor of a polyimine precursor resin The nitrogen-containing compound having an equilibrium constant of the mismatching reaction between the ions of the above metals is 6 or less, and is in the range of 9 to 12. C 97134815 86