CN104662198A

CN104662198A - Electrically conductive material and method for producing same

Info

Publication number: CN104662198A
Application number: CN201380049266.9A
Authority: CN
Inventors: 深泽宪正; 梶井智代; 佐野义之; 关根信博; 清冈隆一
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2012-09-20
Filing date: 2013-09-11
Publication date: 2015-05-27
Anticipated expiration: 2033-09-11
Also published as: JP5594449B2; TWI577556B; TW201420350A; CN104662198B; KR20150058097A; KR102027193B1; WO2014045972A1; JPWO2014045972A1

Abstract

Provided is a method for producing an electrically conductive material having an electrically conductive layer having a proper thickness without requiring the bonding with an adhesive agent and without requiring the use of a vacuum facility. The present invention is a method for producing an electrically conductive material, comprising the steps of: applying a dispersion, which contains 0.5 mass% or more of microparticles (2) of at least one metal selected from the group consisting of gold, silver, copper and platinum which are protected by a compound having a nitrogen atom, a sulfur atom, a phosphorus atom or an oxygen atom, on an insulating base (1) to form a non-electrically-conductive layer (3); and subjecting the base (1) having the non-electrically-conductive layer (3) formed thereon to electroless plating to form an electrically-conductive layer.

Description

Conductive material and manufacture method thereof

Technical field

The present invention relates to the manufacture method of the conductive material being used as use in printed circuit board laminated substrate aptly.In addition, the invention still further relates to the conductive material using this manufacture method to manufacture.

Background technology

Use in printed circuit board laminated substrate is the material of the structure that the material of low-k and the thin layer of electroconductibility are laminated.All the time, such as, flexible copper-clad plywood (FCCL) uses following method to manufacture: the method using the caking agent of epoxy resin to be engaged with Copper Foil by thermotolerance macromolecule membrane, on copper-clad surface coating resin solution and make the methods such as its drying.

In recent years, due to miniaturization, the high speed of electronics, requiring densification, the high performance of tellite, in order to tackle these requirements, requiring to develop to there is surface smoothing and the tellite of enough thin conductive layer (copper foil layer).

But, use the method for epoxide resin adhesive to there is the shortcoming that thermotolerance is low, insulating reliability is also poor.In addition, in the manufacture method of aforementioned use Copper Foil, manufacture while pull out the Copper Foil limit being rolled into web-like, therefore there is the difficulty in process, thus Copper Foil cannot be made enough thin, in addition, in order to improve the adaptation with macromolecule membrane, need the surface roughening of Copper Foil, thus fully cannot tackle the densification of printed circuit board (PCB), requirement that namely high performance suppresses the transmission loss under high frequency (GHz frequency band), high transmission speed (tens of Gbps) scope.

Therefore, for the requirement of the high performance of printed circuit board (PCB), such as disclose a kind of do not use joint by caking agent and on macromolecule membrane the Copper thin film substrate (such as with reference to patent documentation 1) of stacked copper lamina.In the manufacture method of this Copper thin film substrate, use sputtering method, the first layer copper film layer is set on thermotolerance insulating substrate surface, this first layer is formed the copper thick film layers utilizing and electroplate and obtain.

The Copper thin film substrate recorded in aforementioned patent literature 1 can make copper foil layer thinner, therefore the densification of printed circuit board (PCB), the requirement of high performance can be tackled, but it use the method for the sputtering needing vacuum apparatus, therefore have that operation is numerous and diverse and the problem such as cost is high, substrate sizes is limited in equipment.

Therefore, do not use the joint by caking agent just can to make the manufacturing process of the use in printed circuit board laminated substrate that conductive layer (copper foil layer) is enough thin as in manufacture without the need to vacuum apparatus, disclose following method: be filmed by coating metal particulate on the base material of insulativity and carry out heat-agglomerating and form the conductive layer of metal, this conductive layer carries out plating, obtains the method (such as with reference to patent documentation 2 ~ 3) of the conductive copper layers of foil of necessary thickness thus.

In aforementioned patent literature 2, disclose the manufacture method of the multilayer board comprising following operation: (1) by containing the mutual welding because of heat treated, primary particle size is that the dispersion of the metallic film precursor particles of below 200nm to be coated on insulated substrate and to carry out heat treated, formation metallic film form the operation of conductive layer thus; (2) on aforementioned metal film, carry out electrolytic coating and form the operation of metallic membrane.

In addition, a kind of use in printed circuit board substrate and manufacture method thereof is disclosed in aforementioned patent literature 3, the feature of described use in printed circuit board substrate is: on insulativity base material, have the 1st conductive layer and the 2nd conductive layer formed thereon, aforementioned 1st conductive layer is formed with the form of the coating layer comprising the electroconductibility ink of the metallic particles of 1-500nm, aforementioned 2nd conductive layer formed with the form of coating layer.

In aforesaid method, passing through on insulativity base material, form conductive metal layer and electroplate, thus the aspect not using vacuum apparatus can obtain the conductive film layer of suitable thickness is excellent, but in order to implement electrolytic coating, need to be pre-formed the conductive metal film with sufficient electroconductibility.Such as, in aforementioned patent literature 2, as the volumetric resistivity value for this purpose and required for the metallic film used, be recommended as 1 × 10 ^-4below Ω cm, be more preferably 1 × 10 ^-5below Ω cm.In order to form the conductive layer demonstrating this low-resistivity, must make to be coated on contained dispersion agent and the volatilization of other organism in the dispersion of the electroconductibility ink on insulativity base material, metallic membrane precursor particles by heating, decomposing and from coating layer removing, forming the state of fully welding between particle.

But, to the dispersion liquid of these small metallic particles and metallic film precursor granules be coated with and the film heat-agglomerating obtained and form conductive film when, be difficult to fully landfill void among particles, can form internal residual has more lacunose metallic film.In addition, although the particle shape in film changes because of welding and Grain growth, link between the particle of a part, film entirety usually can be observed the phenomenon that coating density reduces., there is following problem in its result: occur to show sufficient electroconductibility and cannot carry out plating situation, namely enable carry out time that plating also needs to grow very much or the non-conduction portion that occurs owing to producing local and cause poor plating, plating the problem such as ununiformity.In addition, like this, in the coating metallic film that density is low, space is many in local, there is its space part becomes destruction starting point and causes conductive layer from problems such as isolator base material strippings.

As the countermeasure of this problem, propose in aforementioned patent literature 3: fill the space in the first conductive layer that isolator base material is formed by utilizing Chemical metal plating, thus eliminate the destruction starting point that poor flow, minimizing can become the reason of stripping, but the space by heat-agglomerating in the conductive film of welding usually exists with the form in isolated space in film inside, liquid is impermeable, therefore, sometimes still exist with the form in space after electroless plating, sufficient solution can not be called.

In addition, as the catalyzer of electroless plating, usual use palladium, but when using expensive palladium as catalyst metal, not only the cost of electroless plating treatment process becomes large, and can there is following problem: when filling the space of the conductive layer formed because of heat-agglomerating by using the electroless plating of palladium catalyst, palladium becomes the state be irregularly preferentially absorbed in conductive layer, the removing of palladium can not be carried out fully in etching work procedure afterwards, the reason etc. causing circuit substrate characteristic to reduce can be become.

Therefore, as the electroless plating catalyzer of cheapness not using palladium, such as, provide a kind of silver salt that uses as the method (such as with reference to patent documentation 4) of catalyzer.The method is following method: adding in the aqueous solution containing silver salt and tensio-active agent relative to silver salt is the reductive agent of 2 ~ 4 times moles, forms the silver-colored water-sol, makes it contact with plated body, gives silver colloid and carries out electroless plating.But the method exists following shortcoming: need a large amount of reductive agents, production cost is high, and the stability of the silver-colored water-sol formed is low, easily produces aggregate and precipitate.In addition, in method disclosed in the document, as plated body, exemplified with the fiber composition such as paper, non-woven fabrics, glass, pottery and plastics, but in fact only used paper, cloth etc. " porous material " as plated body, give catalyzer in its vesicular structure utilizing catalyzer " to hang over " plated body, on the base material with level and smooth surface, when evenly giving catalyzer to whole of base material, be difficult to method disclosed in application of aforementioned patent documentation 4.

In addition, also describe and comprise silver salt 0.01 ~ 100mmol/L, anion surfactant 0.01 ~ 0.5wt.% and be the electroless plating catalyzer liquid (such as with reference to patent documentation 5) of reductive agent of 0.1 ~ 0.8 times mole relative to silver salt, this catalyzer liquid, relative to the catalyzer liquid that silver salt is 0.1 ~ 0.8 times mole, reduction dose ratio aforementioned patent literature 4 is few, has good stability.

In the method described in above-mentioned patent documentation 4,5, plated body is immersed in rare dispersion liquid of silver colloid, interaction mainly through the electrostatic on silver colloid and plated body surface makes silver colloid be attached to plated body surface, as electroless plating catalyzer and use, the adhesion amount of silver colloid controls by dipping time, but when being applied to the large-area base materials such as the insufficient and then use in printed circuit board laminated substrate of the catalyst concn be attached on plated body, need to carry out for a long time in large steeping vat, thus more difficult in practical application.In addition, for the method for such absorption naturally in a liquid, because silver colloid is low to the adsorptivity of plated body, therefore, in washing step after giving silver colloid catalyzer, electroless plating, catalyst substance (silver colloid) easily comes off from plated body, plating can occur and separate out the problems such as decomposition uneven, cause promoting plating bath because polluting plating liquid.Also refer to silver coating colloid on plated body in these documents and give the possibility of catalyzer, but there is following problem: for the silver colloid of disclosed such lower concentration, the silver colloid of q.s cannot be given on plated body by coating, uniform plating cannot be implemented on plated body, and, when disclosed silver colloid is concentrated, can assemble, cannot coating masking be carried out.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 9-136378 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2006-305914 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2010-272837 publication

Patent documentation 4: Japanese Laid-Open Patent Publication 64-068478 publication

Patent documentation 5: Japanese Unexamined Patent Publication 10-030188 publication

Summary of the invention

the problem that invention will solve

The present invention makes in view of the problem of above-mentioned prior art, and the problem that the present invention will solve is, provides the manufacture method with the conductive material of the conductive layer of suitable thickness not needing to engage, do not use vacuum apparatus by caking agent.More specifically, the object of the present invention is to provide the manufacture method of conductive material, described conductive material is by not needing to be coated on converting uneven conductive film to containing the layer of metal particle and need not worry that the characteristic caused by palladium catalyst reduces, the easier and method that reliability is high and utilize sufficient dhering strength laminated conductive layer on isolator base material on base material.And then, the present invention also aims to, provide and use that this manufacture method manufactures, that use in printed circuit board laminated substrate can be used as aptly conductive material.

for the scheme of dealing with problems

The present inventor etc. conduct in-depth research to solve above-mentioned problem; found that; obtained by coating method, comprise the catalytic activity being demonstrated excellent electroless plating by the dielectric layer of metal particle containing gold and silver, copper, platinum that specific compound is protected on various isolator base material; and play a role as the basis of the plating film causing strong adaptation, thus complete the present invention.

Namely, the manufacture method that the invention provides conductive material and the conductive material using this manufacture method and obtain, the feature of described manufacture method is, there is following operation: (1) is at the upper Coating dispersions (B) of insulativity base material (A), form the operation of non-conductive layer (C), the metal particle (b2) of more than a kind that be selected from the group that gold and silver, copper and platinum be made up of by the compound (b1) with nitrogen-atoms, sulphur atom, phosphorus atom or Sauerstoffatom protected of described dispersion liquid (B) containing certain content; (2) base material with non-conductive layer (C) obtained in (1) carries out electroless plating, forms the operation of conductive layer (D).

the effect of invention

According to the present invention, the high performance conductive material that can utilize in high-density installation field with low cost manufacture, tellite substrate, printed circuit board (PCB) and do not need vacuum apparatus, also do not use organic adhesive.

Accompanying drawing explanation

Fig. 1 is the schematic diagram in the cross section of the mode representing the base material being formed with non-conductive layer (C) on insulativity base material (A).

Fig. 2 is the schematic diagram in the cross section of the mode representing the base material being formed with non-conductive layer (C) on insulativity base material (A).

Fig. 3 is the schematic diagram representing the cross section being formed with a mode of the conductive material of conductive layer (D) on the base material of Fig. 1 by electroless plating.

Fig. 4 is the schematic diagram representing the cross section being formed with a mode of the conductive material of conductive layer (D) on the base material of Fig. 2 by electroless plating.

Fig. 5 represents the schematic diagram being formed with the cross section of a mode of the conductive material of metal conducting layer (E) on the conductive layer (D) of Fig. 3 by plating.

Fig. 6 represents the schematic diagram being formed with the cross section of a mode of the conductive material of metal conducting layer (E) on the conductive layer (D) of Fig. 4 by plating.

Fig. 7 is the electron micrograph in example 2 the Argent grain film formed on Kapton being sintered at 100 DEG C the film surface after 5 minutes.

Fig. 8 has carried out black white binarization to calculate surface-coated rate, in example 2 the Argent grain film formed on Kapton has been sintered at 100 DEG C the electron micrograph (electron micrograph of Fig. 7 is carried out black white binarization) on the film surface after 5 minutes.

Fig. 9 is the electron micrograph in embodiment 3 the Argent grain film formed on Kapton being sintered at 100 DEG C the film surface after 5 minutes.

Figure 10 has carried out black white binarization to calculate surface-coated rate, in embodiment 3 the Argent grain film formed on Kapton has been sintered at 100 DEG C the electron micrograph (electron micrograph of Fig. 9 is carried out black white binarization) on the film surface after 5 minutes.

Figure 11 is the electron micrograph in example 4 the Argent grain film formed on Kapton being sintered at 100 DEG C the film surface after 5 minutes.

Figure 12 has carried out black white binarization to calculate surface-coated rate, in example 4 the Argent grain film formed on Kapton has been sintered at 100 DEG C the electron micrograph (electron micrograph of Figure 11 is carried out black white binarization) on the film surface after 5 minutes.

Figure 13 is the electron micrograph Argent grain film formed on Kapton being sintered at 100 DEG C the film surface after 5 minutes in embodiment 5.

Figure 14 has carried out black white binarization to calculate surface-coated rate, the Argent grain film formed on Kapton has been sintered at 100 DEG C the electron micrograph (electron micrograph of Figure 13 is carried out black white binarization) on the film surface after 5 minutes in embodiment 5.

Figure 15 is the electron micrograph Kapton adsorbing Argent grain being sintered at 180 DEG C the film surface after 30 minutes in comparative example 1.

Figure 16 has carried out black white binarization to calculate surface-coated rate, the Kapton adsorbing Argent grain has been sintered at 180 DEG C the electron micrograph of the film surface after 30 minutes in comparative example 1.

Figure 17 is the electron micrograph Argent grain film formed on Kapton being sintered at 180 DEG C the film surface after 30 minutes in comparative example 6.

Figure 18 is the electron micrograph Argent grain film formed on Kapton being sintered at 180 DEG C the film cross section after 30 minutes in comparative example 6.

Figure 19 is the electron micrograph Argent grain film formed on Kapton being sintered at 210 DEG C the film surface after 5 minutes in embodiment 85.

Figure 20 has carried out black white binarization to calculate surface-coated rate, the Argent grain film formed on Kapton has been sintered at 210 DEG C the electron micrograph (electron micrograph of Figure 19 is carried out black white binarization) on the film surface after 5 minutes in embodiment 85.

Embodiment

The present invention is described in detail below.

< insulativity base material (A) >

As the insulativity base material (A) used in the present invention, such as can be suitable for using: the starting material such as the vibrin such as polyimide resin, polyethylene terephthalate, PEN, liquid crystalline polymers, polyesteramide resin, cyclic olefin polymer, paper phenol, Epoxide cellulose paper, epoxy glass, ABS resin, glass, pottery, it can tackle any form of flexible material, rigid material, rigidity flexible material.Thinner can the using as film of these insulativity base materials (A), and thicker can using as thin slice, plate.

In flexible substrate purposes, the film of aforementioned polyimide, vibrin can be used, as polyimide resin, such as can be suitable for using the film such as Kapton (Du Pont-Toray Co., Ltd.), UPILEX (the emerging product in space portion), Apical (Kaneka Corporation), Pomiran (waste river chemistry).In addition, as vibrin, the VECSTAR series (KURARAY CO., LTD.) using liquid crystalline polymers can be suitable for.In addition, these films can use, also can use with continuous thin film state with the state cutting into a certain size.

The insulativity base material (A) used in the invention described above can have the through hole connecting its surface and the back side.Through hole can utilize the known conventional methods such as boring, laser to be formed.

For the object improving insulativity base material (A) and non-conductive layer (C) and then the adaptation with the plating film obtained in operation afterwards, before the dispersion liquid (B) of the metal particle that the insulativity base material (A) used in the present invention can be stated after application, carry out surface treatment.As the surface treatment method of insulativity base material (A), the various method of suitable selection, such as, can be suitable for using the physical methods such as UV process, ozonize, corona treatment, Cement Composite Treated by Plasma.In addition, when insulativity base material (A) is for polyimide resin, the chemical process of the substrate surface with alkali aqueous solution process polyimide resin can also be used.When insulativity base material (A) is for vibrin, preferably in advance UV process, corona treatment or Cement Composite Treated by Plasma are carried out to the surface of vibrin.These surface treatment methods can carry out separately, also can carry out multiple method continuously.

Dispersion liquid (B) > of < metal particle

In order to form non-conductive layer of the present invention (C) and coating dispersion liquid (B) in the contained catalyzer of metal particle (b2) as electroless plating on aforementioned dielectric base material (A) work, it is the anisotropy composite particles etc. of the alloy of gold and silver, copper, the particle of platinum and these metals, core-shell particle, such as Jin-Yin core shell, gold-copper core shell, silver-copper core shell particle, these metallic particles.In the present invention, aforementioned metal particulate (b2) only can use one, also can mix multiple use.From the viewpoint of the easy degree of industrial acquisition, cost, as metal species, preferably use the particle of silver and copper.In addition, even if there is oxidation overlay film, sulfuration overlay film on the surface of metal particle (b2), as long as the degree worked as chemical plating catalyst is then also harmless.

As the shape of aforementioned metal particulate (b2), as long as can carry out being coated with on insulativity base material (A), stable dispersion liquid (B) can be obtained just be not particularly limited, can be suitable for selecting being used alone according to object the metal particle of the different shape such as spherical, lensing, polyhedral, tabular, bar-shaped, wire, or the multiple particulate be obtained by mixing.

For the size of aforementioned metal particulate (b2), utilize electron microscope to observe particle shape and observe shape be circle, polyhedral time, preferably its diameter is 1 ~ 200nm, from the viewpoint of dispersiveness, the stability of metal particle in dispersion liquid (B), more preferably use the metal particle of 2 ~ 100nm.And then, from the viewpoint of effectively forming finer and close and uniform conductive layer (D) by electroless plating, be particularly preferably the metal particle of 5 ~ 50nm.

When the observation image of the electron microscope of metal particle (b2) has lensing, bar-shaped, wire etc. relative to minor axis, long axisymmetric shape, preferably, its minor axis is 1 ~ 200nm, is more preferably 2 ~ 100nm, more preferably 5 ~ 50nm.The size distribution being dispersed in the metal particle (b2) in dispersion liquid (B) can be single dispersing, also can for having the mixture of the particle of the particle diameter of aforementioned preferred particle size range.

The dispersion liquid (B) used in the present invention is that aforementioned metal particulate (b2) disperses in various dispersion medium; aforementioned metal particulate (b2) needs to keep long dispersion stabilization and can not assemble in dispersion medium, merges, precipitates; therefore, the protective material of the surface organic compound of metal particle (b2) is protected.In addition; aforementioned metal particulate (b2) above forms non-conductive layer (C) by its dispersion liquid (B) being coated on aforementioned dielectric base material (A); it works as electroless plating catalyzer; but plating carries out in a liquid; therefore; need this non-conductive layer (C) can not peel off from base material in plating liquid, the protective material of preferred aforementioned metal particulate (b2) has the effect of the adaptation improving aforementioned dielectric base material (A) and non-conductive layer (C).

From the viewpoint; in the present invention; as the compound (b1) for the protection of metal particle (b2); the compound (b1) with nitrogen-atoms, sulphur atom, phosphorus atom or Sauerstoffatom must be used, can be suitable for according to the application target of the dispersion liquid of metal particle (b2) (B) selecting the metal particle disperseed, the kind of dispersion solvent used and the base material (A) etc. of coating metal particulate.These specific atoms can be included in separately in compound (b1), but from the viewpoint of effectively showing aforementioned function, preferably in 1 molecule, have two or more different atom.

Do containing such atom not of the same race in protectant compound (b1) to use, such as can with amino (-NH ₂), carboxyl (-COOH), hydroxyl (-OH), sulfydryl (-SH), phosphate (H ₂pO ₄-), quaternary ammonium group (-NRR ' R " ₄ ⁺) the form of the functional groups such as, quaternary phosphine base, cyano group (-CN), ether (-O-), thioether group (-S-), disulfide group (-S-S-) contains.These functional groups can contain separately in a part, it is multiple also can to have in a part; in addition; as protective material, when using independent compound (b1), also can use the multiple compound (b1) with such functional group simultaneously.

As aforesaid compound (b1), specifically, as low-molecular-weight compound, such as, can list: DMAE, 2-DEAE diethylaminoethanol, 2-dimethylamino Virahol, 3-diethylamino-1-propyl alcohol, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, 2-methyl amino ethanol, 4-dimethylamino-n-butyl alcohol, formic acid, acetic acid, propionic acid, butyric acid, isopropylformic acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tetradecanoic acid, oleic acid, linolic acid, linolenic acid, stearic acid, oxalic acid, tartrate, phthalic acid, methacrylic acid, citric acid, vinylformic acid, phenylformic acid, cholic acid, quadrol, propylamine, butylamine, Trimethylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, trioctylphosphine amine, dodecyl-dimethyl amine, butylethanolamine, bromination thiocholine, allyl sulfhydrate, spicy thioalcohol, decyl mercaptan, Dodecyl Mercaptan, Cys, sodium sulfosuccinate, Sodium dodecylbenzene sulfonate etc.

In addition, as the compound of high molecular, such as can be suitable for utilizing in molecule the polymer with one or more polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyoxyethylene glycol, polyethylene glycol-propylene glycol copolymers, polymine, PPI, polypyrrole, poly-(methyl) acrylate, the contour molecular cell of polystyrene, when there are these polymer unit multiple, these polymer unit Direct Bonding or the compound by amido linkage, ester bond, ether (-O-), thioether group (-S-) bonding can be used.And then a part for these high molecular ends can by amino (-NH ₂), the replacement such as carboxyl (-COOH), carboxylicesters (-COOR:R is selected from methyl, ethyl, propyl group), hydroxyl (-OH), sulfydryl (-SH), can be suitable for being used in high molecular end and have-OP (O) (OH) ₂the phosphate-based ,-SR that represents (R be carbon number 1 ~ 18 alkyl, substituent phenyl can be had on phenyl ring or have select the aralkyl oxy of the alkoxyl group of free hydroxyl, carbon number 1 ~ 18, carbon number 1 ~ 18, substituent phenoxy group can be had on phenyl ring, the alkyl of the carbon number 1 ~ 8 of more than 1 functional group in the group of the alkoxy carbonyl composition of carboxyl, the salt of carboxyl, 1 valency of carbon number 1 ~ 18 or the alkyl-carbonyl oxygen base of multivalence and 1 valency of carbon number 1 ~ 18 or multivalence.) compound of functional group that represents.These polymers can be used alone and also can multiple mixing use simultaneously.

Wherein, masking, the adaptation of the non-conductive layer (C) on the dispersion stabilization, insulativity base material (A) of dispersion liquid (B), as the number-average molecular weight of aforesaid compound (b1), the scope of preferred use 1000 ~ 50000, in addition, as its structure, can use especially aptly there is polymine block and polyoxyethylene glycol block compound (P1), (methyl) acrylic acid or the like polymkeric substance (P2) and comprise the organic compound (P3) of ad hoc structure of thioether group (thioether bond).

The aforementioned compound (P1) with polymine block and polyoxyethylene glycol block such as can by deriving the terminal hydroxyl of commercially available polyoxyethylene glycol as active group and making itself and commercially available polymine carry out chemical bonding and obtain, and can be used in number-average molecular weight especially is aptly that on amino in the polymine of 500 ~ 50000, bonding number-average molecular weight is the compound of the polyoxyethylene glycol of 500 ~ 5000.The compound (P1) used in the present invention has the ad hoc structure of polymine block and polyoxyethylene glycol block, also can import other structure further.

In addition, as aforementioned (methyl) acrylic polymers (P2) that can be suitable in the present invention using, can list: make to have (methyl) esters of acrylic acid macromonomer of polyglycol chain and have-OP (O) (OH) ₂(methyl) acrylic ester monomer of phosphate residue represented be polymerized and obtains (methyl) acrylic polymers (such as reference No. 4697356th, Japanese Patent) under the existence of chain-transfer agent with the functional group that-SR (R as hereinbefore) represents.

And then, as the aforementioned organic compound (P3) comprising the ad hoc structure of thioether group (thioether bond) that can be suitable in the present invention using, the Sulfide-containing Hindered organic compound (P3) (such as with reference to No. 4784847th, Japanese Patent) using following general formula (1) to represent can be suitable for.

X-(OCH ₂CHR ¹) _n-O-CH ₂-CH(OH)-CH ₂-S-Z (1)

(in formula (1), X is C ₁~ C ₈alkyl, R ¹for hydrogen atom or methyl, n is the integer of the repeat number of expression 2 ~ 100, R ¹each repeating unit be independently, can be the same or different, Z is C ₂~ C ₁₂alkyl, allyl group, aryl, aralkyl ,-R ²-OH ,-R ²-NHR ³, or-R ²-COR ⁴(wherein, R ²for C ₂~ C ₄alkylidene chain, R ³for hydrogen atom, C ₂~ C ₄acyl group, C ₂~ C ₄alkoxy carbonyl or C can be had on aromatic nucleus ₁~ C ₄alkyl or C ₁~ C ₈the substituent benzyloxycarbonyl of alkoxyl group, R ⁴for hydroxyl, C ₁~ C ₄alkyl or C ₁~ C ₈alkoxyl group.) group that represents.〕

The aforesaid compound (b1) used in the present invention can add when the manufacture of metal particle (b2), also can add after manufacture metal particle (b2).In addition, in dispersion liquid (B), as the solvent for dispersed metal particulate (b2), as long as metal particle (b2) can be made stably to disperse, make solvent good to the wettability of aforementioned dielectric base material (A) under metal particle (b2) dispersed state, above can form liquid film at aforementioned dielectric base material (A), be not particularly limited, all kinds of SOLVENTS can be used, any number of in the mixed solvent of water, water and water miscible organic solvent, water-free organic solvent.

As the aforementioned water miscible solvent that can mix with water, such as can list: the alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, the ketone such as acetone, 2-butanone, the polyvalent alcohol such as ethylene glycol, glycerine, other ester class, the glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methyl proxitol acetate, butyl diglycol acetic ester, these solvents can be used alone or mix multiple use.

In addition, in dispersion liquid (B), as the aforementioned organic solvents for making metal particle (b2) disperse, the aforementioned water miscible solvent that can mix with water can be listed, such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the alcohols such as the trimethyl carbinol, acetone, the ketones such as 2-butanone, ethylene glycol, the polyvalent alcohols such as glycerine, other ester class, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methyl proxitol acetate, the glycol ethers such as butyl diglycol acetic ester, the solvent that can use these independent solvents or multi-solvents is mixed, and not mixing water.In this situation, contain little water because of moisture absorption etc. sometimes, but and unintentionally mix with water, therefore, treat as water-free organic solvent in the present invention.

In addition, in dispersion liquid (B), as the aforementioned organic solvents for making metal particle (b2) disperse, the organic solvent do not mixed with water can be listed, such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, octadecane, nonadecane, eicosane, the long chain alkanes such as trimethylpentane, hexanaphthene, tetramethylene, the cyclic alkane such as cyclooctane, benzene, toluene, dimethylbenzene, trimethylbenzene, the aromatic hydrocarbonss such as dodecylbenzene, hexanol, enanthol, octanol, decyl alcohol, hexalin, the alcohol such as terpinol, these solvents can be used alone or multiple used in combination.

As the manufacturing process of the dispersion liquid used in the present invention (B), be not particularly limited, various method can be used manufacture, such as, can make in the metal particle dispersion utilizing the vapor phase process such as the method for evaporation in rough vacuum gas to manufacture in a solvent, also can reducing metal compound and directly prepare the dispersion liquid of metal particle in the liquid phase.The solvent composition of dispersion liquid when gas phase, liquid phase method all can be added dispersion liquid when changing manufacture by exchange of solvent, solvent and are coated with as required and suitably.In gas phase, liquid phase method, from the viewpoint of the easy degree of the stability of dispersion liquid, manufacturing process, particularly preferably can use liquid phase method.

As the manufacturing process of the dispersion liquid (B) in aforementioned liquid phase method, can be suitable for using in the liquid phase, under the existence of aforesaid compound (b1) by the method that metallic compound reduces, the method recorded in Japanese Unexamined Patent Publication 2008-037884 publication, Japanese Unexamined Patent Publication 2008-037949 publication, Japanese Unexamined Patent Publication 2008-03818 publication, Japanese Unexamined Patent Publication 2010-007124 publication can be used to manufacture.Such as can operate as follows: after the aforesaid compound (P1) with polymine block and polyoxyethylene glycol block is dissolved in an aqueous medium or disperseing; add metallic compound wherein; and mix reductive agent after combinationally using complexing agent as required and forming uniform dispersion or with complexing agent simultaneously; thus; the metal be reduced becomes nano particle (having the particulate of nanoscale size), meanwhile obtains the aqueous dispersion of the metal particle protected by aforesaid compound (P1).

In addition; as the manufacturing process utilizing the dispersion liquid (B) of liquid phase method used in the present invention, such as can be suitable for using record in Japanese Patent No. 4697356 publications method, under aforementioned (methyl) acrylic polymers (P2) protectant existence the method for reducing metal compound.

In addition; as the manufacturing process utilizing the dispersion liquid (B) of liquid phase method used in the present invention; can be suitable for being used in the method for reducing metal compound under organic compound (P3) protectant existence of the aforementioned ad hoc structure containing thioether group (thioether bond); can under the existence of aforesaid Sulfide-containing Hindered organic compound (P3), through metallic compound and the operation of solvent and the operation of reducing metal compound being obtained the water dispersion (B) of metal particle.

And then, a mode of the metal particle (b2) used in the present invention is the core-shell particle of silver-colored core-copper shell, as the manufacturing process of the dispersion liquid (B) of this metal particle, can through the operation of the nano particle of silver, aforementioned Sulfide-containing Hindered organic compound (P3), Red copper oxide (I) and/or cupric oxide (II) and solvent and the operation generating the shell of copper by using reductive agent reductive copper oxide around silver nano-grain being obtained the dispersion liquid (B) of the core shell particle of silver-colored core-copper shell.The silver nano-grain used in present method can use commercially available silver nano-grain, also can use the silver nano-grain utilizing the manufacture method of the dispersion liquid of aforementioned metal particulate to obtain.

In the present invention, directly can use the aqueous dispersion of the metal particle utilizing aforesaid method to obtain, or, also can use and have passed through remaining complexing agent, reductive agent or be used as counter ion contained in the silver compound of raw material etc. by a kind of method in the various method of purification such as ultrafiltration process, the precipitator method, centrifugation, underpressure distillation, drying under reduced pressure or combine the purification procedures that two or more method is carried out and the dispersion obtained, it can also be used to change concentration (nonvolatile component), dispersion medium and the dispersion etc. that obtains further.

As operable metallic compound in the manufacturing process of the dispersion liquid (B) of the metal particle in these liquid phase methods, salt, the oxide compound of the element for the formation of metal particle (b2), i.e. gold and silver, copper, the platinum used in aforementioned the present invention can be used, from the viewpoint of solvability, acetate, nitrate, vitriol, muriate, acetylacetonate etc. can be listed as preference.Wherein preferably nitrate or acetate.But, even if be insoluble compound, can with the form of complexing agent as ammonia, amine compound, hydrazine class, azanol class with metallic ion coordination and formed there is deliquescent complex compound time, also can use the insoluble compound of metal oxide and so on.

Such as, when metallic element is gold, platinum family, tetra chlorauric acid, Tetrachloroplatinate etc. can be used.In addition, when metal species is copper, except Cu (OAc) can be used ₂, Cu (NO ₃) ₂, CuCl ₂, Cu (HCOO) ₂, Cu (CH ₃cOO) ₂, Cu (CH ₃cH ₂cOO) ₂, CuCO ₃, CuSO ₄, C ₅h ₇cuO ₂in addition, the basic salt, the such as Cu (OAc) that carboxylate salt heating are obtained can also similarly be used ₂cuO.When metal species is silver, can use Silver Nitrate, silver suboxide, silver acetate, silver chloride, silver sulfide etc., when processing in form of an aqueous solutions, from the viewpoint of its solubleness, Silver Nitrate is preferred.

As the metal particle (b2) in the dispersion liquid (B) that the present invention uses containing concentration, from the viewpoint of forming non-conductive layer (C) by being coated with this dispersion liquid at insulativity base material (A), in this dispersion liquid (B), need the metal particle (b1) containing more than 0.5 quality %.That is, time excessive rarefied, the distribution of the metal particle (b2) sometimes on insulativity base material (A) is too sparse and cannot form film, is difficult to form non-conductive layer (C).On the other hand, time too dense, the stacked number being coated on the metal particle (b2) on non-conductive layer (C) becomes too much, exist to form conductive layer by sintering, the worry of the effect on the basis that cannot give full play to the plating film as the strong adaptation of display.From the viewpoint, as the metal particle in the dispersion liquid used in the present invention (B) containing concentration, be necessary for more than 0.5 quality %, be preferably below 20wt%, be more preferably 0.7 ~ 15wt%, from the viewpoint of coating masking, more preferably 1 ~ 10wt%.

In dispersion liquid used in the present invention (B), to improve coating masking for main purpose, various surface tension modifier can be added as required, flow agent uses.About the addition of these surface tension modifier, flow agent, relative to dispersion liquid, in effective constituent preferably containing below 2.0 quality %, particularly preferably in effective constituent containing below 0.5 quality %.

The coating > of < dispersion liquid (B)

In the present invention, as the method at aforementioned dielectric base material (A) the aforementioned dispersion liquid of upper coating (B), non-conductive layer (C) can be formed well, be not particularly limited, according to the shape of used insulativity base material (A), size, the various printing coating method of the suitable selection such as hard and soft degree, specifically, can list: gravure coating process, flexographic printing process, relief printing plate method, method quoted by relief printing plate, silk screen print method, micro-contact-printing, reversal printing method, air knife coating method (air doctor coater), scraper for coating method, air knife coating method (air knife coater), extrusion coated method, Dipcoat method, angle stripper coating method, kiss-coating method, casting painting method, spraying method, gunite, mould is coated with method (die method), spin-coating method, stick coating method, Dipcoat method etc.

As the method for the aforementioned dispersion liquid of two sided coatings (B) of the aforementioned dielectric base material (A) in film, thin slice, tabular, as long as non-conductive layer (C) can be formed well to be just not particularly limited, suitable selection various printing coating gimmick, two sides can be formed simultaneously, also can carry out the coating of another side after coating one side.

After the dispersion liquid (B) of metal particle (b2) is coated insulativity base material (A), through coated film drying and form non-conductive layer (C).The drying of coated film can at room temperature be carried out, and also can carry out heat drying.In addition, can blow when drying, also can not specially blow.During air-supply, can heat air delivery, also can only at room temperature blow.In addition, drying can be carried out in an atmosphere, also can carry out under the displacement atmosphere such as nitrogen, argon gas or air-flow, can also carry out under vacuo.In addition, can also carry out under the nitrogen atmosphere being less than concentration of lower explosive limit.

For the drying of coated film, when film, thin slice, plate that aforementioned dielectric base material (A) is sheet, except except the seasoning in coating place, can also carry out under the condition in the moisture eliminators such as air-supply, thermostatic drier.In addition, when aforementioned dielectric base material (A) is for roll film (roll sheet), can then aforementioned printing painting process, in the non-heated arranged or heating space, roll film is moved continuously, carry out drying thus.

< non-conductive layer (C) >

In the present invention; the metal particle (b2) protected by aforesaid compound (b1) at the non-conductive layer (C) of the dispersion liquid (B) of the upper coating metal particulate (b2) of insulativity base material (A) near uniform to configure aforementioned dielectric base material (A) is upper; although also there is the situation that part metals particulate (b2) contacts each other, think as layer it is do not show electroconductibility.In the present invention, the layer that metal particle (b2) evenly configures does not show electroconductibility, is non-conductive referring to, use low-resistivity meter cannot measure the level of the resistance value of film, such as, use Mitsubishi Chemical AnalytechCo., the resistrivity meter of the Loresta series Ltd. manufactured, (resistance of this layer using four-terminal method to record is 9.999 × 10 to confirm no to scale ⁷more than Ω) or overload (even if the voltage applying 90V between terminal also cannot measure constant current) display.

What use in the present invention aforementionedly can carry out heat treated before the electroless plating suitably as required and in subsequent handling at the upper non-conductive layer (C) formed of insulativity base material (A).By heat treated, the adaptation of non-conductive layer (C) and insulativity base material (A) can be improved.In addition; when using printed circuit board (PCB); the high-temperature technologies such as such as soldering may be experienced; because in base material, as protectant compound (b1), the surface conditioner added as required, flow agent, dispersion solvent etc., in this high-temperature technology, sharply volatilization or the words of decomposition gasification can become problem; therefore, recommend during fabrication by carrying out heat treated in advance and removing this composition in advance.

For heat treated, utilize various heating means to process the aforementioned base material being formed with non-conductive layer (C) on insulativity base material (A), the one in electric furnace, retort furnace, vacuum oven, controlled atmosphere generator (atmosphere furnace), rayed heating unit, infrared heating device, microwave heating installation, electron rays heating unit etc. can be used or combinationally use multiple heating unit to carry out.In addition, heat treated as required can in an atmosphere, in vacuum, nitrogen atmosphere, argon atmospher and be less than concentration of lower explosive limit nitrogen atmosphere under carry out.In addition, the aforementioned base material being formed with non-conductive layer (C) on insulativity base material (A) is film, thin slice, the plate of sheet, can carry out in aforementioned heat treatment apparatus device, when for roll film shape, can by making sheet material continuous moving to carry out in the space of electrically heated, light heating, infrared heating, microwave heating.

In addition, in the present invention, the heat treated of non-conductive layer (C) can be carried out with the drying after the upper Coating dispersions (B) of insulativity base material (A) simultaneously, also can carry out drying and heat treated respectively.

In the present invention, the heat treatment temperature of non-conductive layer (C), heat treatment time is according to application target, the raw-material heat resisting temperature of the insulativity base material (A) used is suitable for selecting, be not particularly limited, such as, preferably, when insulativity base material (A) is for polyimide resin, below 400 DEG C, preferably heat-treat for less than 300 DEG C, during for polyethylene terephthalate, heat-treat below 150 DEG C, during for PEN, heat-treat below 200 DEG C, during for liquid crystalline polymers, heat-treat below 380 DEG C, for paper phenol, during Epoxide cellulose paper, heat-treat below 130 DEG C, during for epoxy glass, heat-treat below 150 DEG C, during for ABS resin, heat-treat below 100 DEG C.

The heat treated of non-conductive layer (C) that carry out in the present invention, that formed on insulativity base material (A) as previously mentioned, its object is to the adaptation of raising metal particle (b2) and insulativity base material (A), by the composition removing of high-temperature process by volatilization decomposition gasification, instead of in order to make aforementioned metal particulate (b1) mutually closely sealed, merge and show electroconductibility, it is characterized in that, also keep non-conductive after a heating treatment.

In non-conductive layer (C) that use in the present invention, that formed on aforementioned dielectric base material (A), aforementioned metal particulate (b2) is configured on aforementioned dielectric base material (A), when the stacked number of the metal particle (b2) on thickness direction is too much, by aforesaid heat treated, the junction surface of the mutual welding of more metal particle (b2) can be formed, form uneven welding structure in film entirety, easily become the film demonstrating electroconductibility.There is the conductive film of so uneven welding structure owing to comprising a lot of space in film, therefore bad mechanical strength, the film of this bad mechanical strength is present between insulativity base material (A) and the metallic membrane formed in plating process afterwards, thus plating film can easily be peeled off from insulativity base material (A).In addition, when using the film with so uneven welding structure to carry out electroless plating, namely allow to the space on filling film top, be also difficult to, by the space of the metal lining inner and bottom of landfill welding structure fully, be difficult to the physical strength improving film.From the viewpoint, the stacked number being preferably configured in the aforementioned metal particulate (b2) on aforementioned dielectric base material (A) is less than 5 layers, is more preferably less than 3 layers.The stacked number of metal particle (b2) on insulativity base material (A) can be confirmed by the determining film thickness of the non-conductive layer (C) that utilizes confocal microscope, interfere type microscope, surface-profile measuring instrument etc. to carry out, the surface of non-conductive layer (C) utilizing electron microscope to carry out, cross-section.

In addition, in non-conductive layer (C) that use in the present invention, that formed on aforementioned dielectric base material (A), aforementioned dielectric base material (A) is covered by aforementioned metal particulate (b2), and it works as the seed of plating catalyzer and plating, basal layer in plating process afterwards.When the surface-coated rate brought of aforementioned metal particulate (b2) on insulativity base material (A) surface is too low, the distance between the metallic crystal of precipitation is excessive, mutual bonding of crystallization can not occur, therefore, be difficult to form plating overlay film.On the other hand, when the covering rate on insulativity base material (A) surface that metal particle (b2) brings uprises, the stacked number of the metal particle (b2) of substrate surface becomes many, due to aforementioned heat treated, engage between metal particle (b2), form the many uneven welding structures in space and become conductive film.When forming the conductive film of so uneven welding structure, owing to forming a lot of independently space, thus bad mechanical strength in film inside as previously mentioned, the metal lining film formed in operation afterwards cannot keep stripping strength in practical use.If the surface-coated rate that metal particle (b2) brings is suitable, connection between the metal lining crystallization of then separating out is good, easily forms overlay film, and, metal lining produces anchoring effect by the space between abundant percolated metal particulate (b2), and stripping strength improves.From the viewpoint, the surface-coated rate brought of aforementioned metal particulate (b2) on aforementioned dielectric base material (A) surface from the viewpoint of the plating of subsequent handling, keep plating overlay film from the stripping strength of insulativity base material, be more preferably 20 more than area % and 90 below area %.

In the present invention, the surface-coated rate that aforementioned metal particulate (b2) on aforementioned dielectric base material (A) brings can carry out the surface observation of non-conductive layer (C) by using high-resolution scanning electron microscope (SEM), and calculate metal particle (b2) image observed on image occupy ratio to evaluate.During by the size of the metal particle used in the present invention (b2) to evaluate surperficial covering rate, the observation multiplying power of recommendation about 50,000 times.

In the present invention, also can carry out the patterning of circuit pattern at the upper non-conductive layer (C) formed of aforementioned dielectric base material (A) before the second operation and electroless plating process.As the method for patterning, can list and bring out ablation phenomen by laser radiation and remove the method for unwanted part.As the laser used in this object, the laser of any wavelength of UV laser, visible light lasers, near infrared, infrared light laser can be used.

< Electroless Plating Procedure >

Second operation of the present invention, on the aforementioned base material being provided with non-conductive layer (C) on insulativity base material (A), namely form conductive layer (D) operation by carrying out electroless plating by the upper non-conductive layer (C) formed of aforementioned dielectric base material (A) and implement as the catalyst layer of electroless plating and Seed Layer.

For Electroless Plating Procedure, preferably carry out electroless plating via cleaning process, washing step, catalyst activation operation, washing step.The kind of metal lining is not particularly limited, considers from electroconductibility and industrial usability, preferably carry out electroless copper.This electroless copper can be suitable for using commercially available electroless plating reagent, specifically, and the OICCOPPER that can Okuno Chemical Industries Co., Ltd. be used especially aptly to manufacture.

Be not particularly limited the conductive layer (D) formed by electroless plating in the second operation of the present invention, preferred surface resistivity is 1000 Ω/below, and then, when implementing plating by the 3rd operation, as surface resistivity, be preferably 10 Ω/below.If consider the efficiency being formed metal conducting layer (E) by plating of the 3rd operation, be then more preferably 1 Ω/below.In addition, the thickness of the conductive layer (D) formed by electroless plating, from the viewpoint of the operation efficiency manufactured, is preferably below 1500nm.

< electroplating work procedure >

In the present invention, by aforesaid Electroless Plating Procedure, the conductive material on surface with conductive layer (D) can be obtained, but for improving electroconductibility further or increasing the object of thickness of conductive layer, can also carry out electroplating as the 3rd operation.Now, the metal species formed by plating is not particularly limited, from the viewpoint of electroconductibility, stability, preferably copper, nickel, gold etc., the low and industrial utilization particularly preferably copper from the viewpoint of resistance value.

As electroplating work procedure, be not particularly limited, use various electro-plating method, such as, after the removing of degreasing and/or zone of oxidation is carried out on conductive layer (D) surface that can obtain in operation (2), dipping in plating liquid and being energized, thus form coating layer.

Thickness by electroplating the metal conducting layer (E) obtained is not particularly limited, suitably select according to application target, the conductive layer (D) formed with the electroless plating by the second operation adds up to, be preferably more than 200nm and less than 30 μm, circuit pattern voltinism from the viewpoint of electroconductibility and when using, is more preferably more than 400nm and less than 20 μm.

The conductive material manufactured via aforesaid 2 operations has the non-conductive layer (C) be made up of metal particle (b2) on aforementioned dielectric base material (A), and conductive layer (D) is laminated with on this non-conductive layer (C), in addition, the conductive material obtained by 3 operations has the non-conductive layer (C) formed by metal particle (b2) on aforementioned dielectric base material (A), and is laminated with conductive layer (D) and metal conducting layer (E) thereon.For conductive material of the present invention, the metal species of metal particle (b2) can be all identical metal with the metal species of the conductive layer (D) or conductive layer (D) and metal conducting layer (E) that are formed thereon formation, also can be metal species different separately.Such as, in a mode of conductive material of the present invention, the non-conductive layer (C) on insulativity base material (A) is formed by silver-colored particulate, and the conductive layer (D) formed thereon is formed by copper.In addition, as other mode, can list: the non-conductive layer (C) on insulativity base material (A) is formed by copper particulate, the conductive layer (D) that formed thereon and metal conducting layer (E) are also formed by copper.And then, as other mode, can also list: the non-conductive layer (C) on insulativity base material (A) is by being core with silver, being that the core-shell particle of shell is formed with copper, and the conductive layer (D) formed thereon and metal conducting layer (E) are formed by copper.

It should be noted that, in conductive material of the present invention, for the non-conductive layer (C) formed by metal particle (b2) on insulativity base material (A), after formation conductive layer (D), the space between filler metal particulate (b2) by the formation of conductive layer (D), thus also can not as the independently non-conductive layer (C) and existing of the essence on insulativity base material (A).

About the formation of conductive material of the present invention, schematic diagram shown in Fig. 1 ~ Fig. 6.Such conductive material, thus can especially aptly as the laminated substrate needing the use in printed circuit board of carrying out fine rule processing due to the excellent adhesion of insulativity base material (A) and conductive layer.

Embodiment

Below enumerate embodiment to illustrate in greater detail the present invention, but the present invention is not limited to these embodiments.It should be noted that, in case of no particular description, " % " expression " quality % ".

The equipment used in the present invention is as described below.

¹h-NMR: Jeol Ltd.'s manufacture, AL300,300Hz

Tem observation: Jeol Ltd. manufactures, JEM-2200FS

SEM observes: Hitachi manufactures, ultrahigh resolution field emission type scanning electronic microscope S-800 or KEYENCE CORPORATION manufactures, VE-9800

TGA measures: SII NanoTechnology Inc. manufactures, TG/DTA6300

Plasma absorption spectrum: Hitachi Co., Ltd manufactures, UV-3500

Dynamic light scattering particle size determination device: Otsuka Electronics Co., Ltd. manufactures, FPAR-1000

Surface resistivity pH-value determination pH: Mitsubishi chemical Co., Ltd manufactures, low-resistivity meter Loresta EP (4 terminal method)

Surface-coated rate measures: the ultrahigh resolution field emission type scanning electronic microscope S-800 that the surface-coated rate that the metal particle of substrate surface brings uses Hitachi to manufacture, Coating dispersions is observed and dried surface with multiplying power 50,000 times, observation image is carried out after two-value turns to black white image, calculate relative to imaging surface entirety area, the occupied area of metal particle, thus calculate surface-coated rate.

Peeling strength test: A & D Corp. manufactures Tensilon universal testing machine RTC-1210A: the strip being 1cm from base material stripping by plating overlay film, obtains the tensile strength in 180 DEG C of directions, measures stripping strength thus.

(manufacture of the dispersion liquid of metal particle)

< has the synthesis > of the compound (P1) of polymine block and polyoxyethylene glycol block

Synthesis example 1 (there is the synthesis of the compound (P1-1) of polyoxyethylene glycol (PEG)-branched polyethylenimine (PEI) structure)

1-1 [synthesis of tolylsulfonyl polyethylene glycol]

Be prepared in respectively in chloroform 150ml and mix single terminal methoxy group polyethylene glycol (hereinafter referred to as PEGM) (number-average molecular weight (Mn) 5000) (manufacture of Aldrich company) 150g (30mmol) and pyridine 24g (300mmol) and the solution obtained, and the solution that toluene sulfonyl chloride 29g (150mmol) and chloroform 30ml Homogeneous phase mixing are obtained.

Stir the mixing solutions of PEGM and pyridine below at 20 DEG C, limit drips the toluene solution of toluene sulfonyl chloride wherein.After dropping terminates, react 2 hours at 40 DEG C.After reaction terminates, add chloroform 150ml and dilute, after 5%HCl aqueous solution 250ml (340mmol) cleaning, clean with saturated aqueous common salt and water.After the chloroformic solution sodium sulfate obtained is carried out drying, utilize vaporizer by solvent distillation removing, carry out drying further.Yield is 100%.Utilize ¹h-NMR spectrum carries out the ownership (2.4ppm: the methyl of the methyl in tosyl group, 3.3ppm:PEGM end, the EG chain of 3.6ppm:PEG, 7.3 ~ 7.8ppm: the phenyl ring in tosyl group) at each peak, confirms as tolylsulfonyl polyethylene glycol.

1-2 [there is the synthesis of the compound of PEG-side chain PEI structure]

The tolylsulfonyl polyethylene glycol 23.2g (4.5mmol) obtained in above-mentioned 1-1 and branched polymine (Nippon Shokubai Co., Ltd's manufacture, EPOMIN SP200) 15.0g (1.5mmol) is dissolved in after in N,N-DIMETHYLACETAMIDE (hereinafter referred to as DMA) 180ml; add salt of wormwood 0.12g, react 6 hours at 100 DEG C under nitrogen atmosphere.After reaction terminates, removing solid residue, adds the mixed solvent of ethyl acetate 150ml and hexane 450ml, is precipitated thing.By this precipitate dissolves in chloroform 100ml, again add the mixed solvent of ethyl acetate 150ml and hexane 450ml, make its redeposition.Filtered, under reduced pressure carried out drying.Utilize ¹h-NMR spectrum carries out the ownership (the EG chain of the ethylidene of 2.3 ~ 2.7ppm: side chain PEI, the methyl of 3.3ppm:PEG end, 3.6ppm:PEG) at each peak, confirms as the compound (P1-1) with PEG-side chain PEI structure.Yield is 99%.

Synthesis example 2 (there is the synthesis of the bisphenol A type epoxy resin structured compound (P1-2) of PEG-side chain PEI-)

2-1 [modification of epoxy resin]

Bisphenol A type epoxy resin EPICLON AM-040-P (Dainippon Ink Chemicals's manufacture) 37.4g (20mmol), 4-phenylphenol 2.72g (16mmol) are dissolved in after in DMA100ml, add 65% acetic triphenyl phosphonium ethanolic soln 0.52ml, react 6 hours at 120 DEG C under nitrogen atmosphere.After placing cooling, be added drop-wise in large water gaging, the throw out obtained is cleaned with a large amount of water further.Carry out drying under reduced pressure after being filtered by redeposition purified, obtain modified bisphenol A type epoxy resin.The yield of the product obtained is 100%.

Carry out ¹h-NMR measures the integration ratio investigating epoxy group(ing), result, residual 0.95 oxirane ring in 1 molecule bisphenol A type epoxy resin, confirms that the modified epoxy obtained is the epoxy resin of the mono-functional with bisphenol A skeleton.

2-2 [there is the synthesis of the bisphenol A type epoxy resin structured compound (P1-2) of PEG-side chain PEI-]

To compound (P1-1) 20g (0.8mmol) with PEG-side chain PEI structure obtained in synthesis example 1 is dissolved in the solution obtained in methyl alcohol 150ml, the mono-functional's epoxy resin 4.9g (2.4mmol) dripping the bisphenol A-type modification by above-mentioned epoxy resin obtained under nitrogen atmosphere is dissolved in the solution obtained in acetone 50ml, afterwards, stir 2 hours at 50 DEG C, thus react.After reaction terminates, under reduced pressure by solvent distillation removing, and then carry out drying under reduced pressure, obtain that there is the bisphenol A type epoxy resin structured compound of PEG-branched PEI-(P1-2) thus.Yield is 100%.

Synthesis example 3 (has the synthesis of the compound (P1-3) of PEG-side chain PEI-naphthalene type epoxy resin structural

3-1 [modification of epoxy resin]

Naphthalene type epoxy resin ICLON HP-4700 (Dainippon Ink Chemicals's manufacture) 44.5g (80mmol), 4-phenylphenol 29.9g (176mmol) are dissolved in after in DMA200ml, add 65% acetic triphenyl phosphonium ethanolic soln 1.36ml, react 6 hours at 120 DEG C under nitrogen atmosphere.After placing cooling, be added drop-wise in water 150ml, by the throw out washed with methanol that obtains 2 times, afterwards, at 60 DEG C, carry out drying under reduced pressure, obtain modification naphthalene type epoxy resin.Yield is 100%.

Carry out ¹h-NMR measures the integration ratio investigating epoxy group(ing), result, and in 1 molecule naphthalene type epoxy resin, residual 0.99 oxirane ring, confirms as the naphthalene type epoxy resin of mono-functional.

3-2 [there is the synthesis of the compound (P1-3) of PEG-side chain PEI-naphthalene type epoxy resin structural]

To compound (P1-1) 4.65g (0.5mmol) with PEG-side chain PEI structure obtained in above-mentioned synthesis example 1 is dissolved in the solution obtained in methyl alcohol 40ml, drip under nitrogen atmosphere and mono-functional's epoxy resin 1.16g (1.1mmol) of the naphthalene skeleton obtained in above-mentioned 3-1 be dissolved in the solution obtained in acetone 15ml, back at 50 DEG C, stir 2 hours limits make it react.After reaction terminates, under reduced pressure by solvent distillation removing, carry out drying under reduced pressure further, obtain the compound (P1-3) with PEG-side chain PEI-naphthalene type epoxy resin structural thus.Yield is 100%.

Synthesis example 4 (there is the synthesis of the compound (P1-4) of PEG-side chain PEI-polystyrene structure)

To compound (P1-1) 1.22g (0.049mmol) with PEG-side chain PEI structure obtained in synthesis example 1 is dissolved in the solution obtained in water 44g, add 2mol/L hydrochloric acid 1.9g and styrene monomer 1.92g (18.4mmol), limit is stirred limit and is added 70% tertbutyl peroxide (TBHP) 0.45g (5.0mmol) at 80 DEG C under nitrogen atmosphere, reacts 2 hours.After cooling, carry out purifying by dialysis, obtain the water dispersion of the compound (P1-4) with PEG-side chain PEI-polystyrene structure.Yield is 100%.

Synthesis example 5 (there is the synthesis of the compound (P1-5) of PEG-side chain PEI-polypropylene glycol backbone amino manthanoate structure)

5-1 [synthesis of polypropylene glycol (PG) backbone amino manthanoate]

In dipropylene glycol diglycidylether EPICLON 705 (Dainippon Ink Chemicals's manufacture) 20.1g (50mmol), dibutylamine 13.0g (101mmol) was dripped with 0.5 hour under nitrogen atmosphere at 70 DEG C, 90 DEG C of reactions 7 hours, obtain two end dibutylamino PG reaction solns.Then, in the mixing solutions of vulcabond 19.4g (100mmol), stannous octoate 0.04g (0.1mmol) and chloroform 80g, at 40 DEG C, drip two end dibutylamino PG reaction solns of above-mentioned synthesis with 0.5 hour, at 50 DEG C, carry out addition reaction in 5 hours.And then, at 40 DEG C, dripped cyclohexane methanol 5.7g (50mmol) with 20 minutes, carry out addition reaction in 5 hours at 50 DEG C, obtain the solution of polypropylene glycol backbone amino manthanoate.

5-2 [there is the synthesis of the compound (P1-5) of PEG-side chain PEI-polypropylene glycol backbone amino manthanoate structure]

To the macromolecular compound 16.0g with PEG-side chain PEI structure obtained in above-mentioned synthesis example 1 is dissolved in the solution obtained in chloroform 30ml, dripped with 10 minutes under nitrogen atmosphere and the solution 2.76g (2mmol) of the polypropylene glycol backbone amino manthanoate obtained in above-mentioned 5-1 is dissolved in the solution obtained in chloroform 10ml, then stir 2 hours limits below at 40 DEG C and make it react.After reaction terminates, add the mixed solvent 340g that water and acetone are 1 to 1 (volume ratio), under reduced pressure by chloroform and acetone distillation removing, obtain the water dispersion of the compound (P1-5) with PEG-side chain PEI-polypropylene glycol backbone amino manthanoate structure.Yield is 100%

Synthesis example 6 (there is the synthesis of the compound (P1-6) of PEG-side chain PEI-polycarbonate backbone carbamate structures)

6-1 [synthesis of polycarbonate backbone carbamate]

In the mixing solutions of vulcabond 19.4g (100mmol), stannous octoate 0.04g (0.1mmol) and chloroform 100g, polycarbonate diol 49.0g (50mmol) was dripped with 0.5 hour under nitrogen atmosphere at 40 DEG C, afterwards, at 50 DEG C, carry out addition reaction in 5 hours, obtain the reaction soln of two terminal isocyanate carbamates.Then, in two terminal isocyanate urethane reaction solution of synthesis, cyclohexane methanol 5.7g (50mmol) was dripped with 20 minutes at 40 DEG C, afterwards, at 50 DEG C, carry out addition reaction in 5 hours, obtain single terminal isocyanate polycarbonate backbone urethane reaction solution.

6-2 [there is the synthesis of the compound (P1-6) of PEG-side chain PEI-polycarbonate backbone carbamate structures]

To the macromolecular compound 16.0g with PEG-side chain PEI structure obtained in synthesis example 1 is dissolved in the solution obtained in chloroform 30ml, dripped with 10 minutes single terminal isocyanate polycarbonate backbone urethane reaction solution 7.0g (2mmol) obtained by above-mentioned synthesis 5-1 under nitrogen atmosphere and be dissolved in the solution obtained in chloroform 10ml, afterwards, stirring 2 hours limits on 40 DEG C of limits makes it react.After reaction terminates, interpolation water and acetone are the mixed solvent 340g of 1 to 1 (volume ratio), under reduced pressure by chloroform and acetone distillation removing, obtain the water dispersion of the compound (P1-6) with PEG-side chain PEI-polycarbonate backbone carbamate structures.Yield is 100%.

The synthesis > of < (methyl) acrylic polymers (P2)

Synthesis example 7 (synthesis of (methyl) acrylic polymers (P2-1) containing methoxycarbonyl ethylmercapto group and phosphate residue)

Methylethylketone (hereinafter referred to as MEK) 32 parts and ethanol 32 parts is added, warming while stirring to 80 DEG C in nitrogen gas stream in the four-hole boiling flask possessing thermometer, stirrer and reflux exchanger.Then, the mixture comprising methacrylic acid phosphorus acyloxy ethyl ester 20 parts, methoxy polyethylene glycol methacrylate-styrene polymer (molecular weight 1000) 80 parts, mercapto-propionate 4.1 parts, MEK80 part is dripped respectively with 2 hours, and comprise the mixture of polymerization starter " 2; 2 '-azo two (2,4-methyl pentane nitrile) " (with Guang Chun medicine Co., Ltd. product V-65) 0.5 part, MEK5 part.After dropping terminates, within every 4 hours, add 2 " day oil PERBUTYL (registered trademark) O " (Japan Oil Co's manufactures) 0.3 part, stir 12 hours at 80 DEG C.In the resin solution obtained, add water carry out Phase inversion emulsification, after decompression desolventizing, add water to regulate concentration, thus obtain the aqueous solution of (methyl) acrylic polymers of non-volatile content 76.8%.This resin by the weight-average molecular weight of gel permeation chromatography with polystyrene conversion be 4300, acid number is for 97.5mgKOH/g.

Synthesis example 8 (synthesis of (methyl) acrylic polymers (P2-2) containing 2-(2-ethyl hexyl oxy carbonyl) ethylmercapto group and phosphate residue)

Thiohydracrylic acid-2-ethylhexyl 11.2 parts is used to replace the mercapto-propionate 4.1 parts of synthesis example 7, in addition, to operate equally with synthesis example 7, obtain the aqueous solution of (methyl) acrylic polymers (P2-2) of non-volatile content 73.2%.The weight-average molecular weight of this polymkeric substance is 4100, acid number is 98.1mgKOH/g.

Synthesis example 9 (synthesis of (methyl) acrylic polymers (P2-3) containing 2,3-dihydroxyl rosickyite base and phosphate residue)

Thioglycerin 4.1 parts is used to replace the thiohydracrylic acid-2-ethylhexyl 11.2 parts of synthesis example 8, in addition, to operate equally with synthesis example 8, obtain the aqueous solution of (methyl) acrylic polymers (P2-3) of non-volatile content 70.1%.The weight-average molecular weight of this polymkeric substance is 5500, acid number is 95.1mgKOH/g.

Synthesis example 10 (synthesis of (methyl) acrylic polymers (P2-4) containing 2-hydroxyeththylthio and phosphate residue)

THIOGLYCOL 2 parts is used to replace the thiohydracrylic acid 2-ethylhexyl 11.2 parts of synthesis example 8, in addition, to operate equally with synthesis example 8, obtain the aqueous solution of (methyl) acrylic polymers (P2-4) of non-volatile content 56.4%.Weight-average molecular weight is 6700, acid number is 94.9mgKOH/g.

Synthesis example 11 (synthesis of (methyl) acrylic polymers (P2-5) containing Carboxymethylsulfanyl and phosphate residue)

Use Thiovanic acid 2 parts to replace the thiohydracrylic acid-2-ethylhexyl 11.2 parts of synthesis example 8, in addition, to operate equally with synthesis example 8, obtain the aqueous solution of (methyl) acrylic polymers (P2-5) of non-volatile content 65.1%.Weight-average molecular weight is 6800, acid number is 92.1mgKOH/g.

Synthesis example 12 (synthesis of (methyl) acrylic polymers (P2-6) containing dodecyl sulfenyl and phosphate residue)

Lauryl mercaptan 6 parts is used to replace the thiohydracrylic acid-2-ethylhexyl 11.2 parts of synthesis example 8, in addition, to operate equally with synthesis example 8, obtain the aqueous solution of (methyl) acrylic polymers (P2-6) of non-volatile content 77.7%.Weight-average molecular weight is 9600, acid number is 97.0mgKOH/g.

< contains the synthesis > of the organic compound (P3) of thioether group (thioether bond)

Synthesis example 13

(polyoxyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain))

[chemical formula 1]

Potassium tert.-butoxide (100.8g is added in the dehydrated toluene of 1000g, 0.8983mol) stir, in this mixture, toluene (2000g) solution of MPEG-550 (molecular weight 2000,600g) was at room temperature dripped with 3 hours.After keeping this state at room temperature to stir 2 hours, be warming up to 40 DEG C, then stir 2 hours.In this mixture, drip Epicholorohydrin (168g, 1.82mol) at the same temperature, stir 5.5 hours at 40 DEG C.Filter reaction mixture, and filtrate is concentrated, in the residue obtained, add chloroform again dissolve, it is cleaned 5 times with water.In chloroform layer, add dry aluminum oxide and decolour, filtering aluminum oxide, and filtrate is concentrated.Utilize toluene/normal hexane that concentrated residue is carried out redeposition purifying, collect the solid generated and carry out drying under reduced pressure, obtain 507.0g title compound (yield 82%).

¹h-NMR (deuterochloroform): δ=3.9-3.4 (m, polyglycol chain etc.), 3.43 (dd, 1H, J=6.0,5.7Hz, oxyethane ring adjoins one in methylene radical hydrogen), 3.38 (s, 3H, PEG terminal methoxy group), 3.16 (m, 1H, oxyethane ring methyne hydrogen), 2.79 (m, 1H, oxyethane ring terminal methylene hydrogen), 2.61 (m, 1H, oxyethane ring terminal methylene hydrogen).

[3-(3-(methoxyl group (polyethoxye) oxyethyl group)-2-hydroxyl rosickyite base) methyl propionate

The synthesis of (compound to polyoxyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition 3-mercapto-propionate)]

[chemical formula 2]

At the aforementioned polyoxyethylene glycol methyl glycidyl ether (molecular weight 2000 of methoxy poly (ethylene glycol) obtained, 3-mercapto-propionate (221mg is added 1.00g), 1.84mmol) and 1mol/L tetrabutyl ammonium fluoride/tetrahydrofuran solution (100 μ L, heat up 0.10mmol), stir 1 hour at 70 ~ 75 DEG C.After cooling, add water 20mL and ethyl acetate 20mL in the mixture, fully stir, leave standstill separatory.Afterwards, then by aqueous layer with ethyl acetate (20mL) 2 times are cleaned.When adding sodium sulfate in water layer, separate out oily matter, therefore, with methylene dichloride (20mL × 3 time), it is extracted.Collect dichloromethane layer, after carrying out drying by anhydrous sodium sulphate, concentrate drying solidifies, and obtains the title Sulfide-containing Hindered organic compound (P3-1) (yield about 89%) of 0.94g.By ¹h-NMR is known, is the purity without the need to special purifying.

¹h-NMR (deuterochloroform): δ=3.9-3.4 (m, polyglycol chain etc.), 3.70 (s, 3H, METH), 3.38 (s, 3H, PEG terminal methoxy group), 2.84 (t, 2H, J=7.2Hz, mercaptan compound side S adjoins methylene radical), 2.70 (dd, 1H, J=5.4, 13.5Hz, polyether compound side S adjoins methylene radical), 2.64 (t, 2H, J=7.2Hz, ester carbonyl group α position methylene radical hydrogen), 2.62 (dd, 1H, J=7.5, 13.5Hz, polyether compound side S adjoins methylene radical), 2.34 (br, 1H, OH).

Synthesis example 14

[3-(methoxyl group (polyethoxye) oxyethyl group)-2-hydroxyl rosickyite ethyl]

The synthesis of (compound to polyoxyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition ethyl thioglycolate)]

[chemical formula 3]

Use ethyl thioglycolate (174mg, 1.45mmol) replace the 3-mercapto-propionate (221mg of synthesis example 13,1.84mmol), in addition, to operate equally with synthesis example 13, obtain the title Sulfide-containing Hindered organic compound (P3-2) (yield about 98%) of 1.04g.

¹h-NMR (deuterochloroform): δ=4.19 (q, 2H, J=6.9Hz, ethyl ester O adjoins methylene radical hydrogen), 3.9-3.4 (m, polyglycol chain etc.), 3.38 (s, 3H, PEG terminal methoxy group), 3.30 (s, 2H ,-SCH ₂cO-), 2.82 (dd, 1H, J=5.1,13.8Hz, polyether compound side S adjoins methylene radical), 2.64 (dd, 1H, J=7.5,13.8Hz, polyether compound side S adjoins methylene radical), 2.58 (br, 1H, OH), 1.29 (t, 3H, J=6.9Hz, ethylacrylate methyl hydrogen).

Synthesis example 15

[2-(3-(methoxyl group (polyethoxye) oxyethyl group)-2-hydroxyl rosickyite base) ethyl propionate

The synthesis of (compound to polyoxyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition ethyl 2-mercaptopropionate)]

[chemical formula 4]

Use ethyl 2-mercaptopropionate (247mg, 1.84mmol) replace the 3-mercapto-propionate (221mg of synthesis example 13,1.84mmol), in addition, to operate equally with synthesis example 13, obtain the Sulfide-containing Hindered organic compound (P3-3) (yield about 95%) of 1.01g.

¹h-NMR (deuterochloroform): δ=4.19 (q, 2H, J=6.9Hz, ethyl ester O adjoins methylene radical hydrogen), 3.9-3.5 (m, polyglycol chain etc.), 3.38 (s, 3H, PEG terminal methoxy group), 2.9-2.6 (dd (4 groups), 2H, polyether compound side S adjoins methylene radical, syn/anti isomer mixture), 1.9 (br, 1H, OH), 1.45 (d, 3H, J=7.2Hz, carboxyl β position methyl), 1.29 (t, 3H, J=6.9Hz, ethylacrylate methyl hydrogen).

Synthesis example 16

[3-(3-(methoxyl group (polyethoxye) oxyethyl group)-2-hydroxyl rosickyite base) n-butyl propionate

The synthesis of (compound to polyoxyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition 3-thiohydracrylic acid butyl ester)]

[chemical formula 5]

Use 3-thiohydracrylic acid butyl ester (243mg, 1.50mmol) replace the 3-mercapto-propionate (221mg of synthesis example 13,1.84mmol), in addition, to operate equally with synthesis example 13, obtain the title Sulfide-containing Hindered organic compound (P3-4) (yield about 58%) of 0.651g.

¹h-NMR (deuterochloroform): δ=4.10 (t, 2H, butyl ester O adjoins methylene radical), 3.9-3.4 (m, polyglycol chain etc.), 3.38 (s, 3H, PEG terminal methoxy group), 2.83 (t, 2H, J=7.2Hz, mercaptan compound side S adjoins methylene radical), 2.71 (dd, 1H, J=5.7, 13.5Hz, polyether compound side S adjoins one in methylene radical hydrogen), 2.62 (t, 2H, J=7.2Hz, alpha site of carboxyl group methylene radical hydrogen), 2.62 (dd, 1H, J=7.2, 13.5Hz, polyether compound side S adjoins one in methylene radical hydrogen), 2.48 (br, 1H, OH), 1.63 (m, 2H, butyl ester methylene radical), 1.37 (m, 2H, butyl ester methylene radical), 0.94 (t, 3H, J=7.4Hz, butyl ester terminal methyl group).

Synthesis example 17

[2-(3-(n-butoxy-poly-(1-methyl ethoxy)-1-methyl ethoxy)-2-hydroxyl rosickyite base) ethyl propionate

The synthesis of (compound to polypropylene glycol butylglycidyl ether (molecular weight 2000 of polypropylene glycol chain) addition ethyl 2-mercaptopropionate)]

The synthesis of polypropylene glycol butylglycidyl ether (molecular weight 2000 of polypropylene glycol chain)

[chemical formula 6]

Use polypropylene glycol monobutyl base ether (molecular weight 2000,600g) replace the MPEG-550 (molecular weight 2000,600g) of synthesis example 13, in addition, to operate equally with synthesis example 13, obtain title compound 510.3g (yield 85%).

¹h-NMR (deuterochloroform): δ=3.7-3.4 (m, polypropylene glycol chain and butyl oxygen contiguous bits methylene radical hydrogen), 3.14 (m, 1H, oxyethane ring methyne hydrogen), 2.79 (m, 1H, oxyethane ring terminal methylene hydrogen), 2.62 (m, 1H, oxyethane ring terminal methylene hydrogen), 1.55 (m, 2H, butyl methylene radical hydrogen), 1.35 (m, 2H, butyl methylene radical hydrogen), 1.15 (md, polytrimethylene methyl hydrogen), 0.91 (t, 3H, J=7.4Hz, butyl terminal methyl group hydrogen)

[chemical formula 7]

At the aforementioned polypropylene glycol butylglycidyl ether (molecular weight 2000 of polypropylene glycol chain obtained, ethyl 2-mercaptopropionate (404mg is added 2.00g), 3.01mmol) and 1mol/L tetrabutyl ammonium fluoride/tetrahydrofuran solution (100 μ L, 0.10mmol), heat up, stir 1 hour at 70 ~ 75 DEG C.After cooling, add water (20mL) and ethyl acetate (20mL) in the mixture, fully stir, leave standstill separatory.Thereafter, then by ethyl acetate washed with water (20mL) carry out 2 cleanings.In ethyl acetate layer, add copper sulfate 5 hydrate (about 1g), stir 10 minutes.Filtering solids composition, concentrates filtrate, obtains the Sulfide-containing Hindered organic compound (P3-5) (2.33g, yield 97%) of title.

¹h-NMR (deuterochloroform): δ=4.19 (q, 2H, J=6.9Hz, ethyl ester O adjoins methyl), 3.6-3.3 (m, polypropylene glycol chain and butyl methylene radical-OCH ₂-etc.), 2.8-2.6 (dd (4 groups), 2H, polyether compound side S adjoins one in methylene radical hydrogen, syn/anti isomer mixture), 2.1 (br, 1H, OH), 1.44 (d, 3H, J=6.9Hz, carboxyl β position methyl), 1.55 (m, 2H, butyl methylene radical hydrogen), 1.35 (m, 2H, butyl methylene radical hydrogen), 1.29 (t, 3H, J=6.9Hz, ethylacrylate methyl), 1.14 (md, polypropylene methyl hydrogen), 0.91 (t, 3H, J=7.5Hz, butyl terminal methyl group hydrogen).

The manufacture > of the dispersion (B) of < metal particle (b2)

Synthesis example 18

In the aqueous solution 138.8g comprising compound (P1-1) 0.592g obtained in above-mentioned synthesis example 1, add silver suboxide 10.0g, stir 30 minutes at 25 DEG C.Then, slowly add dimethylethanolamine 46.0g while stirring, result, reaction soln becomes dark red, generates heat a little, keeps this state and places, and stirs 30 minutes at 25 DEG C.Thereafter, 10% aqueous ascorbic acid 15.2g is slowly added while stirring.Keep this temperature and continue stirring again 20 hours, obtaining the dispersion of dark red.

Add the mixed solvent of Virahol 200ml and hexane 200ml in dispersion liquid after reaction obtained above terminates, stir after 2 minutes, carry out 5 minutes centrifugal concentratings with 3000rpm.After supernatant liquor is removed, in throw out, add the mixed solvent of Virahol 50ml and hexane 50ml, stir after 2 minutes, carry out 5 minutes centrifugal concentratings with 3000rpm.After supernatant liquor is removed, in throw out, add water 20g again, stir 2 minutes, under reduced pressure organic solvent is removed, obtain the aqueous dispersion (B-1) of Argent grain.

Take the dispersion (B-1) obtained, measured by the visible absorption spectra of 10 times of diluents, confirm the peak of plasma absorption spectrum at 400nm place, confirm to generate silver nano-grain.In addition, spherical silver nano-grain (median size 17.5nm) is confirmed as by tem observation.Use the silver-colored containing ratio in TG-DTA mensuration solid, result is 97.2%.Can estimate that compound (P1-1) content in the nonvolatile component in the dispersion obtained by this synthesis method is 2.8% thus.

Synthesis example 19

Prepare respectively compound (P1-2) 20mg (ethylene imine units: 0.15mmol) obtained in above-mentioned synthesis example 2 is dissolved in obtain in water 2.39g solution 2A, Silver Nitrate 0.16g (0.97mmol) is dissolved in obtain in water 1.30g solution 2B, Trisodium Citrate 0.12g (0.48mmol) is dissolved in the solution 2C obtained in water 0.25g.At 25 DEG C, in solution 1A, add solution 1B while stirring, then add solution 1C.Dispersion liquid gradually becomes dark-brown.Stir after 7 days, carry out purifying by dialysis, obtain aqueous dispersions (B-2).

Take 1 part of aqueous dispersions obtained (B-2), measured by the visible absorption spectra of 10 times of diluents, confirm the peak of plasma absorption spectrum at 400nm place, confirm to generate silver nano-grain.In addition, the silver nano-grain of below 20nm is confirmed as by tem observation.

After the solvent distillation of the aqueous dispersions (B-2) obtained being removed, measured by TGA and measure silver content, result is 83%.In addition, the aqueous dispersions obtained did not find gathering, precipitation etc. at 2 months yet, confirmed excellent storage stability.

Synthesis example 20

In synthesis example 19, in solution 2A, add solution 2C, then add solution 1B, in addition, to operate equally with synthesis example 19, obtain aqueous dispersions (B-3).The aqueous dispersions obtained is stablized, and takes 1 part of dispersion liquid, is measured, confirm the peak of plasma absorption spectrum at 400nm place by the visible absorption spectra of 10 times of diluents, confirms to generate silver nano-grain.In addition, by tem observation, the silver nano-grain of below 20nm is confirmed as.

Synthesis example 21

In synthesis example 19, in solution 2A, add solution 2C, stir after 7 days, add solution 2B, then stir 7 days, in addition, to operate equally with synthesis example 19, obtain aqueous dispersions (B-4).The aqueous dispersions obtained is stablized, and takes 1 part of dispersion liquid, is measured, confirm the peak of plasma absorption spectrum at 400nm place by the visible absorption spectra of 10 times of diluents, confirms to generate silver nano-grain.In addition, by tem observation, the silver nano-grain of below 20nm is confirmed as.

Synthesis example 22 ~ 24

In synthesis example 19, use following solution to replace solution 2A, in addition, to operate equally with synthesis example 19, obtain aqueous dispersions (B-5 ~ 7).

[table 1]

	Compound (b1)	Ethylene imine units amount/water
			Synthesis example 22	(P1-3)	0.15mmol/2.41g(20mg)
Synthesis example 23	(P1-5)	0.15mmol/2.41g
			Synthesis example 24	(P1-6)	0.15mmol/2.41g

The aqueous dispersions obtained is all stable, takes 1 part of dispersion liquid, is measured, confirm the peak of plasma absorption spectrum near 400nm by the visible absorption spectra of 10 times of diluents, confirms to generate silver nano-grain.In addition, by tem observation, the silver nano-grain of below 40nm is confirmed as.

Synthesis example 25 (water dispersion of the Production Example 8-Argent grain of the dispersion (B) of metallic particles)

Add in the aqueous dispersions 5.0g (EI unit: 0.41mmol) of the compound (P1-2) obtained in synthesis example 21 and Silver Nitrate 0.02g (0.12mmol) is dissolved in water 5.0g and the silver nitrate aqueous solution that obtains, stir at 25 DEG C.Dispersion liquid gradually becomes light brown.After 7 days, carry out purifying by dialysis, obtain aqueous dispersions (B-8).The aqueous dispersions obtained is stablized, and takes 1 part of dispersion liquid, is measured, confirm the peak of plasma absorption spectrum near 400nm by the visible absorption spectra of 10 times of diluents, confirms to generate silver nano-grain.In addition, by tem observation, the silver nano-grain of below 40nm is confirmed as.

Synthesis example 26

Preparation comprises 85%N, the reductant solution of (methyl) acrylic polymers of obtaining in N-diethyl hydroxylamine 463g (4.41mol), above-mentioned synthesis example 7 (P2-1, be equivalent to non-volatile matter 23.0g) and water 1250g.In addition, (methyl) acrylic polymers (P2-1) being equivalent to obtain in the synthesis example 7 of non-volatile matter 11.5g is dissolved in water 333g, add wherein and Silver Nitrate 500g (2.94mol) is dissolved in water 833g and the solution obtained, fully stir.In this mixture, aforementioned reductant solution was dripped with 2 hours under room temperature (25 DEG C).The reaction mixture membrane filter (pore diameter 0.45 micron) obtained is filtered, make filtrate circulation in hollow fiber type ultrafiltration module (MOLSEP MODULE FB-02 type, molecular weight cut-off 150,000 that DAICEN MEMBRENE-SYSTEMS LTD. manufactures), the water adding the amount corresponding with the amount of filtrate flowed out at any time carries out purifying.After confirming that the specific conductivity of filtrate is 100 below μ S/cm, stop water filling and concentrate.Enriched material is reclaimed, obtains the silver nano-grain dispersion liquid (dispersion medium is water: B-9) (742.9g) of non-volatile content 36.7%.The median size of the Argent grain utilizing dynamic light scattering method to obtain is 39nm, is estimated as 10-40nm from TEM image.Measure the silver content in non-volatile matter by thermogravimetric analysis, result is 94.8w/w% (yield 81%).

Synthesis example 27

Preparation comprises 85%N, (methyl) acrylic polymers (P2-2 is equivalent to non-volatile matter 106mg) obtained in N-diethyl hydroxylamine 5.56g (53.0mmol), above-mentioned synthesis example 8 and the reductant solution of water 15g.In addition, (methyl) acrylic polymers (P2-2) being equivalent to obtain in the synthesis example 8 of non-volatile matter 106mg is dissolved in water 5g, add wherein and Silver Nitrate 6.00g (35.3mmol) is dissolved in the solution obtained in water 10g, fully stir.In this mixture, aforesaid reductant solution was dripped with 2 hours under room temperature (25 DEG C).The reaction mixture membrane filter (pore diameter 0.45 micron) obtained is filtered, make filtrate circulation in hollow fiber type ultrafiltration module (MOLSEP MODULE HIT-1 type, molecular weight cut-off 150,000 that DAICEN MEMBRENE-SYSTEMSLTD. manufactures), the water adding the amount corresponding with the amount of filtrate flowed out at any time carries out purifying.After confirming that the specific conductivity of filtrate is 100 below μ S/cm, stop water filling and concentrate.Reclaim enriched material, obtain the aqueous dispersions (B-10) of the silver nano-grain of non-volatile content about 30%.The particle diameter of this silver nano-grain is estimated as 10-40nm from TEM image.

Synthesis example 28 ~ 31

As compound, the compound (P2-3 ~ 6) of following table is used to replace (methyl) acrylic polymers obtained in synthesis example 8, in addition, carry out same operation with synthesis example 27, all obtain the aqueous dispersions (B-11 ~ 14) of the silver nano-grain of non-volatile content about 30%.The particle diameter of this silver nano-grain is estimated as 10-40nm from TEM image.

[table 2]

	Protective material
		Synthesis example 28	Synthesis example 9 (P2-3)
Synthesis example 29	Synthesis example 10 (P2-4)
		Synthesis example 30	Synthesis example 11 (P2-5)
Synthesis example 31	Synthesis example 12 (P2-6)

Synthesis example 32

(methyl) acrylic polymers obtained in synthesis example 7 (P2-1, be converted into solids component be 0.106g) is dissolved in water 12mL, add 1mol/L nitric acid 12mL wherein, then, add and Silver Nitrate 6.00g (35.3mmol) is dissolved in water 24mL and the solution obtained and trolamine 13.2g (88.3mmoL), stir 2 hours at 60 DEG C, obtain the solution of muddy brown.After cooling, by ultrafiltration module (MOLSEPMODULE HIT-1 type, molecular weight cut-off 150,000,1 that DAICEN MEMBRENE-SYSTEMS LTD. manufactures), circulation purified water carries out purifying until ooze out the transudate of about 1L from ultra filtration unit further.Stop supply purified water and concentrate, obtaining the aqueous dispersions (B-15) (solids component 30w/w%) of the Argent grain of 12.5g.The particle diameter of this silver nano-grain is estimated as 10-40nm from TEM image.

Synthesis example 33

(methyl) acrylic polymers obtained in synthesis example 7 (P2-1, be converted into solids component be 0.106g) is dissolved in water 12mL, add 1mol/L nitric acid 12mL wherein, then, add Silver Nitrate 6.00g (35.3mmol) is dissolved in the solution obtained in water 24mL.At room temperature slowly drip in this solution and DMAE 7.87g (88.3mmoL) is dissolved in the solution obtained in water 15mL.After dropping, at room temperature stir 3 days, obtain the solution of muddy brown.Make it by ultrafiltration module (MOLSEPMODULE HIT-1 type, molecular weight cut-off 150,000,1 that DAICEN MEMBRENE-SYSTEMS LTD. manufactures), and then circulation purified water carry out purifying until ooze out the transudate of about 1L from ultra filtration unit.Stop supply purified water and concentrate, obtaining the aqueous dispersions (B-16) (solids component 30w/w%) of the Argent grain of 12.5g.The particle diameter of this silver nano-grain is estimated as 10-40nm from TEM image.

Synthesis example 34

Preparation comprises 85%N, the reductant solution of (methyl) acrylic copolymer of obtaining in N-diethyl hydroxylamine 5.56g (53.0mmol), synthesis example 7 (P2-1, be equivalent to non-volatile matter 106mg) and water 15g.In addition, (methyl) acrylic polymers (P2-1) being equivalent to obtain in the synthesis example 7 of non-volatile matter 106mg is dissolved in water 5g, add wherein and Silver Nitrate 6.00g (35.3mmol) is dissolved in the solution obtained in water 10g, fully stir.To this mixture, dripped aforesaid reductant solution with 2 hours under ice-cooling.Make the reaction mixture circulation in hollow fiber type ultrafiltration module (MOLSEP MODULE HIT-1 type, molecular weight cut-off 150,000 that DAICENMEMBRENE-SYSTEMS LTD. manufactures) obtained, the water adding the amount corresponding with the amount of filtrate flowed out at any time carries out purifying.The specific conductivity of confirmation filtrate is after 100 below μ S/cm, stops water filling to be also concentrated into about 10mL.While add ethanol in ultrafiltration system, the ethanol of the amount suitable with the amount of filtrate flowed out is added on limit at any time, carries out exchange of solvent.After flowing out the ethanol filtrate of 100mL, concentrate, obtain the alcohol dispersion liquid (B-17) of the silver-containing nanoparticles complex body of non-volatile content about 60%.

Synthesis example 35

(methyl) acrylic polymers obtained in synthesis example 7 (P2-1, be converted into solids component be 2.00g) is dissolved in water 40mL, adds and venus crystals hydrate 10.0g (50.09mmol) is dissolved in the solution obtained in water 500mL.Dripping 80% hydrazine aqueous solution 10g (about 160mmol) wherein with about 2 hours makes it steadily foam, and then at room temperature stirs 1 hour until foaming stops, and obtains solution russet.

Make it by ultrafiltration module (DAICEN MEMBRENE-SYSTEMS LTD. manufacture, molecular weight cut-off 150,000,1), and then circulation has utilized nitrogen bubbling to carry out, and degassed purified water carry out purifying until ooze out the transudate of about 1L from ultra filtration unit.Stop supply de aerated water and concentrate, obtaining aqueous dispersions (B-18) (solids component is about 20w/w%) of 15g.This dispersion liquid is dissolved in ethanol (50mL) and measures ultraviolet-visible absorption spectroscopy, near 600nm, find the absorption being derived from plasma resonance, confirm to generate copper nano particles.The particle diameter of this copper nano particles is estimated as 30-80nm from TEM image.

Synthesis example 36

To in the mixture comprising Sulfide-containing Hindered organic compound (P3-1,0.451g) and the ethylene glycol (10mL) obtained in venus crystals (II) monohydrate (3.00g, 15.0mmol), above-mentioned synthesis example 13, while be blown into the heating of nitrogen limit with the flow of 50mL/ minute, at 125 DEG C, aeration-agitation is carried out degassed in 2 hours.This mixture is returned to room temperature, slowly drips the solution obtained with 7mL water dilution hydrazine hydrate (1.50g, 30.0mmol) with syringe pump.Now, can foam tempestuously due to the nitrogen produced along with initial reduction reaction, therefore should be noted that.Slowly dripped about 1/4 amount with 2 hours, at this moment temporarily stop dropping, stir 2 hours, confirm after foaming calms down, then dripped remaining amount with 1 hour.By the solution warms to 60 DEG C of brown obtained, then stir 2 hours, reduction reaction is terminated.Now, through time take a small amount of reaction soln russet, dilute by the degassed purified water that with the addition of 0.1% hydrazine hydrate, then obtain ultraviolet-visible absorption spectroscopy immediately, observe peak at 570 ~ 580nm place.It is for deriving from the absorption of going back the plasmon absorption shown by native copper of nano-scale.Can confirm thus to generate nano copper particle.

(preparation of water dispersion)

Then, hollow fiber type hyperfiltration membrane assembly (HIT-1-FUS1582,145cm that this reaction mixture manufactures at DAICEN MEMBRENE-SYSTEMS LTD. is made ², molecular weight cut-off 150,000) in circulation, while add the 0.1% hydrazine hydrate aqueous solution with the filtrate equivalent of oozing out, while carry out circulatory purification till the filtrate from ultrafiltration module reaches about 500mL.Stop the supply 0.1% hydrazine hydrate aqueous solution, keep this state and concentrated by ultrafiltration process, obtaining the water dispersion (B-19) of the organic compound of 2.85g and the complex body of nano copper particle.Non-volatile content in dispersion is 16%, metal content in non-volatile matter is 95%.With the observable copper particle of electron microscope, be judged as the particulate of about 20 ~ 60nm.In addition, be now 108nm by the median size of dynamic light scattering determination.Can confirm as from the Wide angle X-ray diffraction of dispersion and go back native copper.

Synthesis example 37 ~ 40

For the Sulfide-containing Hindered organic compound (P3-2 ~ 5) of synthesis example 14 ~ 17, also operate in the same manner as synthesis example 36, prepare dispersion liquid (B-20 ~ 23).Get a part of reaction mixture, measure ultraviolet-visible absorption spectroscopy, results verification to: use any one compound can observe the maximum absorption deriving from nano copper particle surface plasma body resonant vibration between 570 ~ 600nm.

Synthesis example 41

Use propylene glycol monomethyl ether (10mL) to replace the ethylene glycol (10mL) of synthesis example 36, in addition, carry out in the same manner as synthesis example 36, prepare dispersion liquid (B-24).Get a part of reaction mixture, measure ultraviolet-visible absorption spectroscopy, results verification to: between 570 ~ 600nm, observe the maximum absorption deriving from nano copper particle surface plasma body resonant vibration.The particle diameter of this silver nano-grain is estimated as 20-80nm from TEM image.

Synthesis example 42

To in the mixture comprising the Sulfide-containing Hindered organic compound (P3-1,2.254g) obtained in Red copper oxide (I) (5.4g, 37.5mmol), above-mentioned synthesis example 13, the silver nano-grain dispersion liquid (B-9, particle diameter 10-40nm, silver-colored 3.0 milligram-atoms, water solvent) obtained in above-mentioned synthesis example 26, ethanol 80ml and water 20ml, while be blown into nitrogen with the flow of 50mL/ minute, while be heated to 40 DEG C.Add hydrazine monohydrate (7.5g, 150mmol) further in the mixture.Stir 2 hours under the state remaining on 40 DEG C, terminate reduction reaction.

Then, hollow fiber type hyperfiltration membrane assembly (HIT-1-FUS1582,145cm that this reaction mixture manufactures at DAICEN MEMBRENE-SYSTEMS LTD. is made ², molecular weight cut-off 150,000) in circulation, limit add with the filtrate equivalent of oozing out, the 0.1% hydrazine aqueous solution that carried out nitrogen bubbling, limit circulatory purification is until the filtrate from ultrafiltration module reaches about 500mL.Stop the supply 0.1% hydrazine aqueous solution and concentrate, obtaining silver-colored core copper core-shell nanoparticles dispersion liquid (B-25) of 27.9g.Non-volatile content in dispersion liquid is 15%, metal content in non-volatile matter is 95%.With the observable particle of electron microscope, be judged as the particulate of about 40 ~ 80nm.In addition, silver can be confirmed as by the Wide angle X-ray diffraction of dispersion and go back the mixture of native copper.In addition, measuring known by TEM photo and TEM-EDS is silver-colored core copper shell particle.In addition, take the solution russet obtained on a small quantity, spent glycol dilutes, and obtains ultraviolet-visible absorption spectroscopy, and result observes the peak going back the plasmon absorption of 565 ~ 580nm of native copper display of nano-scale.In addition, even if obtaining ultraviolet-visible absorption spectroscopy to ethylene glycol diluent after 1 hour, the peak of plasmon absorption is not reducing yet, it can thus be appreciated that oxidation-resistance is good.

Synthesis example 43 ~ 47

The mixture comprising ethanol 80ml and water 20ml of synthesis example 42 is changed to the mixed solvent of following table, in addition, to operate equally with synthesis example 42, make silver-colored core copper core-shell nanoparticles dispersion (B-26 ~ 30).With the observable particle of electron microscope, be judged as the particulate of about 40 ~ 80nm.In addition, silver can be confirmed as from the Wide angle X-ray diffraction of dispersion and go back the mixture of native copper.

[table 3]

	Mixed solvent	Blending ratio (ml/ml)
			Synthesis example 43	IPA/ water	80/20
Synthesis example 44	Glycol/water	80/20
			Synthesis example 45	Ethanol/water	50/50
Synthesis example 46	Ethanol/water	10/90
			Synthesis example 47	Water	100

Relatively synthesis example 1

Based on the embodiment 1 of patent documentation 4, Silver Nitrate (I) 50 μm of ol are dissolved in pure water 94ml, this solution is stirred on limit tempestuously, while inject the aqueous solution 1ml containing stearyl ammonio methacrylate 10mg and the aqueous solution 5ml containing sodium borohydride 200 μm of ol successively in this solution, result, it is transparent that liquid color is changed to tawny, obtains silver-colored water-sol 100ml.

Relatively synthesis example 2

Based on the embodiment 2 of patent documentation 5, Sulfuric acid disilver salt 10mmol is dissolved in pure water 800ml, in this solution, adds the aqueous solution 100ml containing polyoxyethylene stearyl base ether phosphoric acid 500mg while stirring, make it reach even.Then, the aqueous solution 50ml containing dimethyamine borane 5mmol is added on vigorous stirring limit, limit in this solution, makes it reach uniform mode.When solution colour cataclysm is sorrel, add the aqueous solution 50ml containing 0.02mmol Palladous nitrate.Its result, obtains even and that sorrel is transparent silver-colored particle dispersion liquid 1000ml.

Embodiment 1

(formation of the non-conductive layer on insulativity base material)

Ethanol is added in the water dispersion (B-1) of the Argent grain made in synthesis example 18, form the Argent grain dispersion liquid of silver concentration 5%, water/ethanol (1/1 (w/w)), add the KF-351A (manufacture of Shin-EtsuChemical Co., Ltd.) of 0.1%.Use the K101 rod (wet type thickness 4 μm) of No. 0, with K-controlcoater (K101, RK Print Coat Instruments Ltd, manufacture) the condition of speed scale 10, this dispersion liquid is coated with (rod is coated with) on Kapton (Kapton EN150-C, 38 μm of thick, DuPont-Toray Co., Ltd. manufactures).After making the at room temperature drying of this film, observe the surface of this film, result with scanning electron microscope, the covering rate of the polyimide surface that Argent grain brings is about 90%.Measure the resistance of silver-colored film coated surface, result, owing to being 10 ⁷the resistance of more than Ω and cannot measuring, the film confirming the Argent grain formed on Kapton is dielectric film.

(electroless copper operation)

Using the test film of above-mentioned Argent grain coating Kapton as plating, the electroless plating reagent using Okuno Chemical Industries Co., Ltd. to manufacture carries out electroless plating.The operation of electroless copper is undertaken by the operation sequence via degreasing, washing, activation, washing, electroless plating, washing.Washing is the flowing water washing of 2 minutes.

1. degreasing: use grease-removing agent (ICP Cleaner SC, Okuno Chemical Industries Co., Ltd. manufacture), flood 5 minutes in the treatment solution of 40 DEG C.

2. activate: dipping 2 minutes in the aqueous sulfuric acids of 25 DEG C (about 6%).

3. electroless plating: use chemical bronze plating liquid (OIC COPPER, Okuno Chemical Industries Co., Ltd. manufacture), flood 20 minutes at 55 DEG C in the plating liquid of pH12.5.

The coated side surface integral of the Argent grain of the test film chemically taken out in copper plating bath becomes light red, can confirm to have carried out the electroless plating of copper well.Test film washing, air-dry after at 100 DEG C, carry out the baking of 60 minutes.The sheet resistance value of the copper film formed by electroless plating is 0.04 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.The conductive layer of the copper formed thus is utilized to the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.), result does not confirm stripping, and adaptation is also good.

Embodiment 2 ~ 5

In embodiment 1, by on Kapton, be coated with masking Argent grain film drying at room temperature after, sinter with the temperature shown in following table, time, in addition, operate similarly to Example 1, Kapton is formed the non-conductive layer with (Fig. 7-14) Argent grain of the surface-coated rate shown in following table, operate similarly to Example 1, carry out electroless copper, result, under all sintering temperatures, all form good copper plating film, the conductive material of conductive layer Kapton with copper can be produced on.

[table 4]

Embodiment 7 ~ 13

In embodiment 1, the dispersion of used Argent grain is changed to by the water dispersion (B-1) of the Argent grain made in synthesis example 18 water dispersion (B-2 ~ 8) obtained in synthesis example 19 ~ 25, in addition, operate similarly to Example 1, Kapton is formed the non-conductive layer of Argent grain, operate similarly to Example 1, carry out electroless copper, result, in all of the embodiments illustrated, all form good copper plating film, can be produced on Kapton and there is the conductive material that surface resistivity is the conductive layer of the copper of about 0.04 ~ 0.06 Ω/.

[table 5]

Embodiment 14 ~ 48

In embodiment 7 ~ 13, by on Kapton, be coated with masking Argent grain film drying at room temperature after, with the temperature shown in following table, time sinters, in addition, operate similarly to Example 1, Kapton is formed the non-conductive layer of Argent grain, operate similarly to Example 1, carry out electroless copper, result, all Argent grain dispersions, good copper plating film is all formed under all sintering temperatures, can be produced on Kapton and there is the conductive material that surface resistivity is the conductive layer of the copper of about 0.04 ~ 0.08 Ω/.

[table 6]

Embodiment 49

Use the conductive material of that obtain in embodiment 1, that there is copper on Kapton conductive layer, carry out electroplating (copper sulfate).Copper sulfate plating carries out based on the operation of ordinary method via degreasing, washing, pickling, washing, copper sulfate plating, washing, antirust treatment, washing.

1. degreasing: use grease-removing agent (DP320 Cleaner, Okuno Chemical Industries Co., Ltd. manufacture), flood 5 minutes in the treatment solution of 45 DEG C.

2. pickling: dipping 1 minute in the aqueous sulfuric acids of 25 DEG C (about 5%).

3. copper sulfate plating: use the copper sulfate plating liquid being added with Top Lucina SF-M (Okuno Chemical Industries Co., Ltd.'s manufacture), at 23 DEG C, 2.5A/dm ²condition under dipping 29 minutes.

4. antirust treatment: use rust-preventive agent (Top Rinse CU-5, Okuno Chemical Industries Co., Ltd. manufacture), flood 1 minute at 25 DEG C.

The test film electroplated wipes moisture away after washing, carries out warm air drying afterwards, carries out the baking of 60 minutes at 120 DEG C.The average film thickness of the layers of copper formed on Kapton after plating is 16 μm, can be produced on the conductive material 38 μm of thick Kaptons with 16 μm of thick conductive layer.The stripping strength of the copper that Kapton is formed is 9-10N/cm, demonstrates good dhering strength.

Embodiment 50 ~ 54

In embodiment 49, use the conductive material obtained in embodiment 2 ~ 6 to replace using the conductive material obtained in embodiment 1, electroplate in the same manner as embodiment 49.The average film thickness of the layers of copper that Kapton is formed is 16 μm, can be produced on the conductive material 38 μm of thick Kaptons with 16 μm of thick conductive layer.The stripping strength of the copper that Kapton is formed is as shown in the table demonstrates good dhering strength.

[table 7]

Embodiment	The electro-conductive material used in plating	The stripping strength (N/cm) of the layers of copper after plating
			50	Embodiment 2	9～10
51	Embodiment 3	8～9
			52	Embodiment 4	8～9
53	Embodiment 5	10～11
			54	Embodiment 6	10～11

Embodiment 55 ~ 61

In embodiment 49, the conductive material obtained in the embodiment using following table to record replaces using the conductive material obtained in embodiment 1, electroplates in the same manner as embodiment 49.The average film thickness of the layers of copper that Kapton is formed is 16 μm, can be produced on the conductive material 38 μm of thick Kaptons with 16 μm of thick conductive layer.The stripping strength of the copper that Kapton is formed is as shown in the table demonstrates good dhering strength.

[table 8]

Embodiment	The electro-conductive material used in plating	The stripping strength (N/cm) of the layers of copper after plating
			55	Embodiment 18	10～11
56	Embodiment 23	10～11
			57	Embodiment 28	10～11
58	Embodiment 33	9～10
			59	Embodiment 38	9～10
60	Embodiment 43	9～10
			61	Embodiment 48	10～11

Embodiment 62 ~ 69

In embodiment 1,7 ~ 13, use alcoholic dispersion replacement use water dispersion (B-1) being exchanged for the Argent grain of ethanol by water solvent, the alcoholic dispersion of silver concentration 5% is coated on Kapton, in addition, to operate equally with embodiment 1,7 ~ 13, after Kapton carries out coating drying, sintering to the non-conductive layer of silver, carry out electroless plating, be produced on Kapton and there is the conductive material that surface resistivity is the conductive layer of the copper of 0.04-0.05 about Ω/.

Use these conductive materials, to operate equally with embodiment 49, electroplate.The average film thickness of the layers of copper that Kapton is formed is 16 μm, can be produced on the conductive material 38 μm of thick Kaptons with 16 μm of thick conductive layer.The stripping strength of the copper that Kapton is formed is 9 ~ 11N/cm, demonstrates good stripping strength.

[table 9]

Embodiment 70 ~ 71

In embodiment 62, to the alcoholic dispersion of silver concentration 5%, on Kapton silver coating non-conductive layer and carry out drying, under the sintering temperature of 100 DEG C or 270 DEG C, sintering is after 5 minutes, carries out electroless plating.The surface resistivity of the layers of copper on Kapton is about 0.04 ~ 0.05 Ω/.Use this conductive material, operate same with embodiment 49 is electroplated.The average film thickness of the layers of copper that Kapton is formed is 16 μm, can be produced on the conductive material 38 μm of thick Kaptons with 16 μm of thick conductive layer.The stripping strength of the copper that Kapton is formed is as shown in the table demonstrates good dhering strength.

[table 10]

Comparative example 1

In the Argent grain dispersion liquid make Kapton in relatively Production Example 1, dipping 10 minutes, makes Kapton surface adsorption silver colloid, after the at room temperature drying of this film, at 180 DEG C, sinters 30 minutes.Observe the surface (Figure 15,16) of this film with scanning electron microscope, result, the covering rate of the polyimide surface that Argent grain brings is 8%.

(electroless copper operation)

Adsorbed the Kapton of silver colloid to this, operated similarly to Example 1, carried out Electroless Plating Procedure, result, the part being adsorbed on the silver colloid on surface departs from degreasing fluid dipping.The precipitation of the copper in electroless copper operation is speckled uneven precipitation, account for all surfaces long-pending about 30%.

Comparative example 2

Utilize vaporizer from the silver-colored water-sol comparing making Production Example 1 except anhydrating and simmer down to 0.5%.Now, silver colloid is assembled, and dispersion liquid heterogeneous.When using this concentrated solution to operate similarly to Example 1 to be coated on Kapton, uniform film cannot be obtained.Thereafter, carry out Electroless Plating Procedure although attempt to operate similarly to Example 1, the silver colloid aggregation being attached to surface departs from degreasing fluid dipping, and the precipitation of copper does not occur.

Comparative example 3

In the Argent grain dispersion liquid make Kapton in relatively Production Example 2, dipping 10 minutes, makes Kapton surface adsorption silver colloid, after the at room temperature drying of this film, at 180 DEG C, sinters 30 minutes.Observe the surface of this film with scanning electron microscope, result, the covering rate of the polyimide surface that Argent grain brings is 15%.

(electroless copper operation)

Adsorbed the Kapton of silver colloid to this, operation carries out Electroless Plating Procedure, result similarly to Example 1, and the part being adsorbed on the silver colloid on surface departs from degreasing fluid dipping.The precipitation of the copper in electroless copper operation is speckled uneven precipitation, account for all surfaces long-pending about 40%.

Comparative example 4

Utilize vaporizer from the Argent grain dispersion liquid comparing making Production Example 2 except anhydrating and being concentrated into 1%.Now, silver colloid is assembled, and dispersion liquid heterogeneous.This concentrated solution is operated similarly to Example 1 when being coated on Kapton, uniform film cannot be obtained.

Adsorbed the Kapton of silver colloid to this, operation carries out Electroless Plating Procedure, result similarly to Example 1, and the part being attached to the silver colloid aggregation on surface departs from degreasing fluid dipping.The precipitation of the copper in electroless copper operation is speckled uneven precipitation, account for all surfaces long-pending about 50%.

Comparative example 5

Operate equally with the embodiment 1 of patent documentation 2, after obtaining Red copper oxide dispersion, to operate equally with embodiments of the invention 1, coating (rod is coated with) is on Kapton.After the at room temperature drying of this film, at 350 DEG C, sinter 60 minutes.Observe the surface of this film with scanning electron microscope, result, the covering rate of the polyimide surface that copper particle brings is 100%.

Using the test film of the Kapton of above-mentioned band electroconductibility copper membrana granulosa as plating, operate similarly to Example 1, carry out electroless plating, result, the sheet resistance value of the copper film formed by electroless plating is 0.04 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.Operate similarly to Example 1, the conductive layer of copper is utilized to the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.), result, peel off for whole that is bonded with adhesive tape.

Comparative example 6

In embodiment 1, silver concentration is changed to 22% by 5%, in addition, operate similarly to Example 1, use the K101 rod (wet type thickness 6 μm) of No. 0, under the condition of the speed scale 10 of K-control coater (K101, RK PrintCoat Instruments Ltd. manufactures), the dispersion liquid of Argent grain is coated with (rod is coated with) on Kapton (Kapton EN150-C, 38 μm of thick, Du Pont-Toray Co., Ltd. manufactures).After the at room temperature drying of this film, at 180 DEG C, sinter 30 minutes.The surface of this film is observed with scanning electron microscope, result, the covering rate of the polyimide surface that Argent grain brings is 100% (Figure 17), and the average stacked number of the nanometer silver of the polyimide surface converted by thickness is 6 layers (Figure 18).Measure the resistance of silver-colored film coated surface, result, define the conductive film that surface resistivity is about 0.4 Ω/.

(electroless copper operation)

Using the test film of the Kapton of above-mentioned band conductive silver membrana granulosa as plating, operate similarly to Example 1, carry out electroless plating, result, the sheet resistance value of the copper film formed by electroless plating is 0.04 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.Operate similarly to Example 1, the conductive layer of copper is utilized to the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.), result, peel off for whole that is bonded with adhesive tape.

Comparative example 7

Use the base material on 38 μm of thick Kaptons with the conductive layer of copper obtained after utilizing the method for comparative example 1 to carry out electroless plating process, to operate equally with embodiment 49, carry out electroplating (copper sulfate).The average film thickness of the layers of copper formed on Kapton after plating is 16 μm.The stripping strength of the copper that Kapton is formed is about 1N/cm, for closely sealed bad.

Comparative example 8

In comparative example 1, do not carry out electroless copper process, use the Kapton of conductive layer with silver, to operate equally with embodiment 49, carry out electroplating (copper sulfate).The average film thickness of the layers of copper formed on Kapton after plating is about 15 μm.The stripping strength of the copper that Kapton is formed is about 1N/cm, for closely sealed bad.

Embodiment 72

(formation of the non-conductive layer on insulativity base material)

Add ethanol in the water dispersion (B-9) made in synthesis example 26, form the Argent grain dispersion liquid of silver concentration 5%, water/ethanol (1/1 (w/w)).Use the K101 rod (wet type thickness 4 μm) of No. 0, under the condition of the speed scale 10 of K-control coater (K101, RK Print Coat Instruments Ltd. manufactures), this dispersion liquid is coated with (rod is coated with) on Kapton (Kapton EN150-C, 38 μm of thick, Du Pont-Toray Co., Ltd. manufactures).After the at room temperature drying of this film, carry out the sintering of 5 minutes at 250 DEG C, by the surface of scanning electron microscope viewing film, result, the covering rate of the polyimide surface that Argent grain brings is about 95%.Measuring the resistance of silver-colored film coated surface, result, is 10 ⁷thus the resistance of more than Ω cannot measure, and confirms that the film formed by Argent grain formed on Kapton is dielectric film.

(electroless copper operation)

Using the test film of above-mentioned Argent grain coating Kapton as plating, the plating reagent using Okuno Chemical Industries Co., Ltd. to manufacture carries out electroless plating.The operation of electroless copper is undertaken by the flow chart via degreasing, washing, activation, washing, electroless plating, washing.Washing is the flowing water washing of 2 minutes.

1. degreasing: use grease-removing agent (OPC190 Cleaner, Okuno Chemical Industries Co., Ltd. manufacture), flood 5 minutes in the treatment solution of 60 DEG C.

Chemically the coated side surface integral of the Argent grain of the test film of copper plating bath taking-up is light red, can confirm and carry out the electroless plating of copper well.Test film washing, air-dry after at 100 DEG C, carry out the baking of 60 minutes.The sheet resistance value of the copper film formed by electroless plating is 0.04 Ω/, can be produced on the conductive material thick Kapton of 38 μm of insulativity base material with the conductive layer of copper.The conductive layer of the copper formed thus carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and unconfirmed to peeling off, adaptation is also good.

Embodiment 73

In embodiment 72, aqueous dispersions (B-10 ~ 16) is used to replace dispersion liquid (B-9), in addition, to operate equally with embodiment 72, be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.The sheet resistance value of copper film counts about 0.04 Ω/ with all material, and conductive layer carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and unconfirmed to peeling off, adaptation is also good.

Embodiment 74

In embodiment 72, change to dispersion liquid (B-17) and replace dispersion liquid (B-9), and form the alcohol dispersion liquid of Argent grain 5%, in addition, to operate equally with embodiment 72, be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.The sheet resistance value of copper film counts about 0.04 Ω/ with all material, and conductive layer carries out the result of the belt stripping test utilizing cellophane tape (NichibanCo., Ltd. manufacture), and unconfirmed to peeling off, adaptation is also good.

Embodiment 75

Be used in that obtain in embodiment 72 ~ 74, that there is the conductive layer of copper on 38 μm of thick Kaptons conductive material, operate equally with embodiment 49, carry out electroplating (copper sulfate).The average film thickness of the layers of copper formed on Kapton after plating is respectively 16 μm.The stripping strength of the copper that Kapton is formed is about 9 ~ 10N/cm, demonstrates good adaptation.

Embodiment 76

(formation of the non-conductive layer on insulativity base material)

Add ethanol in the water dispersion (B-18) of the copper particle made in synthesis example 35, form the copper particle dispersion of copper concentration 5%, water/ethanol (1/1 (w/w)).Use the K101 rod (wet type thickness 4 μm) of No. 0, under the condition of the speed scale 10 of K-control coater (K101, RK Print Coat Instruments Ltd. manufactures), this dispersion liquid is coated with (rod is coated with) on Kapton (KaptonEN150-C, 38 μm of thick, Du Pont-Toray Co., Ltd. manufactures).After the at room temperature drying of this film, carry out the sintering of 5 minutes at 250 DEG C, by the surface of scanning electron microscope viewing film, result, the covering rate of the polyimide surface that copper particle brings is about 95%.When measuring the resistance of silver-colored film coated surface, be 10 ⁷the resistance of more than Ω, thus cannot measure, and what confirm to be formed on Kapton is dielectric film by the granuloplastic film of copper.

(electroless copper operation)

Using above-mentioned copper particle coating Kapton as the test film of plating, use the plating reagent (OIC COPPER) that Okuno Chemical Industries Co., Ltd. manufactures, flood 20 minutes at 55 DEG C in the plating liquid of pH12.5, carry out electroless plating.

Chemically the coated side surface integral of the copper particle of the test film of copper plating bath taking-up is light red, can confirm to have carried out the electroless plating of copper well.Test film washing, air-dry after at 100 DEG C, carry out the baking of 60 minutes.The sheet resistance value of the copper film formed by electroless plating is 0.04 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.The conductive layer of the copper formed thus carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and unconfirmed to peeling off, adaptation is also good.

Embodiment 77

In embodiment 76, use dispersion liquid (B-19) to replace dispersion liquid (B-18), in addition, to operate equally with embodiment 76, carry out the coating of the copper particle on Kapton, electroless copper.The surface resistivity of copper plate is 0.04 Ω/, can be produced on the conductive material thick Kapton of 38 μm of insulativity base material with the conductive layer of copper.The conductive layer of the copper formed thus carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and unconfirmed to peeling off, adaptation is also good.

Embodiment 78

In embodiment 76, change to dispersion liquid (B-20 ~ 24) and replace dispersion liquid (B-18), in addition, to operate equally with embodiment 76, carry out the coating of the copper particle on Kapton, electroless copper.The surface resistivity of the copper plate of all films is 0.04 ~ 0.05 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.When the conductive layer of the copper formed thus is for any one, carry out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), all unconfirmed to peeling off, adaptation is also good.

Embodiment 79

In embodiment 76, the water dispersion (B-25) changing to the silver-colored core-copper shell particle obtained in synthesis example 42 replaces dispersion liquid (B-18), in addition, to operate equally with embodiment 76, carry out the silver-colored core-coating of copper shell particle on Kapton, electroless copper.The polyimide surface covering rate of silver core-copper shell particle is about 80%, after 250 DEG C of sintering, is measured confirm by silver-colored core-granuloplastic film of copper shell still for non-conductive by surface resistivity.The surface resistivity of the copper plate after electroless plating is 0.04 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.When the conductive layer of the copper formed thus is for any one, carry out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), all unconfirmed to peeling off, adaptation is also good.

Embodiment 80

In embodiment 79, change to dispersion liquid (B-26 ~ 30) and replace dispersion liquid (B-25), dispersion medium composition is not changed and by the concentration adjustment of silver-colored core-copper shell particle be only 5% dispersion liquid to operate equally with embodiment 79, carry out the silver-colored core-coating of copper shell particle on Kapton, electroless copper.After polyimide surface is coated with being sintered at 250 DEG C by silver-colored core-granuloplastic film of copper shell of masking, measure to confirm to be all still non-conductive by surface resistivity.The surface resistivity of the copper plate after electroless plating is 0.04 ~ 0.05 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.When the conductive layer of the copper formed thus is for any one, carry out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), all unconfirmed to peeling off, adaptation is also good.

Embodiment 81

Use in embodiment 76 ~ 80 that obtain, that there is the conductive layer of copper on 38 μm of thick Kaptons conductive material, to operate equally with embodiment 49, carry out electroplating (copper sulfate).The average film thickness of the layers of copper formed on Kapton after plating is respectively 16 μm.The stripping strength of the copper that Kapton is formed is about 9 ~ 10N/cm, demonstrates good adaptation.

Embodiment 82

In embodiment 1, embodiment 72, insulativity base material is changed to the Kapton of following table by Kapton EN150-C, in addition, with embodiment 1, embodiment 72 is same operates, silver coating particle on film, is formed after comprising the non-conductive layer of Argent grain, to operate equally with embodiment 1,72, carry out electroless plating, result, for all the conductive layer that surface resistivity is the copper of 0.04 ~ 0.05 Ω/ can be formed on Kapton time any one.Carry out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), confirm layers of copper unstripped, define the film with sufficient adaptation.

[table 11]

Base material	Base material manufacturers	Film thickness
			Kapton 100-EN	Du Pont-Toray Co.,Ltd.	25μm
UPILEX-25S	The emerging product in space portion	25μm

Use these conductive materials, to operate equally with embodiment 49, carry out electroplating (copper sulfate).The average film thickness of the layers of copper formed on Kapton after plating is 16 μm.The stripping strength of the copper that Kapton is formed is about 8 ~ 10N/cm, obtains sufficient stripping strength.

Embodiment 83

In embodiment 1, embodiment 72, insulativity base material is changed to the epoxy glass plywood (thickness 3mm) of solar one-tenth Co., Ltd. manufacture by Kapton EN150-C, in addition, with embodiment 1, embodiment 72 is same operates, Coating dispersions on epoxy glass plywood, after forming the non-conductive layer containing Argent grain, to operate equally with embodiment 1,72, carry out electroless plating, as a result, for all the conductive layer that surface resistivity is the copper of 0.04 ~ 0.05 Ω/ can be formed on epoxy glass plywood time any one.Carry out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), confirm layers of copper unstripped, define the copper film with sufficient adaptation.Use this conductive material, operate same with embodiment 49 carries out electroplating (copper sulfate), result, and the average film thickness of the layers of copper formed on epoxy glass plywood after plating is 16 μm.

Embodiment 84

In embodiment 1, embodiment 72, insulativity base material is changed to KURARAY VECSTAR CT-Z by Kapton EN150-C, in addition, with embodiment 1, embodiment 72 is same operates, Coating dispersions on film, after forming the non-conductive layer containing Argent grain, to operate equally with embodiment 1,72, carry out electroless plating, result, for all the conductive layer that surface resistivity is the copper of 0.04 ~ 0.05 Ω/ can be formed on VECSTAR CT-Z film time any one.

Embodiment 85

(formation of the non-conductive layer on insulativity base material)

In embodiment 1, the Argent grain dispersion liquid of 0.5% is used to replace the Argent grain dispersion liquid of silver concentration 5%,, in addition, operate similarly to Example 1, at Kapton (Kapton EN150-C, 38 μm of thick, Du Pont-Toray Co., Ltd. manufacture) upper coating (rod is coated with) Argent grain dispersion liquid, after drying at room temperature, carries out the sintering of 210 DEG C, 5 minutes, as a result, surface-coated rate is 23%.

(electroless copper operation)

Using above-mentioned Argent grain coating Kapton as the test film of plating, use based on document (“ Now for めっ I textbook " electroplate research association's volume, daily magazine Industrial Co., Ltd (2011)) and the chemical plating fluid of making carries out electroless plating.The operation of electroless copper is undertaken by the flow chart via degreasing, washing, activation, washing, electroless plating, washing.Washing is the flowing water washing of 2 minutes.

3. electroless plating: use aforementioned “ Now for めっ I textbook " the following A P2 operation recorded in 302 pages, carry out the electroless plating process of 20 minutes.

AP2 operation

[table 12]

Copper sulfate	10g/L
		EDTA·2Na	30g/L
Formaldehyde (37%)	3mg/L
		Dipyridyl	Some
Polyoxyethylene glycol	Some
		pH	12.2
Bath temperature	70℃

The coated side surface integral of the Argent grain of the test film chemically taken out in copper plating bath is light red, can confirm to have carried out the electroless plating of copper well.Test film washing, air-dry after at 100 DEG C, carry out the baking of 60 minutes.The sheet resistance value of the copper film formed by electroless plating is 0.04 Ω/, can be produced on conductive material insulativity base material i.e. 38 μm of thick Kaptons with the conductive layer of copper.The conductive layer of the copper formed thus carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and unconfirmed to peeling off, adaptation is also good.

(plating)

Use the conductive material on polyimide with conductive layer obtained thus, operate same with embodiment 49 carries out electroplating (copper sulfate).

The test film electroplated wipes moisture away after washing, then carries out warm air drying, carries out the baking of 60 minutes at 120 DEG C.The average film thickness of the layers of copper formed on Kapton after plating is 16 μm, can be produced on the conductive material 38 μm of thick Kaptons with 16 μm of thick conductive layer.The stripping strength of the copper that Kapton is formed is about 8N/cm, demonstrates good dhering strength.

Embodiment 86

(formation of the non-conductive layer on insulativity base material)

Operate similarly to Example 1, the Argent grain dispersion liquid of 5% is coated with (rod is coated with) on Kapton (Kapton EN100-C, 25 μm of thick, Du Pont-Toray Co., Ltd. manufactures).After the at room temperature drying of this film, upset surface and the back side, operate silver coating coating fluid overleaf too.After drying at room temperature, carry out the sintering of 210 DEG C, 5 minutes.Measure the resistance of silver-colored film coated surface, result, two sides is 10 ⁷the resistance of more than Ω, thus cannot measure, and must arrive the Kapton that two sides has non-conductive layer.

This film is operated similarly to Example 1 and carries out electroless copper process, the conductive material insulativity base material i.e. two sides of 25 μm of thick Kaptons with the conductive layer of copper can be produced on.The conductive layer of the copper formed thus carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and two sides is all unconfirmed to peeling off, and adaptation is also good.

Use the conductive material on polyimide two sides with conductive layer obtained thus, to operate equally with embodiment 49, carry out the electro-coppering of 10 minutes, result, the conductive material that 25 μm of thick polyimide two sides have 5-6 μm of thick layers of copper respectively can be produced on.

Embodiment 87

(there is the formation of the non-conductive layer on the insulativity base material of through hole)

At Kapton (Kapton EN150-C, 38 μm of thick, Du Pont-Toray Co., Ltd. manufacture) on, eyelet punch is used to form the through hole of 6mm φ, in addition, to operate equally with embodiment 86, form the non-conductive layer of silver on the two sides of Kapton, carry out electroless copper process.

The conductive layer of the copper formed thus carries out the result of the belt stripping test utilizing cellophane tape (manufacture of Nichiban Co., Ltd.), and two sides is all unconfirmed to peeling off, and adaptation is also good.Make probes touch surface and the two sides, the back side of electric tester, energising can be confirmed, confirm surface and be connected by through hole with two sides, the back side.

utilizability in industry

In the present invention; use the dispersion liquid containing the metal particle protected by the compound with specific atoms more than specified quantitative; electro-conductive material is manufactured by the operation comprising certain working procedure; therefore, vacuum apparatus can not be needed, not with using organic adhesive with high performance conductive material, tellite substrate or printed circuit board (PCB) that low cost manufacture can utilize in high-density installation field.

Claims

1. a manufacture method for conductive material, is characterized in that, has following operation:

(1) at the upper Coating dispersions (B) of insulativity base material (A), form the operation of non-conductive layer (C), the metal particle (b2) of more than a kind that be selected from the group that gold and silver, copper and platinum be made up of by the compound (b1) with nitrogen-atoms, sulphur atom, phosphorus atom or Sauerstoffatom protected of described dispersion liquid (B) containing more than 0.5 quality %;

(2) electroless plating is carried out to the base material with non-conductive layer (C) obtained in (1), form the operation of conductive layer (D).

2. the manufacture method of conductive material according to claim 1, wherein, also has following operation:

(3) base material with conductive layer (D) obtained in (2) is electroplated, conductive layer (D) is formed the operation of metal conducting layer (E).

3. the manufacture method of conductive material according to claim 1 and 2, wherein, insulativity base material (A) is for by shaping to polyimide resin, liquid crystalline polymers or glass epoxy resin and base material that is that obtain.

4. the manufacture method of conductive material according to claim 3, is characterized in that, insulativity base material (A) is film, the base material of thin slice, tabular.

5. the manufacture method of conductive material according to claim 4, is characterized in that, the insulativity base material (A) of film, thin slice, tabular has the through hole connecting its surface and the back side.

6. the manufacture method of the conductive material according to any one of Claims 1 to 5, is characterized in that, the number-average molecular weight of described compound (b1) is the scope of 3000 ~ 50000.

7. the manufacture method of the conductive material according to any one of claim 1 ~ 6, wherein, described compound (b1) comprises the atom of more than two kinds of nitrogen-atoms, sulphur atom, phosphorus atom or Sauerstoffatom in 1 molecule.

8. the manufacture method of the conductive material according to any one of claim 1 ~ 7, wherein, described compound (b1) is for having the compound of amino, carboxyl, hydroxyl, sulfydryl, phosphate, quaternary ammonium group, quaternary phosphine base, cyano group, ether, thioether group or disulfide group.

9. the manufacture method of the conductive material according to any one of claim 1 ~ 8, wherein, the Sulfide-containing Hindered organic compound (P3) that described compound (b1) represents for having the compound (P1) of polymine block and polyoxyethylene glycol block, following (methyl) acrylic polymers (P2) or following general formula (1)

Described (methyl) acrylic polymers (P2) makes to have polyglycol chain (methyl) esters of acrylic acid macromonomer and has-OP (O) (OH) ₂(methyl) acrylic ester monomer of phosphate residue represented is polymerized and obtains under the existence of chain-transfer agent with the functional group that-SR represents, wherein, in-SR, R is the alkyl of carbon number 1 ~ 18, substituent phenyl can be had on phenyl ring, or have and select free hydroxyl, the alkoxyl group of carbon number 1 ~ 18, the aralkyl oxy of carbon number 1 ~ 18, substituent phenoxy group can be had on phenyl ring, carboxyl, the salt of carboxyl, the alkyl of the carbon number 1 ~ 8 of the functional group of more than 1 in the group of 1 valency of 1 valency of carbon number 1 ~ 18 or the alkyl-carbonyl oxygen base of multivalence and carbon number 1 ~ 18 or the alkoxy carbonyl composition of multivalence,

X-(OCH ₂CHR ¹) _n-O-CH ₂-CH(OH)-CH ₂-S-Z(1)

In formula (1), X is C ₁~ C ₈alkyl, R ¹for hydrogen atom or methyl, n is the integer of the repeat number of expression 2 ~ 100, R ¹each repeating unit be independently, can be the same or different, Z is C ₂~ C ₁₂alkyl, allyl group, aryl, aralkyl ,-R ²-OH ,-R ²-NHR ³, or-R ²-COR ⁴the group represented, wherein, R ²for C ₂~ C ₄alkylidene chain, R ³for hydrogen atom, C ₂~ C ₄acyl group, C ₂~ C ₄alkoxy carbonyl or C can be had on aromatic nucleus ₁~ C ₄alkyl or C ₁~ C ₈the benzyloxycarbonyl of alkoxyl group alternatively base, R ⁴for hydroxyl, C ₁~ C ₄alkyl or C ₁~ C ₈alkoxyl group.

10. the manufacture method of the conductive material according to any one of claim 1 ~ 9, wherein, the median size of described metal particle is the scope of 1 ~ 200nm.

The manufacture method of 11. conductive materials according to any one of claim 1 ~ 10, wherein, the containing ratio of the metal particle (b2) in described dispersion liquid (B) is the scope of 0.5 ~ 20wt%.

The manufacture method of 12. conductive materials according to any one of claim 1 ~ 11, wherein, described non-conductive layer (C) is the layer that the mode being the scope of 20 ~ 90 area % with the covering rate of the metal particle (b2) on insulativity base material (A) surface is formed.

The manufacture method of 13. conductive materials according to any one of claim 1 ~ 12, wherein, described non-conductive layer (C) is with the metal particle layer of the number of plies laminated metal particulate (b1) of less than 5 layers on insulativity base material (A).

The manufacture method of 14. conductive materials according to any one of claim 1 ~ 14, wherein, the resistance value of described non-conductive layer (C) is 10 ⁷more than Ω.

The manufacture method of 15. conductive materials according to any one of claim 1 ~ 14, is characterized in that, described non-conductive layer (C) is formed at the two sides of insulativity base material (A) of film, thin slice, tabular.

16. 1 kinds of conductive materials, is characterized in that, it utilizes the manufacture method according to any one of claim 1 ~ 15 to obtain.

17. conductive materials according to claim 16, it is use in printed circuit board laminated substrate.