CN104662198B

CN104662198B - Conductive material and its manufacture method

Info

Publication number: CN104662198B
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; 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: 2017-06-13
Anticipated expiration: 2033-09-11
Also published as: TWI577556B; JPWO2014045972A1; CN104662198A; KR20150058097A; WO2014045972A1; TW201420350A; JP5594449B2; KR102027193B1

Abstract

The present invention provide need not be engaged by bonding agent, do not use vacuum equipment the conductive layer with suitable thickness conductive material manufacture method.The manufacture method of conductive material of the invention has following operation：The Coating dispersions in insulating properties base material (1); the operation of non-conductive layer (3) is formed, the dispersion liquid contains the metal particle (2) selected from more than a kind in the group being made up of gold, silver, copper and platinum by the compound protection with nitrogen-atoms, sulphur atom, phosphorus atoms or oxygen atom more than 0.5 mass %；Chemical plating is carried out to the base material (1) with the non-conductive layer (3), the operation of conductive layer is formed.

Description

Conductive material and its manufacture method

Technical field

Manufacture method the present invention relates to can suitably be used as the conductive material of use in printed circuit board laminated substrate.This Outward, the conductive material the invention further relates to be manufactured using the manufacture method.

Background technology

Use in printed circuit board laminated substrate is the structure that the material of low-k is laminated with the thin layer of electric conductivity Material.All the time, for example, flexible copper-clad plywood (FCCL) is manufactured using following method：Use epoxy resin Method that bonding agent engages heat resistance macromolecule membrane with Copper Foil, on copper-clad surface the solution of coating resin and dry it etc. Method.

In recent years, due to electronic equipment miniaturization, high speed, it is desirable to the densification of tellite, high-performance Change, in order to tackle these requirements, it is desirable to develop the printed circuit with the smooth and sufficiently thin conductive layer (copper foil layer) in surface Substrate.

However, haveing the shortcomings that heat resistance is low, insulating reliability is also poor using the method for epoxide resin adhesive.This Outward, in the manufacture method of foregoing use Copper Foil, manufactured when the Copper Foil being rolled into a roll is pulled out, therefore existed in treatment Difficulty, thus Copper Foil cannot be made sufficiently thin, additionally, in order to improve adaptation with macromolecule membrane, it is necessary to by the table of Copper Foil Face be roughened so that densification, the high performance that cannot fully tackle printed circuit board (PCB) suppress high-frequency (5 GHz band), The requirement of the transmission loss under high transmission speed (tens of Gbps) scope.

Therefore, for printed circuit board (PCB) high performance requirement, for example disclose a kind of use by bonding agent Engagement and on macromolecule membrane be laminated copper lamina Copper thin film substrate (referring for example to patent document 1).The Copper thin film substrate In manufacture method, using sputtering method, ground floor copper film layer is set on heat resistance insulating substrate surface, is formed on the ground floor The copper thick film layers obtained using plating.

Copper thin film substrate described in aforementioned patent literature 1 can make copper foil layer relatively thin, therefore can tackle printed circuit board (PCB) Densification, the requirement of high performance, but it use the method for the sputtering for needing vacuum equipment, thus exist operation it is numerous and diverse and High cost, the problems such as equipment aspect substrate sizes are limited.

Accordingly, as without vacuum equipment and not using and can just make conductive layer (copper by the engagement of bonding agent in manufacture Layers of foil) sufficiently thin use in printed circuit board laminated substrate autofrettage, disclose following method：By the base material in insulating properties Upper coating metal particulate is filmed and carries out heat-agglomerating and form the conductive layer of metal, and plating is carried out on the conductive layer, Thus the method (referring for example to patent document 2~3) of the conductive copper layers of foil of necessary thickness is obtained.

In aforementioned patent literature 2, the manufacture method of the multilayer board including following operation is disclosed：(1) will contain because Heat and mutually welding, primary particle size is for the dispersion of metallic film precursor particles of below 200nm is coated on insulation On substrate and heated, be consequently formed metallic film and form the operation of conductive layer；(2) it is enterprising in aforementioned metal film Row electrolytic coating and form the operation of metal film.

Additionally, disclosing a kind of use in printed circuit board substrate and its manufacture method, the printing in aforementioned patent literature 3 Circuit board substrate is characterised by：There is the 1st conductive layer and the 2nd conductive layer being formed thereon in insulating properties base material, it is preceding State the 1st conductive layer constituted in the form of the coating layer of the electric conductivity ink of the metallic particles comprising 1-500nm, foregoing 2nd conductive layer Constituted in the form of coating layer.

In the above method, conductive metal layer and electroplated by being formed in insulating properties base material, from without using Vacuum equipment is excellent in terms of can obtaining the conductive film layer of appropriate thickness, but in order to implement electrolytic coating, it is necessary in advance Form the conductive metal film with sufficient electric conductivity.For example, in aforementioned patent literature 2, as making for this purpose Volumetric resistivity value required for metallic film, is recommended as 1 × 10^-4Below Ω cm, more preferably 1 × 10^-5Below Ω cm. The conductive layer of this low-resistivity is shown to be formed, it is necessary to make to be coated on the electric conductivity in insulating properties base material by heating Contained dispersant and other organic matters volatilize, decompose and removed from coating layer in ink, the dispersion of metal film precursor particles, shape Into the state of abundant welding between particle.

But, film obtained from the dispersion liquid of these small metallic particles and metallic film precursor granules will be coated with Heat-agglomerating and in the case of forming conductive film, it is difficult to fully fill void among particles, can be formed internal residual have compared with Lacunose metallic film.In addition, although the grain shape in film changes because of welding and Grain growth, a part of Intergranular links, but film integrally usually can be observed the phenomenon of coated density reduction.As a result, there is a problem of as follows： Generation can not show sufficient electric conductivity and cannot carry out that situation, the i.e. enable of plating carries out that plating is also required to grow very much when Between or the problems such as occur due to producing poor plating, the inhomogeneities of plating caused by local non-conduction portion.Additionally, picture So, local coated density is low, in the metallic film more than space, exist its space part turn into destruction starting point and cause conductive layer from The problems such as insulator base material is peeled off.

As the countermeasure of the problem, proposed in aforementioned patent literature 3：Insulation is filled by using Chemical metal plating The space in the first conductive layer formed on body base material, so as to eliminate poor flow, reduce the destruction that can turn into the reason for peeling off Starting point, but the space usually presence in the form of isolating space inside film by heat-agglomerating in the conductive film of welding, Liquid is impermeable, therefore, exist still in the form of space after chemical plating sometimes, sufficient solution can not be referred to as.

Additionally, as the catalyst of chemical plating, usually using palladium, but when using the palladium of costliness as catalyst metals, Not only the cost of chemical plating treatment process becomes big, and can there is a problem of as follows：Chemical plating by using palladium catalyst is come During the space of the conductive layer that filling is formed by heat-agglomerating, palladium turns into the state being irregularly preferentially absorbed into conductive layer, The removing of palladium can not be sufficiently carried out in etching work procedure afterwards, the reason for causing the circuit substrate characteristic to reduce etc. can be turned into.

Accordingly, as the cheap chemical plating catalyst for not using palladium, for example, one kind is provided and uses silver salt as catalysis The method (referring for example to patent document 4) of agent.The method is following method：In the aqueous solution containing silver salt and surfactant Middle addition forms the silver-colored hydrosol relative to the reducing agent that silver salt is 2~4 times moles, it is contacted with plated body, assigns silver colloid And carry out chemical plating.But, the method haves the shortcomings that as follows：Substantial amounts of reducing agent is needed, production cost is high, and is formed The silver-colored hydrosol stability it is low, easily produce aggregate and precipitate.Additionally, in method disclosed in the document, as plated body, example The fiber compositions such as paper, non-woven fabrics, glass, ceramics and plastics are shown, but paper, cloth etc. have been only used effectively as plated body " porous material ", it utilizes catalyst " to hang over " in the loose structure of plated body to assign catalyst, with smooth table On the base material in face, when uniformly assigning catalyst to base material entire surface, it is difficult to the method disclosed in application aforementioned patent literature 4.

Additionally, also describe comprising 0.01~100mmol/L of silver salt, 0.01~0.5wt.% of anion surfactant, And relative to chemical plating catalyst liquid (referring for example to patent document 5) of the reducing agent that silver salt is 0.1~0.8 times mole, should The catalyst liquid that it relative to silver salt is 0.1~0.8 times mole that catalyst liquid is, reduction dose ratio aforementioned patent literature 4 is few, surely It is qualitative good.

In the method described in above-mentioned patent document 4,5, plated body is immersed in dilute dispersion liquid of silver colloid, mainly Silver colloid is set to be attached to plated body surface by the interaction of silver colloid and the electrostatic on plated body surface, as urging for chemical plating Agent and use, the adhesion amount of silver colloid is controlled by dip time, but is applied to be attached to the catalyst concn on plated body not , it is necessary to be carried out for a long time in big dipping tank fully and then during the base material of large area such as use in printed circuit board laminated substrate, thus It is more difficult in practical application.Additionally, for such method adsorbed naturally in a liquid, because silver colloid is to plated body Adsorptivity is low, therefore, in washing step, the chemical plating after assigning elargol body catalyst, catalyst material (silver colloid) is easily Come off from plated body, it may occur that the problems such as plating separates out decomposition that is uneven, causing promotion plating bath because polluting plating liquid.This Also refer to be coated with silver colloid and assign the possibility of catalyst on plated body in a little documents, but there is a problem of as follows：It is right The silver colloid of the low concentration as disclosed, it is impossible to assign the silver colloid of q.s, nothing on plated body by coating Method implements uniform plating on plated body, also, when disclosed silver colloid is concentrated, it may occur that aggregation, it is impossible to applied Cloth masking.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 9-136378 publications

Patent document 2：Japanese Unexamined Patent Publication 2006-305914 publications

Patent document 3：Japanese Unexamined Patent Publication 2010-272837 publications

Patent document 4：Japanese Unexamined Patent Application 64-068478 publications

Patent document 5：Japanese Unexamined Patent Publication 10-030188 publications

The content of the invention

Problems to be solved by the invention

The present invention be in view of above-mentioned problem of the prior art and make, the problem to be solved by the present invention is that, there is provided no Needs engaged by bonding agent, do not use vacuum equipment the conductive layer with suitable thickness conductive material manufacturer Method.More specifically, it is an object of the invention to provide the manufacture method of conductive material, the conductive material is by not The layer containing metal particle that needs will be coated on base material is converted into uneven conductive film and does not have to concern to be urged by palladium Caused by agent characteristic reduction, the method that easier and reliability is high and on insulator base material utilize sufficient dhering strength Laminated conductive layer.And then, the present invention also aims to, there is provided it is being manufactured using the manufacture method, can be suitable Ground is used as the conductive material of use in printed circuit board laminated substrate.

The scheme for solving problem

The present inventor etc. have made intensive studies to solve above-mentioned problem, as a result find, obtained by rubbing method, bag Containing protected by specific compound containing gold, silver, copper, the metal particle of platinum dielectric layer in various insulator base materials On show the catalysis activity of excellent chemical plating, and also basis as the plating film for triggering strong adaptation plays a role, So as to complete the present invention.

That is, the present invention provides the manufacture method of conductive material and using conductive material obtained from the manufacture method, The manufacture method is characterised by, with following operation：(1) Coating dispersions (B) in insulating properties base material (A), form The operation of non-conductive layer (C), the dispersion liquid (B) is containing certain content by with nitrogen-atoms, sulphur atom, phosphorus atoms or oxygen The metal particle (b2) selected from more than a kind in the group being made up of gold, silver, copper and platinum of compound (b1) protection of atom；(2) Chemical plating is carried out on the base material with non-conductive layer (C) obtained in (1), the operation of conductive layer (D) is formed.

The effect of invention

In accordance with the invention it is possible to the high performance electric conductivity that can be utilized in high-density installation field with low cost manufacture Material, tellite substrate, printed circuit board (PCB) without vacuum equipment, also do not use organic adhesive.

Brief description of the drawings

Fig. 1 is a section for mode for representing the base material that non-conductive layer (C) is formed with insulating properties base material (A) Schematic diagram.

Fig. 2 is a section for mode for representing the base material that non-conductive layer (C) is formed with insulating properties base material (A) Schematic diagram.

Fig. 3 is to represent a mode for being formed with the conductive material of conductive layer (D) by chemical plating on the base material of Fig. 1 Section schematic diagram.

Fig. 4 is to represent a mode for being formed with the conductive material of conductive layer (D) by chemical plating on the base material of Fig. 2 Section schematic diagram.

Fig. 5 is to represent the conductive material for being formed with metal conducting layer (E) by plating on the conductive layer (D) of Fig. 3 One schematic diagram in the section of mode.

Fig. 6 is to represent the conductive material for being formed with metal conducting layer (E) by plating on the conductive layer (D) of Fig. 4 One schematic diagram in the section of mode.

Fig. 7 be in example 2 by Kapton formed Argent grain film sintered at 100 DEG C 5 minutes it The electron micrograph on film surface afterwards.

Fig. 8 be carried out to calculate surface covering rate black white binarization, in example 2 will be thin in polyimides The Argent grain film formed on film sinters the electron micrograph on 5 minutes film surfaces afterwards (by the electronics of Fig. 7 at 100 DEG C Microphotograph carries out black white binarization).

Fig. 9 be in embodiment 3 by Kapton formed Argent grain film sintered at 100 DEG C 5 minutes it The electron micrograph on film surface afterwards.

Figure 10 be carried out to calculate surface covering rate black white binarization, in embodiment 3 will be in polyimides The Argent grain film formed on film sinters the electron micrograph on 5 minutes film surfaces afterwards (by the electricity of Fig. 9 at 100 DEG C Sub- microphotograph carries out black white binarization).

Figure 11 be in example 4 by Kapton formed Argent grain film sintered at 100 DEG C 5 minutes it The electron micrograph on film surface afterwards.

Figure 12 be carried out to calculate surface covering rate black white binarization, in example 4 will be in polyimides The Argent grain film formed on film sinters the electron micrograph on 5 minutes film surfaces afterwards (by the electricity of Figure 11 at 100 DEG C Sub- microphotograph carries out black white binarization).

Figure 13 be in embodiment 5 by Kapton formed Argent grain film sintered at 100 DEG C 5 minutes it The electron micrograph on film surface afterwards.

Figure 14 be carried out to calculate surface covering rate black white binarization, will be in polyimides in embodiment 5 The Argent grain film formed on film sinters the electron micrograph on 5 minutes film surfaces afterwards (by the electricity of Figure 13 at 100 DEG C Sub- microphotograph carries out black white binarization).

Figure 15 is that the Kapton that Argent grain will have been adsorbed in comparative example 1 sinters 30 minutes afterwards at 180 DEG C Film surface electron micrograph.

Figure 16 is black white binarization have been carried out to calculate surface covering rate, silver will have been adsorbed in comparative example 1 The Kapton of grain sinters the electron micrograph of 30 minutes film surfaces afterwards at 180 DEG C.

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

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

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

Figure 20 be carried out to calculate surface covering rate black white binarization, will be in polyimides in embodiment 85 The Argent grain film formed on film sinters the electron micrograph on 5 minutes film surfaces afterwards (by the electricity of Figure 19 at 210 DEG C Sub- microphotograph carries out black white binarization).

Specific embodiment

The present invention is described in detail below.

＜ insulating properties base materials (A) ＞

As the insulating properties base material (A) used in the present invention, for example, can suitably use：It is polyimide resin, poly- to benzene The polyester resin such as naphthalate, PEN, liquid crystal polymer, polyesteramide resin, cycloolefin gather The raw material such as compound, paper phenol, Epoxide cellulose paper, expoxy glass, ABS resin, glass, ceramics, it copes with flexible material, rigidity Any form of material, rigid flexible material.These insulating properties base materials (A) are relatively thin can be used as film, and thicker Can be used as thin slice, plate.

In flexible substrate purposes, it is possible to use foregoing polyimides, the film of polyester resin, as polyimides tree Fat, for example, can suitably use Kapton (Du Pont-Toray Co., Ltd.s), UPILEX (the emerging product in space portion), Apical The films such as (Kaneka Corporation), Pomiran (waste river chemistry).Additionally, as polyester resin, can suitably use liquid The VECSTAR series (KURARAY CO., LTD.) of crystalline polymer.Additionally, these films can be cutting into a certain size State using, can also be used with continuous filminess.

The insulating properties base material (A) used in the invention described above can have the through hole for connecting its surface and the back side.Run through Hole can be formed using the known conventional method such as drilling, laser.

For improve insulating properties base material (A) and non-conductive layer (C) so that with the plating film that obtains in the operation after Adaptation purpose, the dispersion liquid (B) of the metal particle that the insulating properties base material (A) that uses can be stated after application in the present invention It is surface-treated before.As the surface treatment method of insulating properties base material (A), various methods are suitably selected, for example may be used Suitably to use the physical methods such as UV treatment, ozone treatment, sided corona treatment, corona treatment.Additionally, insulating properties base material (A) During for polyimide resin, it is also possible to use the chemical method of the substrate surface with aqueous alkali treatment polyimide resin.Absolutely When edge base material (A) is polyester resin, the surface of polyester resin carried out in advance preferably UV treatment, sided corona treatment or wait from Daughter is processed.These surface treatment methods can be carried out individually, it is also possible to be carried out continuously multiple methods.

Dispersion liquid (B) ＞ of ＜ metal particles

Contained metal particle (b2) exists in the dispersion liquid (B) being coated with to form non-conductive layer of the invention (C) Worked as the catalyst of chemical plating on aforementioned dielectric base material (A), it is gold, silver, copper, the particle of platinum and these gold The alloy of category, core-shell particle, such as gold-silver core shell, gold-copper core shell, silver-copper core shell particle, these metallic particles it is each to Different in nature composite particles etc..In the present invention, aforementioned metal particulate (b2) can be using only one kind, it is also possible to mix various use.From From the viewpoint of industrial acquisition easy degree, cost, as metal species, the particle of silver and copper is preferably used.Even if additionally, There is oxidation overlay film, vulcanization overlay film on the surface of metal particle (b2), as long as the degree worked as chemical plating catalyst Even then.

As the shape of aforementioned metal particulate (b2), as long as can be coated in insulating properties base material (A), stabilization can be obtained Dispersion liquid (B) be just not particularly limited, can suitably be selected according to purpose be used alone spherical, lenticular, polyhedral, The variously-shaped metal particle such as tabular, bar-shaped, wire, or various particulates being obtained by mixing.

For the size of aforementioned metal particulate (b2), grain shape and observation shape are being observed using electron microscope During for circle, polyhedral, preferably its a diameter of 1~200nm is dispersed, stability in dispersion liquid (B) from metal particle Viewpoint consideration, more preferably uses the metal particle of 2~100nm.And then, it is finer and close and equal from that can be effectively formed by chemical plating From the viewpoint of even conductive layer (D), the particularly preferably metal particle of 5~50nm.

The observation image of the electron microscope of metal particle (b2) has lenticular, bar-shaped, wire etc. relative to short axle, length During axisymmetric shape, it is preferred that its minor axis be 1~200nm, more preferably 2~100nm, more preferably 5~ 50nm.The particle diameter distribution of the metal particle (b2) being dispersed in dispersion liquid (B) can be single dispersing, or with foregoing excellent The mixture of the particle of the particle diameter of the particle size range of choosing.

The dispersion liquid (B) used in the present invention is that aforementioned metal particulate (b2) disperses in various decentralized media, Aforementioned metal particulate (b2) needs to keep prolonged dispersion stabilization without assembling in decentralized medium, merging, precipitate, because This, the surface of metal particle (b2) is protected with the protective agent of organic compound.Additionally, aforementioned metal particulate (b2) by by its Dispersion liquid (B) is coated on aforementioned dielectric base material (A) and forms non-conductive layer (C), and it is risen as chemical plating with catalyst Act on, but plating is carried out in a liquid, accordingly, it would be desirable to the non-conductive layer (C) will not be from base material in plating liquid Peel off, preferably the protective agent of aforementioned metal particulate (b2) has raising aforementioned dielectric base material (A) close with non-conductive layer (C) The effect of conjunction property.

From the viewpoint, in the present invention, as the compound (b1) for protecting metal particle (b2), it is necessary to make With the compound (b1) with nitrogen-atoms, sulphur atom, phosphorus atoms or oxygen atom, can be according to the dispersion liquid of metal particle (b2) (B) application target and suitably select scattered metal particle, the species of dispersion solvent that is used and coating metal particulate Base material (A) etc..These specific atoms can be individually included in compound (b1), but from effectively showing foregoing function Viewpoint considers there is two or more different atom preferably in 1 molecule.

In order that containing such atom not of the same race in being used as protectant compound (b1), for example can with amino (- NH₂), carboxyl (- COOH), hydroxyl (- OH), sulfydryl (- SH), phosphate (H₂PO₄-), quaternary ammonium group (- NRR ' R "₄ ⁺), quaternary phosphines base, cyanogen The form of the functional groups such as base (- CN), ether (- O-), thioether group (- S-), disulfide group (- S-S-) contains.These functional groups can be with Individually contain in a molecule, can also in a molecule have it is various, additionally, as protective agent, using single compound (b1) when, it is also possible to while using various compounds (b1) with such functional group.

As aforesaid compound (b1), specifically, as the compound of low-molecular-weight, for example, can include：2- bis- Methyl amino ethanol, 2- DEAE diethylaminoethanols, 2- dimethylaminos isopropanol, 3- diethylamino -1- propyl alcohol, 2- dimethyl It is amino-2-methyl -1- propyl alcohol, 2- methyl amino ethanols, 4- dimethylaminos-n-butyl alcohol, formic acid, acetic acid, propionic acid, butyric acid, different Butyric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, dodecylic acid, tetradecanoic acid, oleic acid, linoleic acid, leukotrienes, Stearic acid, oxalic acid, tartaric acid, phthalic acid, methacrylic acid, citric acid, acrylic acid, benzoic acid, cholic acid, ethylenediamine, third Amine, butylamine, Trimethylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, lauryl amine, tridecyl amine, tetradecy lamine, ten Five amine, cetylamine, trioctylphosphine amine, dodecyl-dimethyl amine, butylethanolamine, bromination thiocholine, allyl sulfhydrate, pungent sulphur Alcohol, decyl mercaptan, lauryl mercaptan, Cys, sodium sulfosuccinate, neopelex etc..

Additionally, as the compound of HMW, for example can suitably using having one or more polyethylene in molecule It is alcohol, PVP, polyethylene glycol, polyethylene glycol propylene glycol copolymers, polyethyleneimine, PPI, poly- The macromolecule of the molecular cells high such as pyrroles, poly- (methyl) acrylate, polystyrene, during with various these high score subelements, Can be bonded and form using these high score subelement Direct Bondings or by amido link, ester bond, ether (- O-), thioether group (- S-) Compound.And then, a part of of these high molecular ends can be by amino (- NH₂), carboxyl (- COOH), carboxylate (- COOR：R is selected from methyl, ethyl, propyl group), hydroxyl (- OH), the substitution such as sulfydryl (- SH), can suitably use at high molecular end End has-OP (O) (OH)₂(R is the alkyl of carbon number 1~18, can have substitution base on phenyl ring the phosphate-based ,-SR for representing Phenyl or with select free hydroxyl, the alkoxy of carbon number 1~18, the aralkyl oxy of carbon number 1~18, can be on phenyl ring The alkyl carbonyl epoxide and carbon number 1 of phenoxy group, carboxyl, the salt of carboxyl, 1 valency of carbon number 1~18 or multivalence with substitution base~ More than 1 alkyl of the carbon number of functional group 1~8 in the group of 18 1 valency or the alkoxy carbonyl composition of multivalence.) represent official The compound that can be rolled into a ball.These macromolecules can be used alone and various can also mix while using.

The Film making properties of the non-conductive layer (C) in dispersion stabilization wherein, from dispersion liquid (B), insulating properties base material (A), From the viewpoint of adaptation, as the number-average molecular weight of aforesaid compound (b1), 1000~50000 scope is preferably used, this Outward, as its structure, can with it is particularly suitable using the compound (P1) with polyethyleneimine block and polyethylene glycol block, The polymer (P2) of (methyl) acrylic compounds and the organic compound (P3) of the ad hoc structure comprising thioether group (thioether bond).

The foregoing compound (P1) with polyethyleneimine block and polyethylene glycol block for example can be by will be commercially available The terminal hydroxyl derivative of polyethylene glycol is for active group and it is chemically bonded with commercially available polyethyleneimine and is obtained, Can be being bonded the equal molecule of number on particularly suitable the amino using in the polyethyleneimine that number-average molecular weight is 500~50000 Measure the compound of the polyethylene glycol for 500~5000.The compound (P1) used in the present invention has polyethyleneimine embedding The ad hoc structure of section and polyethylene glycol block, it is also possible to further import other structures.

Additionally, as foregoing (methyl) acrylic polymer (P2) that can suitably use in the present invention, Ke Yilie Enumerate：Make (methyl) the esters of acrylic acid macromonomer with polyglycol chain and there is-OP (O) (OH)₂The phosphoric acid of expression (methyl) acrylic ester monomer of ester residue is deposited in the chain-transferring agent of the functional group that is represented with-SR (R is as hereinbefore) (methyl) acrylic polymer obtained from lower polymerization (referring for example to Japanese Patent Publication No. 4697356).

And then, as having for the foregoing ad hoc structure comprising thioether group (thioether bond) that can suitably use in the present invention Machine compound (P3), can be suitably using the Sulfide-containing Hindered organic compound (P3) of following formulas (1) expression (referring for example to Japanese special Perhaps No. 4784847).

X-(OCH₂CHR¹)_n-O-CH₂-CH(OH)-CH₂-S-Z (1)

(in formula (1), X is C₁~C₈Alkyl, R¹It is hydrogen atom or methyl, n is the integer of the repeat number of expression 2~100, R¹Each repeat unit be independent, can be the same or different, Z is C₂~C₁₂Alkyl, pi-allyl, aryl, aralkyl Base ,-R²-OH、-R²-NHR³Or-R²-COR⁴(wherein, R²It is C₂~C₄Alkylidene chain, R³It is hydrogen atom, C₂~C₄Acyl group, C₂~C₄Alkoxy carbonyl or can have C on aromatic rings₁~C₄Alkyl or C₁~C₈Alkoxy substitution base benzyl Epoxide carbonyl, R⁴It is hydroxyl, C₁~C₄Alkyl or C₁~C₈Alkoxy.) represent group.〕

In the present invention using aforesaid compound (b1) can be added in the manufacture of metal particle (b2), it is also possible to system Make addition after metal particle (b2).Additionally, in dispersion liquid (B), as the solvent for dispersed metal particulate (b2), as long as For metal particle (b2) can be made stably to disperse, in the case where metal particle (b2) dispersed state is made to aforementioned dielectric base material (A) wetability is good, the solvent of liquid film can be formed on aforementioned dielectric base material (A), is not particularly limited, and can make Use various solvents, be in water, water and mixed solvent, the water-free organic solvent of water miscible organic solvent it is any number of Can.

As the foregoing water miscible solvent that can mix with water, for example, can include：Methyl alcohol, ethanol, normal propyl alcohol, isopropyl Polyalcohol, other esters such as the ketones such as the alcohols such as alcohol, n-butanol, isobutanol, the tert-butyl alcohol, acetone, 2- butanone, ethylene glycol, glycerine, Ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methyl proxitol The glycol ethers such as acetic acid esters, butyl diglycol acetic acid esters, these solvents can be used alone or mix various use.

Additionally, in dispersion liquid (B), as making metal particle (b2) scattered aforementioned organic solvents, can enumerate Go out the foregoing water miscible solvent that can mix with water, such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, tertiary fourth The polyalcohols such as ketone, ethylene glycol, the glycerine such as the alcohols such as alcohol, acetone, 2- butanone, other esters, ethylene glycol monomethyl ether, ethylene glycol Dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methyl proxitol acetate, butyl diglycol second The glycol ethers such as acid esters, it is possible to use single these solvents or the solvent for mixing multi-solvents, without mixing water. In this case, contain little water because of moisture absorption etc. sometimes, but it is not intended that and mix with water, therefore, in the present invention as not Aqueous organic solvent is treated.

Additionally, in dispersion liquid (B), as making metal particle (b2) scattered aforementioned organic solvents, can enumerate Go out the organic solvent not mixed with water, such as hexane, heptane, octane, nonane, decane, hendecane, dodecane, tridecane, 14 The long chain alkanes such as alkane, pentadecane, hexadecane, octadecane, nonadecane, eicosane, trimethylpentane, hexamethylene, cyclobutane, ring are pungent The aromatic hydrocarbons such as the cyclic alkanes such as alkane, benzene,toluene,xylene, trimethylbenzene, detergent alkylate, hexanol, enanthol, octanol, decyl alcohol, The alcohol such as cyclohexanol, terpineol, these solvents can be used alone or various be used in mixed way.

As the autofrettage of the dispersion liquid (B) used in the present invention, it is not particularly limited, it is possible to use various methods are made Make, for example, the metal particle dispersion of the vapor phase methods such as the evaporation in using low vacuum gas manufacture can be made in a solvent, Can in the liquid phase reducing metal compound and directly prepare the dispersion liquid of metal particle.Gas phase, liquid phase method can be according to need The solvent group of dispersion liquid when wanting and dispersion liquid during manufacture is changed suitably by exchange of solvent, solvent addition with coating Into.In gas phase, liquid phase method, from the aspect of the easy degree of stability, manufacturing process from dispersion liquid, can particularly preferably use Liquid phase method.

As the autofrettage of the dispersion liquid (B) in foregoing liquid phase method, can suitably use in the liquid phase, in aforesaid compound (b1) method for reducing metallic compound in the presence of, it is possible to use Japanese Unexamined Patent Publication 2008-037884 publications, Japanese Unexamined Patent Publication Described in 2008-037949 publications, Japanese Unexamined Patent Publication 2008-03818 publications, Japanese Unexamined Patent Publication 2010-007124 publications Method is manufactured.Can for example operate as follows：Make the foregoing compound with polyethyleneimine block Yu polyethylene glycol block (P1) after dissolving in an aqueous medium or disperse, metallic compound is added to, and be applied in combination complexing agent as needed And formed after uniform dispersion or with complexing agent while mixing reducing agent, thus, the metal being reduced turns into nanometer Grain (has the particulate of nanoscale size), at the same time obtains by the aqueous dispersion of the metal particle of aforesaid compound (P1) protection Body.

Additionally, the autofrettage of the dispersion liquid (B) as the utilization liquid phase method used in the present invention, such as can suitably use Method described in No. 4697356 publications of Japanese Patent, in the protectant presence of foregoing (methyl) acrylic polymer (P2) The method of lower reducing metal compound.

Additionally, the autofrettage of the dispersion liquid (B) as the utilization liquid phase method used in the present invention, can suitably use preceding State the ad hoc structure containing thioether group (thioether bond) organic compound (P3) it is protectant in the presence of reducing metal compound Method, can be in the presence of foregoing Sulfide-containing Hindered organic compound (P3), by the work for mixing metallic compound with solvent The operation of sequence and reducing metal compound and obtain the aqueous 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 core-copper shell, is made It is the autofrettage of the dispersion liquid (B) of the metal particle, can passes through nano particle, the foregoing Sulfide-containing Hindered organic compound of silver (P3) operation that, cuprous oxide (I) and/or cupric oxide (II) mix with solvent and by using reducing agent reductive copper oxide The operation of the shell of copper is generated around silver nano-grain and the dispersion liquid (B) of the core shell particle of silver core-copper shell is obtained.This method The middle silver nano-grain for using can use commercially available silver nano-grain, it is also possible to use the dispersion liquid using aforementioned metal particulate The silver nano-grain that obtains of manufacture method.

In the present invention, can directly using the water-borne dispersions of the metal particle obtained using the above method, or, also may be used Ultrafiltration is used with using have passed through counter ion counterionsl gegenions contained to remaining complexing agent, reducing agent or in the silver compound as raw material etc. 1 kind of method in the various method of purification such as method, the precipitation method, centrifugation, vacuum distillation, drying under reduced pressure combines two or more method Dispersion obtained from the purification procedures for carrying out, can also make it further change concentration (nonvolatile component), dispersion and be situated between Dispersion obtained from matter etc..

The metallic compound that can be used in autofrettage as the dispersion liquid (B) of the metal particle in these liquid phase methods, Element, the i.e. gold, silver for forming metal particle (b2), copper, the salt of platinum, the oxidation used in the foregoing present invention can be used Thing, from from the aspect of dissolubility, can include the conducts such as acetate, nitrate, sulfate, chloride, acetylacetonate Preference.Wherein preferably nitrate or acetate.But, even if be insoluble compound, can in the form of complexing agent picture When ammonia, amines, hydrazine, azanol class are formed with deliquescent complex compound with metallic ion coordination like that, it is also possible to make With the insoluble compound of metal oxide etc.

For example when metallic element is for gold, platinum family, it is possible to use tetra chlorauric acid, Tetrachloroplatinate etc..Additionally, metal species are copper When, except Cu (OAc) can be used₂、Cu(NO₃)₂、CuCl₂、Cu(HCOO)₂、Cu(CH₃COO)₂、Cu(CH₃CH₂COO)₂、 CuCO₃、CuSO₄、C₅H₇CuO₂In addition, basic salt, such as Cu obtained from carboxylate is heated can also similarly be used (OAc)₂·CuO.Metal species for silver when, it is possible to use silver nitrate, silver oxide, silver acetate, silver chlorate, silver sulfide etc., with When the form of the aqueous solution is processed, from from the aspect of its solubility, silver nitrate is preferred.

Metal particle (b2) in the dispersion liquid (B) used as the present invention contains concentration, from must by insulation The dispersion liquid is coated with property base material (A) and from the viewpoint of forming non-conductive layer (C), it is necessary to contain in the dispersion liquid (B) The metal particle (b1) of more than 0.5 mass %.That is, when excessive rarefied, metal particle (b2) in insulating properties base material (A) sometimes It is distributed excessively sparse and film cannot be formed, it is difficult to forms non-conductive layer (C).On the other hand, when excessively dense, it is coated on non-leading The stacking number of the metal particle (b2) on electric layers (C) becomes excessive, exist formed by sintering conductive layer, cannot be abundant Play the worry of the basic effect as the plating film for showing strong adaptation.From the viewpoint, as in the present invention Metal particle in the dispersion liquid (B) for using contains concentration, it is necessary to be more than 0.5 mass %, preferably below 20wt%, more Preferably 0.7~15wt%, from from the viewpoint of coating Film making properties, more preferably 1~10wt%.

It is main purpose to improve coating Film making properties in dispersion liquid used in the present invention (B), can adds as needed Plus various surface tension modifiers, levelling agent are used.Addition on these surface tension modifiers, levelling agent, relatively In dispersion liquid, preferably comprise as active ingredients below 2.0 mass %, particularly preferably contain 0.5 mass % as active ingredients Below.

The coating ＞ of ＜ dispersion liquids (B)

In the present invention, as the method for being coated with aforementioned dielectric base material (A) foregoing dispersion liquid (B), can be well Non-conductive layer (C) is formed, is not particularly limited, it is shape, size according to the insulating properties base material (A) for being used, hard and soft Degree etc. suitably selects various printing painting methods, specifically, can include：Gravure coating process, hectographic printing Method, relief printing plate method, relief printing plate quote method, 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, transferring roller Rubbing method, kiss-coating method, casting coating, spraying process, gunite, die coating method (die method), spin-coating method, stick coating method, dipping Rubbing method etc..

As film, thin slice, the foregoing dispersion liquid of the two sided coatings (B) of the aforementioned dielectric base material (A) of tabular method, As long as can well form non-conductive layer (C) to be just not particularly limited, various printing coating gimmicks are suitably selected, can To form two sides simultaneously, it is also possible to carry out the coating of another side after one side is coated.

After the dispersion liquid (B) of metal particle (b2) coated into insulating properties base material (A), the shape by the drying of coated film Into non-conductive layer (C).The drying of coated film can be carried out at room temperature, it is also possible to be thermally dried.Additionally, when drying Can be blown, it is also possible to do not blown specially.During air-supply, can be with heat air delivery, it is also possible to only blow at room temperature.This Outward, drying can be carried out in an atmosphere, it is also possible to be carried out in the case where nitrogen, argon gas etc. replace atmosphere or air-flow, can also be true Carried out under sky.Further, it is also possible to be carried out under the nitrogen atmosphere less than concentration of lower explosive limit.

For the drying of coated film, in the case of film, thin slice, plate of the aforementioned dielectric base material (A) for sheet, except Coat beyond the natural drying in place, can also in the driers such as air-supply, thermostatic drier under conditions of carry out.Additionally, preceding Insulating properties base material (A) is stated in the case of roll film (roll sheet), can then foregoing printing painting process, what is set Continuously move roll film in non-heated or heating space, be thus dried.

＜ non-conductive layers (C) ＞

In the present invention, the non-conductive layer of the dispersion liquid (B) of coating metal particulate (b2) in insulating properties base material (A) (C) be the metal particle (b2) protected by aforesaid compound (b1) on aforementioned dielectric base material (A) near uniform configuration and Into, although the situation that part metals particulate (b2) is contacted each other is there is also, but it is not show electric conductivity to think as layer 's.In the present invention, metal particle (b2) uniformly configuration layer do not show electric conductivity, be it is non-conductive refer to, using low Resistrivity meter cannot determine the level of the resistance value of film, for example, using Mitsubishi Chemical Analytech Co., The resistrivity meter of the Loresta series for Ltd. manufacturing, (resistance of this layer measured using four-terminal method is to confirm no to scale 9.999×10⁷More than Ω) or overload (even if between terminal apply 90V voltage cannot also determine constant current) display .

The foregoing non-conductive layer (C) formed in insulating properties base material (A) used in the present invention can suitably basis Need and heated before the chemical plating of subsequent handling.By heat, can improve non-conductive layer (C) with it is exhausted The adaptation of edge base material (A).Additionally, when using printed circuit board (PCB), the high-temperature technologies such as such as soldering may be experienced, due to As protectant compound (b1), the surface conditioner, levelling agent, the dispersion solvent that are added as needed on etc. in the height in base material Drastically problem can be turned into if volatilization or decomposition gasification in warm technique, therefore, it is recommended that during fabrication by carrying out at heating in advance Manage and remove this composition in advance.

For heating, non-conductive layer is formed with insulating properties base material (A) to foregoing using various heating means (C) base material is processed, it is possible to use electric furnace, Muffle furnace, vacuum drying oven, controlled atmosphere generator (atmosphere Furnace), in light irradiation heater, infrared heating device, microwave heating equipment, electron ray heater etc. Various heaters are planted or are applied in combination to carry out.Additionally, heat as needed can in an atmosphere, in vacuum, nitrogen Atmosphere, argon atmospher and less than being carried out under the nitrogen atmosphere of concentration of lower explosive limit.Additionally, it is foregoing be formed with insulating properties base material (A) it is non- In the case that the base material of conductive layer (C) is film, thin slice, the plate of sheet, can be carried out in foregoing heat treatment apparatus device, In the case of for roll film shape, sheet material can be made by electrical heating, light heating, infrared heating, the space of heating using microwave Continuous moving is carried out.

Additionally, in the present invention, the heating of non-conductive layer (C) can disperse with being coated with insulating properties base material (A) Drying after liquid (B) is carried out simultaneously, it is also possible to is dried respectively and is heated.

In the present invention, the heat treatment temperature of non-conductive layer (C), heat treatment time according to application target, used Insulating properties base material (A) raw material heat resisting temperature come suitably select, be not particularly limited, for example, it is preferable that, absolutely It is poly- terephthaldehyde below 400 DEG C, preferably 300 DEG C heat treated below when edge base material (A) is polyimide resin During sour glycol ester, in 150 DEG C of heat treated below, when being PEN, hot place is carried out below 200 DEG C Reason, when being liquid crystal polymer, in 380 DEG C of heat treated below, when being paper phenol, Epoxide cellulose paper, carries out hot place below 130 DEG C Reason, when being expoxy glass, in 150 DEG C of heat treated below, when being ABS resin, in 100 DEG C of heat treated below.

For example preceding institute of heating of non-conductive layer (C) being carried out in the present invention, being formed in insulating properties base material (A) State, its object is to improving the adaptation of metal particle (b2) and insulating properties base material (A), being volatilized by high-temperature process and decomposed The composition of gasification is removed, rather than in order that aforementioned metal particulate (b1) is mutually closely sealed, fusion and show electric conductivity, its feature It is also to keep non-conductive after a heating treatment.

In non-conductive layer (C) being used in the present invention, being formed on aforementioned dielectric base material (A), aforementioned metal is micro- Grain (b2) is configured on aforementioned dielectric base material (A), when the stacking number of the metal particle (b2) on thickness direction is excessive, by preceding The heating stated, can form the junction surface of more metal particle (b2) mutually welding, and uneven melting is formed in film entirety Binding structure, easily becomes the film for showing electric conductivity.Conductive film with such uneven welding structure is due in film In include many spaces, therefore bad mechanical strength, the film of the bad mechanical strength is present in insulating properties base material (A) and the plating after Cover between the metal film formed in operation, so that plating film easily self-insulating property base material (A) can be peeled off.Additionally, using having When the film of such uneven welding structure carries out chemical plating, that is, allow to the space on filling film top, it is also difficult to by plating Cover the space that metal fully fills welding structure inside and bottom, it is difficult to improve the mechanical strength of film.Examined from such viewpoint Consider, the stacking number of the aforementioned metal particulate (b2) being preferably configured on aforementioned dielectric base material (A) is less than 5 layers, more preferably 3 Layer is following.Stacking number of the metal particle (b2) in insulating properties base material (A) can be micro- by using confocal microscope, interference-type The film thickness measuring of the non-conductive layer (C) that mirror, surface-profile measuring instrument etc. are carried out, using electron microscope carry out it is non-conductive Property the layer surface of (C), cross-section confirm.

Additionally, used in the present invention, in the non-conductive layer (C) that is formed on the aforementioned dielectric base material (A), it is foregoing absolutely Edge base material (A) is covered by aforementioned metal particulate (b2), as plating catalyst and plating in its plating process after Seed, basal layer work.When the surface covering rate that the aforementioned metal particulate (b2) on insulating properties base material (A) surface brings is too low, Distance between the metallic crystal of precipitation is excessive, the mutual bonding of crystallization will not occur, accordingly, it is difficult to form plating overlay film.It is another Aspect, the covering rate on insulating properties base material (A) surface that metal particle (b2) brings uprises, the metal particle (b2) of substrate surface When stacking number becomes many, due to foregoing heating, engaged between metal particle (b2), form the uneven welding more than space Structure and turn into conductive film.When forming the conductive film of such uneven welding structure, due to as previously described inside film Many independent spaces, thus bad mechanical strength are formed, the metal lining film formed in the operation after cannot keep practical On peel strength.If the surface covering rate that metal particle (b2) brings is appropriate, the connection between the metal lining crystallization for separating out Well, overlay film is easily formed, also, metal lining produces anchoring to imitate by the space between abundant percolated metal particulate (b2) Really, peel strength is improved.From the viewpoint, the aforementioned metal particulate (b2) on aforementioned dielectric base material (A) surface brings Surface covering rate from the plating of subsequent handling, keep the peel strength of the self-insulating property base material of plating overlay film from the viewpoint of, More preferably more than 20 area % and below 90 area %.

In the present invention, the surface covering rate that the aforementioned metal particulate (b2) on aforementioned dielectric base material (A) brings can lead to Cross carries out the surface observation of non-conductive layer (C) using high-resolution scanning electron microscope (SEM), and calculates observation figure Occupy ratio to be evaluated as upper metal particle (b2) image.The size of the metal particle (b2) by being used in the present invention To evaluate during the covering rate of surface, it is recommended to use 50,000 times or so of observation multiplying power.

In the present invention, the non-conductive layer (C) formed on aforementioned dielectric base material (A) can also be in the second being of operation The patterning of circuit pattern is carried out before learning plating.As the method for patterning, can include and induction is irradiated by laser Ablation phenomen and the method that removes unwanted part.As the laser used in the purpose, it is possible to use UV laser, visible ray Laser, near-infrared, the laser of any wavelength of infrared ray laser.

＜ Electroless Plating Procedures ＞

Second operation of the invention, it is provided with the base material of non-conductive layer (C) in insulating properties base material (A) foregoing Form non-conductive layer (C) of the operation of conductive layer (D) by that will be formed on aforementioned dielectric base material (A) and be used as chemical plating Catalyst layer and Seed Layer simultaneously carry out chemical plating and implement.

For Electroless Plating Procedure, enter preferably via cleaning process, washing step, activation of catalyst operation, washing step Row chemical plating.Species to metal lining is not particularly limited, and considers from electric conductivity and industrial usability, is preferably changed Learn copper facing.The electroless copper can suitably use commercially available chemical plating reagent, specifically, can be with particularly suitable using difficult to understand The OICCOPPER of wild pharmaceuticals industry Co., Ltd. manufacture.

Conductive layer (D) to being formed by chemical plating in the second operation of the invention is not particularly limited, preferred surface electricity Resistance rate is 1000 Ω/below, and then, when implementing to electroplate by the 3rd operation, as surface resistivity, preferably 10 Ω/ Below.If in view of the efficiency that metal conducting layer (E) is formed by plating of the 3rd operation, more preferably 1 Ω/below. Additionally, pass through chemical plating formed conductive layer (D) thickness from manufacture operating efficiency from the viewpoint of, preferably 1500nm with Under.

＜ electroplating work procedures ＞

In the present invention, by foregoing Electroless Plating Procedure, the electric conductivity material that there is conductive layer (D) on surface can be obtained Material, but for the purpose of the thickness for further improving electric conductivity or increase conductive layer, can also be electroplated as the 3rd work Sequence.Now, to being not particularly limited by electroplating the metal species for being formed, from from the viewpoint of electric conductivity, stability, preferably Copper, nickel, gold etc., from resistance value is low and industrial utilization from the viewpoint of particularly preferred copper.

As electroplating work procedure, it is not particularly limited, using various electro-plating methods, for example, can be in operation (2) Conductive layer (D) surface for obtaining is carried out after degreasing and/or the removing of oxide layer, is impregnated in plating liquid and is powered, so that shape Into coating layer.

The thickness of the metal conducting layer (E) to being obtained by plating is not particularly limited, and is suitably selected according to application target , it is total with the conductive layer (D) formed by the chemical plating of the second operation, preferably less than more than 200nm and 30 μm, from From the viewpoint of electric conductivity and circuit pattern when using, more preferably less than more than 400nm and 20 μm.

The conductive material manufactured via 2 foregoing operations has by metal particle on aforementioned dielectric base material (A) (b2) non-conductive layer (C) for constituting, and conductive layer (D) is laminated with the non-conductive layer (C), additionally, passing through 3 operations The conductive material for obtaining has the non-conductive layer (C) formed by metal particle (b2) on aforementioned dielectric base material (A), and Conductive layer (D) and metal conducting layer (E) are laminated with thereon.For conductive material of the invention, the gold of metal particle (b2) Category species and be formed thereon the metal species of the conductive layer to be formed (D) or conductive layer (D) and metal conducting layer (E) can be with All identical metals, or respective different metal species.For example, a mode of conductive material of the invention In, the non-conductive layer (C) in insulating properties base material (A) is formed by silver-colored particulate, and the conductive layer (D) being formed on is formed by copper. Additionally, as other modes, can include：Non-conductive layer (C) in insulating properties base material (A) formed by copper particulate, The conductive layer (D) and metal conducting layer (E) for being formed thereon are also formed by copper.And then, as other modes, can also enumerate Go out：Non-conductive layer (C) in insulating properties base material (A) is formed by the core-shell particle with silver as core, with copper as shell, thereon shape Into conductive layer (D) and metal conducting layer (E) formed by copper.

It should be noted that in conductive material of the invention, in insulating properties base material (A) by metal particle (b2) non-conductive layer (C) for being formed, after conductive layer (D) is formed, metal particle is filled by the formation of conductive layer (D) (b2) space between, so as to can also exist not as the independent non-conductive layer (C) of the essence in insulating properties base material (A).

Composition on conductive material of the invention, shows schematic diagram in Fig. 1~Fig. 6.Such conductive material Due to the excellent adhesion of insulating properties base material (A) and conductive layer, it is used as to need to carry out fine rule processing such that it is able to particularly suitable Use in printed circuit board laminated substrate.

Embodiment

Embodiment is exemplified below to illustrate in greater detail the present invention, but the present invention is not limited to these embodiments.Need It is bright, 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.'s manufacture, JEM-2200FS

SEM is observed：Hitachi manufacture, ultrahigh resolution field emission type SEM S-800 or KEYENCE CORPORATION manufactures, VE-9800

TGA is determined：SII NanoTechnology Inc. manufactures, TG/DTA6300

Plasma absorption spectrum：Hitachi Co., Ltd's manufacture, UV-3500

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

Sheet resistance value is determined：Mitsubishi chemical Co., Ltd's manufacture, low-resistivity meter Loresta EP (4 terminal method)

Surface covering rate is determined：What the surface covering rate that the metal particle of substrate surface brings was manufactured using Hitachi Ultrahigh resolution field emission type SEM S-800, Coating dispersions and dried table are observed with 50,000 times of multiplying power Face, observation image is carried out after two-value turns to black white image, calculating area, the metal particle overall relative to imaging surface Occupied area, so as to calculate surface covering rate.

Peeling strength test：A＆D Co., Ltd. manufactures Tensilon universal testing machines RTC-1210A：By plating overlay film from The strip for 1cm is peeled off on base material, 180 DEG C of tensile strengths in direction are obtained, peel strength is thus determined.

(manufacture of the dispersion liquid of metal particle)

＜ has the synthesis ＞ of the compound (P1) of polyethyleneimine block and polyethylene glycol block

Synthesis example 1 (has the conjunction of the compound (P1-1) of polyethylene glycol (PEG)-branched polyethylenimine (PEI) structure Into)

1-1 [synthesis of tosyl polyethylene glycol]

(number is divided equally to prepare single terminal methoxy group polyethylene glycol (hereinafter referred to as PEGM) of the mixing in chloroform 150ml respectively Son amount (Mn) 5000) (Aldrich manufacture) 150g (30mmol) and solution obtained by pyridine 24g (300mmol), and by first The solution that benzene sulfonyl chloride 29g (150mmol) and chloroform 30ml is uniformly obtained by mixing.

In 20 DEG C of following stirring PEGM and the mixed solution of pyridine, side is added dropwise the toluene solution of toluene sulfochloride thereto. After completion of dropwise addition, reacted 2 hours at 40 DEG C.After reaction terminates, add chloroform 150ml to be diluted, use the 5%HCl aqueous solution After 250ml (340mmol) cleanings, cleaned with saturated aqueous common salt and water.The chloroformic solution that will be obtained is done with sodium sulphate After dry, solvent is distilled off using evaporator, be further dried.Yield is 100%.Utilize¹H-NMR spectrum are carried out respectively Ownership (the 2.4ppm at peak：Methyl, 3.3ppm in tosyl：The methyl of PEGM ends, 3.6ppm：EG chains, 7.3 of PEG ~7.8ppm：Phenyl ring in tosyl), confirm as tosyl polyethylene glycol.

1-2 [has the synthesis of the compound of PEG- side chain PEI structures]

The tosyl polyethylene glycol 23.2g (4.5mmol) and branched ethylene imine that will be obtained in above-mentioned 1-1 (Nippon Shokubai Co., Ltd's manufacture, EPOMIN SP200) 15.0g (1.5mmol) is dissolved in dimethylacetylamide (hereinafter referred to as DMA) after in 180ml, potassium carbonate 0.12g is added, is reacted 6 hours at 100 DEG C under nitrogen atmosphere.After reaction terminates, remove solid Body residue, adds the mixed solvent of ethyl acetate 150ml and hexane 450ml, is precipitated thing.The sediment is dissolved in chloroform In 100ml, the mixed solvent of ethyl acetate 150ml and hexane 450ml is added again, make its reprecipitation.Filtered, in decompression Under be dried.Utilize¹H-NMR spectrum carry out the ownership (2.3~2.7ppm at each peak：The ethylidene of side chain PEI, 3.3ppm： The methyl of PEG ends, 3.6ppm：The EG chains of PEG), confirm as the compound (P1-1) with PEG- side chain PEI structures.Yield It is 99%.

Synthesis example 2 (has the synthesis of the bisphenol A type epoxy resin structured compounds (P1-2) of PEG- side chains PEI-)

2-1 [epoxy resin modified]

By bisphenol A type epoxy resin EPICLON AM-040-P (Dainippon Ink Chemicals's manufacture) 37.4g (20mmol), 4- benzene After base phenol 2.72g (16mmol) is dissolved in DMA100ml, 65% acetic triphenyl phosphonium ethanol solution 0.52ml is added, Reacted 6 hours at 120 DEG C under nitrogen atmosphere.After placing cooling, it is added drop-wise in a large amount of water, the sediment that will be obtained further is used Substantial amounts of water cleaning.Drying under reduced pressure is carried out after reprecipitation purified is filtered, modified bisphenol A type epoxy resin is obtained.Obtain The yield of product is 100%.

Carry out¹H-NMR determines to investigate the integration ratio of epoxy radicals, as a result, remained in 1 molecule bisphenol A type epoxy resin 0.95 epoxide ring, the modified epoxy that confirmation is obtained is the epoxy resin of the mono-functional with bisphenol A skeleton.

2-2 [has the synthesis of the bisphenol A type epoxy resin structured compounds (P1-2) of PEG- side chains PEI-]

Dissolved to compound (P1-1) 20g (0.8mmol) with PEG- side chain PEI structures that will be obtained in synthesis example 1 In solution obtained from the methyl alcohol 150ml, being added dropwise under nitrogen atmosphere will be double obtained from modified by above-mentioned epoxy resin Mono-functional's epoxy resin 4.9g (2.4mmol) of phenol A types be dissolved in acetone 50ml obtained from solution, afterwards, at 50 DEG C Lower stirring 2 hours, so as to be reacted.After reaction terminates, solvent is distilled off under reduced pressure, and then carries out drying under reduced pressure, Thus obtain with PEG- branched PEI- bisphenol A type epoxy resin structured compound (P1-2).Yield is 100%.

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

3-1 [epoxy resin modified]

By naphthalene type epoxy resin EPICLON HP-4700 (Dainippon Ink Chemicals's manufacture) 44.5g (80mmol), 4- phenyl benzene After phenol 29.9g (176mmol) is dissolved in DMA200ml, 65% acetic triphenyl phosphonium ethanol solution 1.36ml is added, Reacted 6 hours at 120 DEG C under blanket of nitrogen.After placing cooling, it is added drop-wise in water 150ml, the sediment that will be obtained is clear with methyl alcohol Wash 2 times, afterwards, drying under reduced pressure is carried out at 60 DEG C, obtain modified naphthalene type epoxy resin.Yield is 100%.

Carry out¹H-NMR is determined to investigate the integration ratio of epoxy radicals, as a result, 0.99 is remained in 1 molecule naphthalene type epoxy resin Epoxide ring, confirms as the naphthalene type epoxy resin of mono-functional.

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

To compound (P1-1) 4.65g with PEG- side chain PEI structures that will be obtained in above-mentioned synthesis example 1 (0.5mmol) be dissolved in methyl alcohol 40ml obtained from solution, the naphthalene skeleton that will be obtained in above-mentioned 3-1 is added dropwise under nitrogen atmosphere Mono-functional's epoxy resin 1.16g (1.1mmol) be dissolved in acetone 15ml obtained from solution, back stirred at 50 DEG C Mixing 2 hours sides reacts it.After reaction terminates, solvent is distilled off under reduced pressure, further carries out drying under reduced pressure, thus To the compound (P1-3) with PEG- side chain PEI- naphthalene type epoxy resin structures.Yield is 100%.

Synthesis example 4 (has the synthesis of the compound (P1-4) of PEG- side chain PEI- polystyrene structures)

To compound (P1-1) 1.22g (0.049mmol) with PEG- side chain PEI structures that will be obtained in synthesis example 1 In solution obtained from being dissolved in water 44g, 2mol/L hydrochloric acid 1.9g and styrene monomer 1.92g (18.4mmol) is added, The following side of being stirred at 80 DEG C of blanket of nitrogen adds 70% TBHP (TBHP) 0.45g (5.0mmol), reacts 2 hours. After cooling, purified by dialysis, obtained the moisture of the compound (P1-4) with PEG- side chain PEI- polystyrene structures A prose style free from parallelism.Yield is 100%.

Synthesis example 5 (has the conjunction of the compound (P1-5) of PEG- side chain PEI- polypropylene glycol backbone amino formic acid ester structures Into)

5-1 [synthesis of polypropylene glycol (PG) backbone amino formic acid esters]

In DPG diglycidyl ether EPICLON 705 (Dainippon Ink Chemicals's manufacture) 20.1g (50mmol), Dibutyl amine 13.0g (101mmol) was added dropwise with 0.5 hour at 70 DEG C under blanket of nitrogen, is reacted 7 hours at 90 DEG C, obtain two ends Dibutylamino PG reaction solutions.Then, in diisocyanate 19.4g (100mmol), tin octoate 0.04g (0.1mmol) and In the mixed solution of chloroform 80g, the two end dibutylamino PG that above-mentioned synthesis was added dropwise with 0.5 hour at 40 DEG C react molten Liquid, carries out addition reaction in 5 hours at 50 DEG C.And then, cyclohexane methanol 5.7g (50mmol) was added dropwise with 20 minutes at 40 DEG C, Addition reaction in 5 hours is carried out at 50 DEG C, the solution of polypropylene glycol backbone amino formic acid esters is obtained.

5-2 [has the synthesis of the compound (P1-5) of PEG- side chain PEI- polypropylene glycol backbone amino formic acid ester structures]

Chlorine is dissolved in the macromolecular compound 16.0g with PEG- side chain PEI structures that will be obtained in above-mentioned synthesis example 1 In solution obtained from imitative 30ml, the polypropylene glycol skeleton ammonia that will be obtained in above-mentioned 5-1 was added dropwise with 10 minutes under nitrogen atmosphere The solution 2.76g (2mmol) of carbamate be dissolved in chloroform 10ml obtained from solution, it is then small in 40 DEG C of following stirrings 2 When side react it.After reaction terminates, it is the mixed solvent 340g of 1 to 1 (volume ratio) to add water and acetone, under reduced pressure by chlorine Imitative and acetone is distilled off, and obtains the compound (P1-5) with PEG- side chain PEI- polypropylene glycol backbone amino formic acid ester structures Aqueous dispersion.Yield is 100%

Synthesis example 6 (has the conjunction of the compound (P1-6) of PEG- side chain PEI- polycarbonate backbone carbamate structures Into)

6-1 [synthesis of polycarbonate backbone carbamate]

In diisocyanate 19.4g (100mmol), the mixed solution of tin octoate 0.04g (0.1mmol) and chloroform 100g In, PCDL 49.0g (50mmol) was added dropwise with 0.5 hour at 40 DEG C under nitrogen atmosphere, afterwards, carried out at 50 DEG C Addition reaction in 5 hours, obtains the reaction solution of two terminal isocyanate carbamates.Then, in two terminal isocyanates of synthesis In acid esters urethane reaction solution, cyclohexane methanol 5.7g (50mmol) was added dropwise with 20 minutes at 40 DEG C, afterwards, 50 Addition reaction in 5 hours is carried out at DEG C, single terminal isocyanate polycarbonate backbone urethane reaction solution is obtained.

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

Chloroform is dissolved in the macromolecular compound 16.0g with PEG- side chain PEI structures that will be obtained in synthesis example 1 In solution obtained from 30ml, it was added dropwise by single terminal isocyanate obtained from above-mentioned synthesis 5-1 with 10 minutes under nitrogen atmosphere Acid esters polycarbonate backbone urethane reaction solution 7.0g (2mmol) be dissolved in chloroform 10ml obtained from solution, it Afterwards, react it when stirring 2 hours at 40 DEG C.After reaction terminates, addition water and the mixing that acetone is 1 to 1 (volume ratio) are molten Agent 340g, chloroform and acetone are distilled off under reduced pressure, obtain with PEG- side chain PEI- polycarbonate backbone carbamic acids The aqueous dispersion of the compound (P1-6) of ester structure.Yield is 100%.

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

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

MEK (hereinafter referred to as MEK) 32 is added in the four-hole boiling flask for possessing thermometer, mixer and reflux condenser 32 parts of part and ethanol, warming while stirring is to 80 DEG C in nitrogen stream.Then, it was added dropwise with 2 hours respectively and includes methacrylic acid 20 parts of phosphorus acyloxy ethyl ester, 80 parts of methoxy polyethylene glycol methacrylate-styrene polymer (molecular weight 1000), mercapto-propionate 4.1 Part, MEK80 part of mixture, and comprising polymerization initiator " 2,2 '-azo double (2,4- methyl pentane nitrile) " (and the pure medicine plant formula of light Commercial firm product V-65) 0.5 part, MEK5 parts of mixture.After completion of dropwise addition, 2 " day oil PERBUTYL (registrations are added within every 4 hours Trade mark) O " 0.3 part of (Japan Oil Co's manufacture), stirred 12 hours at 80 DEG C.Water is added to enter in the resin solution for obtaining Row Phase inversion emulsification, after decompression desolventizing, adds water to adjust concentration, so as to obtain (methyl) of non-volatile content 76.8% The aqueous solution of acrylic polymer.The weight average molecular weight by gel permeation chromatography measure of the resin is with polystyrene conversion For 4300, acid number is 97.5mgKOH/g.

((methyl) acrylic polymer containing 2- (2- ethyl hexyl oxies carbonyl) ethylmercapto groups and phosphate residue of synthesis example 8 The synthesis of compound (P2-2))

Using mercaptopropionic acid -2- Octyl Nitrites, 11.2 parts replace 4.1 parts of the mercapto-propionate of synthesis example 7, in addition, Operation same with synthesis example 7, obtains the aqueous solution of (methyl) acrylic polymer (P2-2) of non-volatile content 73.2%. The weight average molecular weight of the polymer is that 4100, acid number is 98.1mgKOH/g.

((methyl) acrylic polymer (P2-3) containing 2,3- dihydroxy rosickyite bases and phosphate residue of synthesis example 9 Synthesis)

Using thioglycerol, 4.1 parts replace 11.2 parts of the mercaptopropionic acid -2- Octyl Nitrites of synthesis example 8, in addition, with conjunction Equally operated into example 8, obtain the aqueous solution of (methyl) acrylic polymer (P2-3) of non-volatile content 70.1%.This gathers The weight average molecular weight of compound is that 5500, acid number is 95.1mgKOH/g.

(the conjunction of (methyl) acrylic polymer (P2-4) containing 2- hydroxyeththylthios and phosphate residue of synthesis example 10 Into)

Using THIOGLYCOL, 2 parts replace 11.2 parts of the mercaptopropionic acid 2- Octyl Nitrites of synthesis example 8, in addition, with conjunction Equally operated into example 8, obtain the aqueous solution of (methyl) acrylic polymer (P2-4) of non-volatile content 56.4%.Weight is equal Molecular weight is that 6700, acid number is 94.9mgKOH/g.

(the conjunction of (methyl) acrylic polymer (P2-5) containing Carboxymethylsulfanyl and phosphate residue of synthesis example 11 Into)

Using TGA, 2 parts replace 11.2 parts of the mercaptopropionic acid -2- Octyl Nitrites of synthesis example 8, in addition, with synthesis Example 8 is equally operated, and obtains the aqueous solution of (methyl) acrylic polymer (P2-5) of non-volatile content 65.1%.Divide equally again Son amount is 6800, acid number is 92.1mgKOH/g.

(the conjunction of (methyl) acrylic polymer (P2-6) containing dodecyl sulfenyl and phosphate residue of synthesis example 12 Into)

Using lauryl mercaptan, 6 parts replace 11.2 parts of the mercaptopropionic acid -2- Octyl Nitrites of synthesis example 8, in addition, with Synthesis example 8 is equally operated, and obtains the aqueous solution of (methyl) acrylic polymer (P2-6) of non-volatile content 77.7%.Weight Average molecular weight is that 9600, acid number is 97.0mgKOH/g.

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

Synthesis example 13

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

[chemical formula 1]

Potassium tert-butoxide (100.8g, 0.8983mol) is added to be stirred in the dehydrated toluene of 1000g, at room temperature with 3 Hour is to toluene (2000g) solution that MPEG-550 (molecular weight 2000,600g) is added dropwise in the mixture.Keeping should After state is stirred at room temperature 2 hours, 40 DEG C are warming up to, be stirred for 2 hours.At the same temperature to table is added dropwise in the mixture Chloropharin (168g, 1.82mol), stirs 5.5 hours at 40 DEG C.Filtering reactant mixture, and filtrate is concentrated, it is residual what is obtained Add chloroform to dissolve again in slag, it is cleaned with water 5 times.Aluminum oxide is dried to addition in chloroform layer and decolourized, filter Aluminum oxide, and filtrate is concentrated.Concentrated residue is carried out into reprecipitation purifying using toluene/n-hexane, the solid for collecting generation enters Row drying under reduced pressure, obtains 507.0g title compounds (yield 82%).

¹H-NMR (deuterochloroform)：δ=3.9-3.4 (m, polyglycol chain etc.), 3.43 (dd, 1H, J=6.0,5.7Hz, One in oxirane ring adjoining methylene hydrogen), 3.38 (s, 3H, PEG terminal methoxy groups), 3.16 (m, 1H, oxirane ring Methine hydrogen), 2.79 (m, 1H, oxirane ring terminal methylene hydrogen), 2.61 (m, 1H, oxirane ring terminal methylene Hydrogen).

[3- (3- (methoxyl group (polyethoxy) ethyoxyl) -2- hydroxyl rosickyite base) methyl propionate

(to polyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition 3- mercapto-propionates Compound) synthesis]

[chemical formula 2]

In the foregoing polyethylene glycol methyl glycidyl ether (molecular weight 2000,1.00g of methoxy poly (ethylene glycol)) for obtaining Middle addition 3- mercapto-propionates (221mg, 1.84mmol) and 1mol/L tetrabutyl ammonium fluorides/tetrahydrofuran solution (100 μ L, Heated up after 0.10mmol), stirred 1 hour at 70~75 DEG C.After cooling, water 20mL and acetic acid second are added in the mixture Ester 20mL, is sufficiently stirred for, and stands a point liquid.Afterwards, then by aqueous layer with ethyl acetate (20mL) clean 2 times.Sulphur is added in water layer During sour sodium, grease is separated out, therefore, it is extracted with dichloromethane (20mL × 3 time).Dichloromethane layer is collected, with nothing After aqueous sodium persulfate is dried, concentrate drying solidification, (yield is about to obtain title Sulfide-containing Hindered organic compound (P3-1) of 0.94g 89%).By¹H-NMR understands, is the purity without especially purifying.

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

Synthesis example 14

[3- (methoxyl group (polyethoxy) ethyoxyl) -2- hydroxyl rosickyite ethyl]

(the change to polyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition ethyl thioglycolate Compound) synthesis]

[chemical formula 3]

Using ethyl thioglycolate (174mg, 1.45mmol) replace synthesis example 13 3- mercapto-propionates (221mg, 1.84mmol), in addition, operation same with synthesis example 13, obtains title Sulfide-containing Hindered organic compound (P3-2) of 1.04g (yield about 98%).

¹H-NMR (deuterochloroform)：δ=4.19 (q, 2H, J=6.9Hz, ethyl ester O adjoining methylene hydrogen), 3.9-3.4 (m, polyglycol chain etc.), 3.38 (s, 3H, PEG terminal methoxy groups), 3.30 (s, 2H ,-SCH₂CO-), 2.82 (dd, 1H, J= 5.1,13.8Hz, polyether compound side S abut methylene), 2.64 (dd, 1H, J=7.5,13.8Hz, polyether compound side S neighbours Connect methylene), 2.58 (br, 1H, OH), 1.29 (t, 3H, J=6.9Hz, ethylacrylate methyl hydrogen)

Synthesis example 15

[2- (3- (methoxyl group (polyethoxy) ethyoxyl) -2- hydroxyl rosickyite base) ethyl propionate

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

[chemical formula 4]

Using ethyl 2-mercaptopropionate (247mg, 1.84mmol) replace synthesis example 13 3- mercapto-propionates (221mg, 1.84mmol), in addition, operation same with synthesis example 13, obtains Sulfide-containing Hindered organic compound (P3-3) (yield of 1.01g About 95%).

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

Synthesis example 16

[3- (3- (methoxyl group (polyethoxy) ethyoxyl) -2- hydroxyl rosickyite base) n-butyl propionate

(to polyethylene glycol methyl glycidyl ether (molecular weight 2000 of polyglycol chain) addition 3- mercaptopropionic acid butyl esters Compound) synthesis]

[chemical formula 5]

Using 3- mercaptopropionic acids butyl ester (243mg, 1.50mmol) replace synthesis example 13 3- mercapto-propionates (221mg, 1.84mmol), in addition, operation same with synthesis example 13, obtains title Sulfide-containing Hindered organic compound (P3-4) of 0.651g (yield about 58%).

¹H-NMR (deuterochloroform)：δ=4.10 (t, 2H, butyl ester O adjoinings methylene), 3.9-3.4 (m, polyglycol chain Deng), 3.38 (s, 3H, PEG terminal methoxy groups), 2.83 (t, 2H, J=7.2Hz, mercaptan compound side S adjoinings methylene), 2.71 (dd, 1H, J=5.7,13.5Hz, one in polyether compound side S adjoining methylene hydrogen), 2.62 (t, 2H, J=7.2Hz, carboxylic Base α methylene hydrogen), 2.62 (dd, 1H, J=7.2,13.5Hz, one in polyether compound side S adjoining methylene hydrogen), 2.48 (br, 1H, OH), 1.63 (m, 2H, butyl ester methylene), 1.37 (m, 2H, butyl ester methylene), 0.94 (t, 3H, J= 7.4Hz, butyl ester terminal methyl group)

Synthesis example 17

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

(to polypropylene glycol butyl glycidyl ether (molecular weight 2000 of polypropylene glycol chain) addition ethyl 2-mercaptopropionate Compound) synthesis]

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

[chemical formula 6]

Replace the MPEG-550 of synthesis example 13 using polypropylene glycol monobutyl base ether (molecular weight 2000,600g) (molecular weight 2000,600g), in addition, operation same with synthesis example 13 obtains title compound 510.3g (yield 85%).

¹H-NMR (deuterochloroform)：δ=3.7-3.4 (m, polypropylene glycol chain and butyl oxygen contiguous bits methylene hydrogen), 3.14 (m, 1H, oxirane ring methine hydrogen), 2.79 (m, 1H, oxirane ring terminal methylene hydrogen), 2.62 (m, 1H, epoxy second Alkane ring terminal methylene hydrogen), 1.55 (m, 2H, butyl methylene hydrogen), 1.35 (m, 2H, butyl methylene hydrogen), 1.15 (md, it is poly- Propylidene methyl hydrogen), 0.91 (t, 3H, J=7.4Hz, butyl terminal methyl group hydrogen)

[chemical formula 7]

Add in the foregoing polypropylene glycol butyl glycidyl ether (molecular weight 2000,2.00g of polypropylene glycol chain) for obtaining Enter ethyl 2-mercaptopropionate (404mg, 3.01mmol) and 1mol/L tetrabutyl ammonium fluorides/tetrahydrofuran solution (100 μ L, After 0.10mmol), heat up, stirred 1 hour at 70~75 DEG C.After cooling, water (20mL) and second are added in the mixture Acetoacetic ester (20mL), is sufficiently stirred for, and stands a point liquid.Thereafter, then by ethyl acetate washed with water (20mL) carry out 2 cleanings.In second The hydrate of copper sulphate 5 (about 1g) is added in ethyl acetate layer, is stirred 10 minutes.Filtering solid constituent, filtrate is concentrated, and obtains title Sulfide-containing Hindered organic compound (P3-5) (2.33g, yield 97%).

¹H-NMR (deuterochloroform)：δ=4.19 (q, 2H, J=6.9Hz, ethyl ester O adjoinings methyl), (m gathers 3.6-3.3 Propane diols chain and butyl methylene-OCH₂- etc.), 2.8-2.6 is (in dd (4 groups), 2H, polyether compound side S adjoining methylene hydrogen One, syn/anti isomer mixtures), 2.1 (br, 1H, OH), 1.44 (d, 3H, J=6.9Hz, carboxyl β methyl), 1.55 (m, 2H, butyl methylene hydrogen), 1.35 (m, 2H, butyl methylene hydrogen), 1.29 (t, 3H, J=6.9Hz, ethyl ester first Base), 1.14 (md, polypropylene methyl hydrogens), 0.91 (t, 3H, J=7.5Hz, butyl terminal methyl group hydrogen).

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

Synthesis example 18

Silver oxide is added in the aqueous solution 138.8g of compound (P1-1) 0.592g obtained in comprising above-mentioned synthesis example 1 10.0g, stirs 30 minutes at 25 DEG C.Then, dimethylethanolamine 46.0g is slowly added to while stirring, as a result, reaction solution It is changed into dark red, somewhat generates heat, keep the state and place, is stirred 30 minutes at 25 DEG C.Thereafter, it is slowly added to while stirring 10% aqueous ascorbic acid 15.2g.Keep the temperature and be further continued for stirring 20 hours, obtain the dispersion of dark red.

The mixed solvent of isopropanol 200ml and hexane 200ml is added in the dispersion liquid after reaction obtained above terminates, After stirring 2 minutes, 5 minutes centrifugal concentratings are carried out with 3000rpm.After supernatant is removed, isopropanol is added in sediment The mixed solvent of 50ml and hexane 50ml, after stirring 2 minutes, 5 minutes centrifugal concentratings is carried out with 3000rpm.Supernatant is removed Afterwards, add water 20g again in sediment, stir 2 minutes, under reduced pressure remove organic solvent, obtain aqueous point of Argent grain A prose style free from parallelism (B-1).

The dispersion (B-1) for obtaining is taken, is determined by 10 times of visible absorption spectras of dilution, confirmed at 400nm To the peak of plasma absorption spectrum, confirm to generate silver nano-grain.Additionally, confirming as spherical Yin Na by tem observation Rice grain (average grain diameter 17.5nm).The silver-colored containing ratio in solid is determined using TG-DTA, is as a result 97.2%.It is possible thereby to estimate It is 2.8% to calculate compound (P1-1) content in the nonvolatile component in the dispersion obtained by this synthetic method.

Synthesis example 19

Compound (P1-2) 20mg (ethylene imine units that will be obtained in above-mentioned synthesis example 2 are prepared respectively：0.15mmol) Solution 2A obtained from being dissolved in water 2.39g, silver nitrate 0.16g (0.97mmol) is dissolved in obtained from water 1.30g Solution 2B, sodium citrate 0.12g (0.48mmol) is dissolved in water 0.25g obtained from solution 2C.In 25 DEG C of following stirrings While adding solution 1B in solution 1A, solution 1C is subsequently added into.Dispersion liquid gradually becomes dark-brown.After stirring 7 days, by dialysis Purified, obtained aqueous dispersions (B-2).

1 part of aqueous dispersions for obtaining (B-2) is taken, is determined by 10 times of visible absorption spectras of dilution, at 400nm The peak of plasma absorption spectrum is confirmed, confirmation generates silver nano-grain.Additionally, by tem observation confirm as 20nm with Under silver nano-grain.

After the solvent of the aqueous dispersions (B-2) that will be obtained is distilled off, is determined by TGA and silver content is measured, tied Fruit is 83%.Additionally, the aqueous dispersions for obtaining also did not found to assemble at 2 months, precipitate, excellent storage stability is confirmed.

Synthesis example 20

In synthesis example 19, solution 2C is added in solution 2A, solution 1B is subsequently added into, in addition, with synthesis example 19 Same operation, obtains aqueous dispersions (B-3).The aqueous dispersions stabilization for obtaining, takes 1 part of dispersion liquid, by 10 times of dilutions Visible absorption spectra is determined, and the peak of plasma absorption spectrum is confirmed at 400nm, and confirmation generates silver nano-grain.This Outward, by tem observation, the silver nano-grain of below 20nm is confirmed as.

Synthesis example 21

In synthesis example 19, solution 2C is added in solution 2A, after stirring 7 days, add solution 2B, be stirred for 7 days, except this In addition, operation same with synthesis example 19, obtains aqueous dispersions (B-4).The aqueous dispersions stabilization for obtaining, takes 1 part of dispersion liquid, leads to Cross 10 times of visible absorption spectras of dilution to determine, the peak of plasma absorption spectrum is confirmed at 400nm, confirm to generate Silver nano-grain.Additionally, by tem observation, confirming as the silver nano-grain of below 20nm.

Synthesis example 22~24

In synthesis example 19, solution 2A is replaced using following solution, in addition, operation same with synthesis example 19 is obtained 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 for obtaining are stablized, and take 1 part of dispersion liquid, are determined by 10 times of visible absorption spectras of dilution, The peak of plasma absorption spectrum is confirmed near 400nm, confirmation generates silver nano-grain.Additionally, by tem observation, Confirm as the silver nano-grain of below 40nm.

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

Aqueous dispersions 5.0g (the EI units of the compound (P1-2) obtained in synthesis example 21：Being added in 0.41mmol) will Silver nitrate 0.02g (0.12mmol) is dissolved in silver nitrate aqueous solution obtained from water 5.0g, is stirred at 25 DEG C.Dispersion liquid is gradually It is changed into light brown.After 7 days, purified by dialysis, obtained aqueous dispersions (B-8).The aqueous dispersions stabilization for obtaining, takes 1 Part dispersion liquid, is determined by 10 times of visible absorption spectras of dilution, and plasma absorption spectrum is confirmed near 400nm Peak, confirmation generates silver nano-grain.Additionally, by tem observation, confirming as the silver nano-grain of below 40nm.

Synthesis example 26

Prepare and include 85%N, (methyl) propylene obtained in N- diethyl hydroxylamines 463g (4.41mol), above-mentioned synthesis example 7 The reductant solution of acids polymers (P2-1, equivalent to nonvolatile matter 23.0g) and water 1250g.In addition, will be equivalent to not wave (methyl) acrylic polymer (P2-1) obtained in the synthesis example 7 of stimulating food 11.5g is dissolved in water 333g, and adding wherein will Silver nitrate 500g (2.94mol) be dissolved in water 833g obtained from solution, be sufficiently stirred for.Under room temperature (25 DEG C) with 2 hours to Foregoing reductant solution is added dropwise in the mixture.The reactant mixture that will be obtained molecular filter (0.45 micron of pore diameter) mistake Filter, makes filtrate in hollow fiber type ultrafiltration module (the MOLSEP MODULE of DAICEN MEMBRENE-SYSTEMS LTD. manufactures FB-02 types, molecular cut off 15 ten thousand) middle circulation, the water that the amount corresponding with the amount of filtrate of outflow is added at any time are purified.Really The electrical conductivity of filtrate is recognized after below 100 μ S/cm, to stop water filling and concentrating.Concentrate is reclaimed, non-volatile content is obtained (decentralized medium is water to 36.7% silver nano-grain dispersion liquid：B-9)(742.9g).The silver obtained using dynamic light scattering method The average grain diameter of grain is 39nm, and 10-40nm is estimated as from TEM image.Silver content in nonvolatile matter is determined by thermogravimetric analysis, Result is 94.8w/w% (yield 81%).

Synthesis example 27

Prepare and include 85%N, (methyl) third obtained in N- diethyl hydroxylamines 5.56g (53.0mmol), above-mentioned synthesis example 8 The reductant solution of alkene acids polymers (P2-2, equivalent to nonvolatile matter 106mg) and water 15g.In addition, will be equivalent to not wave (methyl) acrylic polymer (P2-2) obtained in the synthesis example 8 of stimulating food 106mg is dissolved in water 5g, is added thereto to nitre Sour silver 6.00g (35.3mmol) be dissolved in water 10g obtained from solution, be sufficiently stirred for.Under room temperature (25 DEG C) with 2 hours to Foregoing reductant solution is added dropwise in the mixture.The reactant mixture that will be obtained molecular filter (0.45 micron of pore diameter) mistake Filter, makes filtrate in hollow fiber type ultrafiltration module (the MOLSEP MODULE of DAICEN MEMBRENE-SYSTEMS LTD. manufactures HIT-1 types, molecular cut off 15 ten thousand) middle circulation, the water that the amount corresponding with the amount of filtrate of outflow is added at any time are purified.Really The electrical conductivity of filtrate is recognized after below 100 μ S/cm, to stop water filling and concentrating.Concentrate is reclaimed, non-volatile content is obtained about The aqueous dispersions (B-10) of 30% silver nano-grain.The particle diameter of the silver nano-grain is estimated as 10-40nm from TEM image.

Synthesis example 28~31

As compound, using the compound (P2-3~6) of following table instead of (methyl) acrylic compounds for being obtained in synthesis example 8 Polymer, in addition, same operation is carried out with synthesis example 27, obtains the silver nano-grain of non-volatile content about 30% Aqueous dispersions (B-11~14).The particle diameter of the silver nano-grain is estimated as 10-40nm from TEM image.

[table 2]

	Protective agent
		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 polymer (P2-1, be converted into solid constituent for 0.106g) that will be obtained in synthesis example 7 is molten Solution adds 1mol/L nitric acid 12mL wherein in water 12mL, and then, be dissolved in for silver nitrate 6.00g (35.3mmol) by addition Solution obtained from water 24mL and triethanolamine 13.2g (88.3mmoL), stir 2 hours at 60 DEG C, obtain the brown of muddiness Solution.After cooling, by ultrafiltration module (the MOLSEP MODULE HIT- that DAICEN MEMBRENE-SYSTEMS LTD. are manufactured 1 type, molecular cut off 150,000,1), further circulation purified water carries out purifying until oozing out oozing out for about 1L from ultra filtration unit Liquid.Stop supply purified water and concentrate, obtain the aqueous dispersions (B-15) (solid constituent 30w/w%) of the Argent grain of 12.5g.Should The particle diameter of silver nano-grain is estimated as 10-40nm from TEM image.

Synthesis example 33

(methyl) acrylic polymer (P2-1, be converted into solid constituent for 0.106g) that will be obtained in synthesis example 7 is molten Solution adds 1mol/L nitric acid 12mL wherein in water 12mL, and then, be dissolved in for silver nitrate 6.00g (35.3mmol) by addition Solution obtained from water 24mL.At room temperature to being slowly added dropwise DMAE 7.87g in the solution (88.3mmoL) be dissolved in water 15mL obtained from solution.After dropwise addition, it is stirred at room temperature 3 days, obtains the brown of muddiness Solution.It is passed to ultrafiltration module (the MOLSEP MODULE HIT-1 of DAICEN MEMBRENE-SYSTEMS LTD. manufactures Type, molecular cut off 150,000,1), and then the purified water that circulates carries out purifying until oozing out the diffusate of about 1L from ultra filtration unit. Stop supply purified water and concentrate, obtain the aqueous dispersions (B-16) (solid constituent 30w/w%) of the Argent grain of 12.5g.The silver The particle diameter of nano particle is estimated as 10-40nm from TEM image.

Synthesis example 34

Prepare and include 85%N, (methyl) acrylic acid obtained in N- diethyl hydroxylamines 5.56g (53.0mmol), synthesis example 7 The reductant solution of analog copolymer (P2-1, equivalent to nonvolatile matter 106mg) and water 15g.In addition, will be equivalent to nonvolatile matter (methyl) acrylic polymer (P2-1) obtained in the synthesis example 7 of 106mg is dissolved in water 5g, is added nitric acid wherein Silver-colored 6.00g (35.3mmol) be dissolved in water 10g obtained from solution, be sufficiently stirred for.To the mixture, under ice-cooling with 2 Hour is added dropwise foregoing reductant solution.Make the reactant mixture for obtaining in hollow fiber type ultrafiltration module (DAICEN Ten thousand) the middle circulation of MOLSEP MODULE HIT-1 types, the molecular cut off 15 of MEMBRENE-SYSTEMS LTD. manufactures, adds at any time Plus the water of the amount corresponding with the amount of filtrate of outflow is purified.The electrical conductivity of filtrate is confirmed after below 100 μ S/cm, to stop Water filling is simultaneously concentrated into about 10mL.While to ethanol is added in ultrafiltration system, the amount suitable with the amount of filtrate of outflow is added on side at any time Ethanol, carries out exchange of solvent.After flowing out the ethanol filtrate of 100mL, concentrated, obtained the argentiferous of non-volatile content about 60% The alcohol dispersion liquid (B-17) of nano-particles reinforcement body.

Synthesis example 35

(methyl) acrylic polymer (P2-1, be converted into solid constituent for the 2.00g) dissolving that will be obtained in synthesis example 7 In water 40mL, addition acetic acid copper hydrate 10.0g (50.09mmol) is dissolved in water 500mL obtained from solution.With about 80% hydrazine aqueous solution 10g (about 160mmol) is added dropwise within 2 hours thereto makes its steady foaming, and then is stirred at room temperature 1 hour directly Stop to foaming, obtain solution russet.

It is passed to ultrafiltration module (DAICEN MEMBRENE-SYSTEMS LTD. manufactures, molecular cut off 150,000,1 It is individual), and then the purified water deaerated using nitrogen bubbling that circulates carries out purifying until oozing out oozing out for about 1L from ultra filtration unit Liquid.Stop supply de aerated water and concentrate, obtain the aqueous dispersions (B-18) (solid constituent about 20w/w%) of 15g.This point is dripped by one Dispersion liquid determines ultraviolet-visible absorption spectroscopy in being dissolved in ethanol (50mL), is found from plasma resonance near 600nm Absorb, confirmation generates copper nano particles.The particle diameter of the copper nano particles is estimated as 30-80nm from TEM image.

Synthesis example 36

Have to comprising the Sulfide-containing Hindered obtained in copper acetate (II) monohydrate (3.00g, 15.0mmol), above-mentioned synthesis example 13 In the mixture of machine compound (P3-1,0.451g) and ethylene glycol (10mL), add when nitrogen is blown into the flow of 50mL/ minutes Heat, air agitation is de-gassed for 2 hours at 125 DEG C.The mixture is recovered to room temperature, is slowly added dropwise with syringe pump and is used 7mL Water dilutes solution obtained from hydrazine hydrate (1.50g, 30.0mmol).Now, due to being produced with initial reduction reaction Nitrogen and can tempestuously foam, it is therefore desirable to note.About 1/4 amount was slowly added dropwise with 2 hours, dropwise addition, stirring 2 is at this moment temporarily ceased Hour, confirm after foaming calms down, then remaining amount was added dropwise with 1 hour.The solution of the brown that will be obtained is warming up to 60 DEG C, then stirs Mix 2 hours, terminate reduction reaction.Now, through when take a small amount of reaction solution russet, with the addition of 0.1% hydrazine water The degassing purified water of compound is diluted, and ultraviolet-visible absorption spectroscopy is obtained immediately after, and peak is observed at 570~580nm. It is the absorption for going back the plasmon absorption shown by native copper from nano-scale.It is possible thereby to confirm to generate receive Rice copper particle.

(preparation of aqueous dispersion)

Then, the hollow fiber type ultrafiltration for making the reactant mixture be manufactured in DAICEN MEMBRENE-SYSTEMS LTD. Membrane module (HIT-1-FUS1582,145cm², molecular cut off 15 ten thousand) in circulation, side adds and the filtrate equivalent oozed out The 0.1% hydrazine hydrate aqueous solution, while be circulated purifying untill the filtrate from ultrafiltration module reaches about 500mL.Stop The 0.1% hydrazine hydrate aqueous solution is supplied, the state is kept and is concentrated by ultrafiltration, obtain the organic compound of 2.85g With the aqueous dispersion (B-19) of the complex of nano copper particle.Non-volatile content in dispersion is 16%, in nonvolatile matter Tenor be 95%.The copper particle obtained with electron microscope observation, is judged as the particulate of 20~60nm or so.Additionally, It is now 108nm by the average grain diameter of dynamic light scattering determination.Be can confirm that as also from the Wide angle X-ray diffraction of dispersion Native copper.

Synthesis example 37~40

For the Sulfide-containing Hindered organic compound (P3-2~5) of synthesis example 14~17, also operated in the same manner as synthesis example 36, made Back-up dispersion liquid (B-20~23).A part of reactant mixture is taken, ultraviolet-visible absorption spectroscopy is determined, results verification is arrived：Using appoint A kind of compound can observe the very big suction from nano copper particle surface plasma body resonant vibration between 570~600nm Receive.

Synthesis example 41

Replace the ethylene glycol (10mL) of synthesis example 36 using propylene glycol monomethyl ether (10mL), in addition, with Synthesis example 36 is similarly carried out, and prepares dispersion liquid (B-24).A part of reactant mixture is taken, ultraviolet-visible absorption spectroscopy is determined, Results verification is arrived：The maximum absorption from nano copper particle surface plasma body resonant vibration is observed between 570~600nm. The particle diameter of the silver nano-grain is estimated as 20-80nm from TEM image.

Synthesis example 42

To comprising the Sulfide-containing Hindered organic compound obtained in cuprous oxide (I) (5.4g, 37.5mmol), above-mentioned synthesis example 13 Silver nano-grain dispersion liquid (B-9, particle diameter 10-40nm, 3.0 milligrams of the silver obtained in (P3-1,2.254g), above-mentioned synthesis example 26 Atom, aqueous solvent), in the mixture of ethanol 80ml and water 20ml, while be blown into nitrogen with the flow of 50mL/ minutes, while being heated to 40 ℃.Further addition hydrazine monohydrate (7.5g, 150mmol) in the mixture.Stirring 2 is small in the state of being maintained at 40 DEG C When, terminate reduction reaction.

Then, the hollow fiber type ultrafiltration for making the reactant mixture be manufactured in DAICEN MEMBRENE-SYSTEMS LTD. Membrane module (HIT-1-FUS1582,145cm², molecular cut off 15 ten thousand) in circulation, side add with ooze out it is filtrate equivalent, enter The 0.1% hydrazine aqueous solution of nitrogen bubbling, side circulatory purification gone until the filtrate from ultrafiltration module reaches about 500mL.Stop supplying To the 0.1% hydrazine aqueous solution and concentrate, obtain silver core copper core-shell nanoparticles dispersion liquid (B-25) of 27.9g.Not waving in dispersion liquid Stimulating food content is that the tenor in 15%, nonvolatile matter is 95%.The particle obtained with electron microscope observation, is judged as 40 The particulate of~80nm or so.Additionally, can confirm that as silver by the Wide angle X-ray diffraction of dispersion and gone back the mixture of native copper.This Outward, determine understand to be silver core copper shell particle by TEM photos and TEM-EDS.Additionally, a small amount of solution russet for obtaining is taken, Spent glycol is diluted, and obtains ultraviolet-visible absorption spectroscopy, as a result observe nano-scale go back that native copper shows 565~ The peak of the plasmon absorption of 580nm.Even if additionally, by obtaining UV, visible light to ethylene glycol dilution after 1 hour Absorption spectrum, the peak of plasmon absorption is not reduced yet, it can thus be appreciated that inoxidizability 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, except this with Outward, operation same with synthesis example 42, makes silver core copper core-shell nanoparticles dispersion (B-26~30).Obtained with electron microscope observation The particle for arriving, is judged as the particulate of 40~80nm or so.Additionally, from the Wide angle X-ray diffraction of dispersion can confirm that for silver and The also mixture of native copper.

[table 3]

	Mixed solvent	Mixed proportion (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

Compare synthesis example 1

Embodiment 1 based on patent document 4,50 μm of ol of silver nitrate (I) is dissolved in pure water 94ml, while being vigorously stirred The solution, while to being implanted sequentially the aqueous solution 1ml containing stearic methyl ammonium 10mg in the solution and contain sodium borohydride 200 μm of aqueous solution 5ml of ol, as a result, liquid color becomes that to turn to yellowish-brown transparent, obtains silver-colored hydrosol 100ml.

Compare synthesis example 2

Embodiment 2 based on patent document 5, silver sulfate 10mmol is dissolved in pure water 800ml, molten to this while stirring The aqueous solution 100ml containing polyoxyethylene stearyl base ether phosphoric acid 500mg is added in liquid, is reached uniform.Then, side is acutely stirred Side is mixed to the aqueous solution 50ml containing dimethyamine borane 5mmol is added in the solution, uniform mode is reached.In solution When color cataclysm is bronzing, the aqueous solution 50ml containing 0.02mmol palladium nitrates is added.As a result, obtaining uniform and bronzing Transparent silver-colored particle dispersion liquid 1000ml.

Embodiment 1

(formation of the non-conductive layer in insulating properties base material)

Addition ethanol in the aqueous dispersion (B-1) of the Argent grain made in synthesis example 18, forms silver concentration 5%, water/second The Argent grain dispersion liquid of alcohol (1/1 (w/w)), KF-351A (the Shin-Etsu Chemical Co., Ltd.s systems of addition 0.1% Make).Using the K101 rods of No. 0 (4 μm of wet type thickness), with K-control coater (K101, RK Print Coat Instruments Ltd, manufacture) speed scale 10 condition, by the dispersion liquid coating (rod painting) in Kapton In (Kapton EN150-C, 38 μ m-thicks, Du Pont-Toray Co., Ltd. manufacture).The film is set to be dried at room temperature for it Afterwards, the surface of the film is observed with scanning electron microscope, as a result, the covering rate of the polyimide surface that Argent grain brings is About 90%.Determine the resistance of silver-colored film coated surface, as a result, due to being 10⁷The resistance of more than Ω and cannot determine, confirm in polyamides The film of the Argent grain formed on imines film is dielectric film.

(electroless copper operation)

Above-mentioned Argent grain is coated with Kapton as the test film of plating, pharmaceuticals industry strain formula meeting in open country difficult to understand is used The chemical plating reagent of society's manufacture carries out chemical plating.The operation of electroless copper is by via degreasing, washing, activation, washing, chemistry Plating, the operational sequence of washing are carried out.The flowing water washed as 2 minutes is washed.

1. degreasing：Using degreasing agent (ICP Cleaner SC, Okuno Chemical Industries Co., Ltd. manufacture), at 40 DEG C of place Impregnated 5 minutes in reason liquid.

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

3. chemical plating：Using chemical bronze plating liquid (OIC COPPER, Okuno Chemical Industries Co., Ltd. manufacture), in pH12.5 Plating liquid at 55 DEG C impregnate 20 minutes.

The coating side surface of the Argent grain of the test film for chemically being taken out in copper plating bath is integrally changed into light red, can confirm that The chemical plating of copper has been carried out well.Test film carries out the baking of 60 minutes after washing, air-drying at 100 DEG C.By chemistry The sheet resistance value for plating the copper film for being formed is 0.04 Ω/, and the polyimides that can be produced on i.e. 38 μ m-thicks of insulating properties base material is thin The conductive material of the conductive layer with copper on film.The conductive layer of the copper to being consequently formed carries out utilizing cellophane tape The belt stripping test of (manufacture of Nichiban Co., Ltd.s), does not as a result confirm stripping, and adaptation is also good.

Embodiment 2~5

In embodiment 1, after the Argent grain film drying at room temperature of masking being coated with Kapton, shown in following table Temperature, the time be sintered, in addition, operate similarly to Example 1, on Kapton formed have following table institute The non-conductive layer of (Fig. 7-14) Argent grain for the surface covering rate shown, operates similarly to Example 1, carries out electroless copper, knot Really, under all of sintering temperature, good copper plating film is respectively formed, leading with copper can be produced on Kapton The conductive material of electric layers.

[table 4]

Embodiment 7~13

In embodiment 1, the dispersion of the Argent grain that will be used is dissipated by the moisture of the Argent grain made in synthesis example 18 Body (B-1) is changed to the aqueous dispersion (B-2~8) obtained in synthesis example 19~25, in addition, operates similarly to Example 1, The non-conductive layer of Argent grain is formed on Kapton, is operated similarly to Example 1, carry out electroless copper, as a result, In all of embodiment, good copper plating film is respectively formed, can be produced on Kapton and be with surface resistivity The conductive material of the conductive layer of the copper of 0.04~0.06 Ω/ or so.

[table 5]

Embodiment 14~48

In embodiment 7~13, after the Argent grain film drying at room temperature of masking is coated with Kapton, following table Shown temperature, time are sintered, and in addition, operate similarly to Example 1, and Argent grain is formed on Kapton Non-conductive layer, operate similarly to Example 1, carry out electroless copper, as a result, all of Argent grain dispersion, all of burning Good copper plating film is all formed under junction temperature, can be produced on Kapton have surface resistivity be 0.04~ The conductive material of the conductive layer of the copper of 0.08 Ω/ or so.

[table 6]

Embodiment 49

Using conductive material obtained in embodiment 1, the conductive layer with copper on Kapton, electricity is carried out Plating (copper sulphate).Copper sulphate plating is based on conventional method via degreasing, washing, pickling, washing, copper sulphate plating, washing, antirust Treatment, the operation of washing are carried out.

1. degreasing：Using degreasing agent (DP320 Cleaner, Okuno Chemical Industries Co., Ltd. manufacture), at 45 DEG C of place Impregnated 5 minutes in reason liquid.

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

3. copper sulphate plating：Use the sulphur for being added with Top Lucina SF-M (Okuno Chemical Industries Co., Ltd.'s manufacture) Sour copper plating liquid, in 23 DEG C, 2.5A/dm²Under conditions of impregnate 29 minutes.

4. antirust treatment：Using antirust agent (Top Rinse CU-5, Okuno Chemical Industries Co., Ltd. manufacture), at 25 DEG C Lower dipping 1 minute.

The test film electroplated wipes moisture away after washing, and heated-air drying is carried out afterwards, and 60 points are carried out at 120 DEG C The baking of clock.The average film thickness of the layers of copper formed on Kapton after plating is 16 μm, can be produced on 38 μ m-thicks The conductive material of the conductive layer with 16 μ m-thicks on Kapton.The stripping of the copper formed on Kapton Intensity is 9-10N/cm, shows good dhering strength.

Embodiment 50~54

In embodiment 49, using the conductive material obtained in embodiment 2~6 instead of using obtaining in embodiment 1 Conductive material, is electroplated in the same manner as embodiment 49.The average film thickness of the layers of copper formed on Kapton is 16 μ M, can be produced on the Kapton of 38 μ m-thicks the conductive material of the conductive layer with 16 μ m-thicks.In polyimides The peel strength of the copper formed on film is as shown in the table to show good dhering strength.

[table 7]

Embodiment	The conductive material used in plating	The peel 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, using the conductive material obtained in the embodiment that following table is recorded instead of using in embodiment 1 The conductive material for obtaining, is electroplated in the same manner as embodiment 49.The average film of the layers of copper formed on Kapton Thickness is 16 μm, can be produced on the Kapton of 38 μ m-thicks the conductive material of the conductive layer with 16 μ m-thicks. The peel strength of the copper formed on Kapton is as shown in the table to show good dhering strength.

[table 8]

Embodiment	The conductive material used in plating	The peel 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, using the Argent grain for being exchanged for by aqueous solvent ethanol alcoholic dispersion instead of using Aqueous dispersion (B-1), the alcoholic dispersion of silver concentration 5% is coated on Kapton, in addition, with embodiment 1, 7~13 same operations, after dry, sintering is coated to silver-colored non-conductive layer on Kapton, carry out chemical plating, The electric conductivity of the conductive layer of the copper for having that surface resistivity is 0.04-0.05 Ω/ or so is produced on Kapton Material.

Using these conductive materials, operation same with embodiment 49 is electroplated.Formed on Kapton The average film thickness of layers of copper is 16 μm, can be produced on the Kapton of 38 μ m-thicks leading for the conductive layer with 16 μ m-thicks Electric material.The peel strength of the copper formed on Kapton is 9~11N/cm, shows that good stripping is strong Degree.

[table 9]

Embodiment 70~71

In embodiment 62, to the alcoholic dispersion of silver concentration 5%, silver coating is non-conductive on Kapton Layer is simultaneously dried, and after being sintered 5 minutes under 100 DEG C or 270 DEG C of sintering temperature, carries out chemical plating.On Kapton Layers of copper surface resistivity for 0.04~0.05 Ω/ or so.Using the conductive material, it is same with embodiment 49 operate into Row plating.The average film thickness of the layers of copper formed on Kapton is 16 μm, can be produced on the polyimides of 38 μ m-thicks The conductive material of the conductive layer with 16 μ m-thicks on film.The peel strength of the copper formed on Kapton is as follows Good dhering strength is shown shown in table.

[table 10]

Comparative example 1

Impregnated 10 minutes in the Argent grain dispersion liquid that Kapton is made in relatively Production Example 1, make polyamides sub- Amine film surface adsorbs silver colloid, after the film is dried at room temperature for, is sintered 30 minutes at 180 DEG C.Use scanning electron The surface (Figure 15,16) of the micro- sem observation film, as a result, the covering rate of the polyimide surface that Argent grain brings is 8%.

(electroless copper operation)

The Kapton of silver colloid is adsorbed to this, has been operated similarly to Example 1, carried out Electroless Plating Procedure, as a result, The part adsorbed in the silver colloid on surface departs from degreaser dipping.The precipitation of the copper in electroless copper operation is spot sample Uneven precipitation, account for all surfaces product 30% or so.

Comparative example 2

It is 0.5% using removing water in the silver-colored hydrosol that evaporator makes from Production Example 1 is compared and concentrating.Now, silver Colloid is aggregated, and dispersion liquid heterogeneous.Operated similarly to Example 1 using the concentrate and be coated on Kapton When upper, it is impossible to obtain uniform film.Thereafter, although attempting to operate similarly to Example 1 carries out Electroless Plating Procedure, but is attached to The silver colloid aggregation on surface departs from degreaser dipping, and the precipitation of copper does not occur.

Comparative example 3

Impregnated 10 minutes in the Argent grain dispersion liquid that Kapton is made in relatively Production Example 2, make polyamides sub- Amine film surface adsorbs silver colloid, after the film is dried at room temperature for, is sintered 30 minutes at 180 DEG C.Use scanning electron The surface of the micro- sem observation film, as a result, the covering rate of the polyimide surface that Argent grain brings is 15%.

(electroless copper operation)

The Kapton of silver colloid is adsorbed to this, operation similarly to Example 1 carries out Electroless Plating Procedure, as a result, The part adsorbed in the silver colloid on surface departs from degreaser dipping.The precipitation of the copper in electroless copper operation is spot sample Uneven precipitation, account for all surfaces product 40% or so.

Comparative example 4

Using removing water in the Argent grain dispersion liquid that evaporator makes from Production Example 2 is compared and be concentrated into 1%.Now, Silver colloid is aggregated, and dispersion liquid heterogeneous.The concentrate is operated similarly to Example 1 and is coated on Kapton When upper, it is impossible to obtain uniform film.

The Kapton of silver colloid is adsorbed to this, operation similarly to Example 1 carries out Electroless Plating Procedure, as a result, A part for the silver colloid aggregation on surface is attached to depart from degreaser dipping.The precipitation of the copper in electroless copper operation is Speckled uneven precipitation, accounts for 50% or so of all surfaces product.

Comparative example 5

Operation same with the embodiment 1 of patent document 2, it is same with embodiments of the invention 1 after obtaining cuprous oxide dispersion Sample is operated, and coating (rod painting) is on Kapton.After the film is dried at room temperature for, sintered 60 minutes at 350 DEG C. The surface of the film is observed with scanning electron microscope, as a result, the covering rate of the polyimide surface that copper particle brings is 100%.

Using the above-mentioned Kapton with electric conductivity copper membrana granulosa as plating test film, similarly to Example 1 Operation, carries out chemical plating, as a result, the sheet resistance value of the copper film formed by chemical plating is 0.04 Ω/, can be produced on absolutely Edge base material is the conductive material of the conductive layer on the Kapton of 38 μ m-thicks with copper.Grasp similarly to Example 1 Make, the conductive layer to copper is carried out using the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.s), as a result, The entire surface for being bonded with adhesive tape is peeling-off.

Comparative example 6

In embodiment 1, silver concentration is changed to 22% by 5%, in addition, is operated similarly to Example 1, use 0 Number K101 rods (6 μm of wet type thickness), in K-control coater (K101, RK Print Coat Instruments Ltd. manufacture) speed scale 10 under conditions of, by the dispersion liquid of Argent grain coating (rod painting) in Kapton (Kapton EN150-C, 38 μ m-thicks, Du Pont-Toray Co., Ltd. manufacture) on.After the film is dried at room temperature for, at 180 DEG C Sintering 30 minutes.The surface of the film is observed with scanning electron microscope, as a result, the polyimide surface that Argent grain brings Covering rate is 100% (Figure 17), and the average stacking number of the Nano Silver of the polyimide surface converted by thickness is 6 layers (Figure 18). Determine the resistance of silver-colored film coated surface, as a result, form the conductive film that surface resistivity is 0.4 Ω/ or so.

(electroless copper operation)

Using the above-mentioned Kapton with conductive silver membrana granulosa as plating test film, it is same with embodiment 1 Sample is operated, and carries out chemical plating, as a result, the sheet resistance value of the copper film formed by chemical plating is 0.04 Ω/, can be produced on Insulating properties base material is the conductive material of the conductive layer on the Kapton of 38 μ m-thicks with copper.Similarly to Example 1 Operation, the conductive layer to copper is carried out using the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.s), knot Really, the entire surface for being bonded with adhesive tape is peeling-off.

Comparative example 7

The tool on the Kapton of 38 μ m-thicks for using the method using comparative example 1 obtained after chemical plating There is the base material of the conductive layer of copper, operation same with embodiment 49 is electroplated (copper sulphate).In Kapton after plating The average film thickness of the layers of copper of upper formation is 16 μm.The peel strength of the copper formed on Kapton is 1N/cm or so, is It is closely sealed bad.

Comparative example 8

In comparative example 1, electroless copper treatment is not carried out, using the Kapton of the conductive layer with silver, with reality Apply example 49 equally to operate, electroplated (copper sulphate).The average film thickness of the layers of copper of formation is on Kapton after plating About 15 μm.The peel strength of the copper formed on Kapton is 1N/cm or so, is closely sealed bad.

Embodiment 72

(formation of the non-conductive layer in insulating properties base material)

Ethanol is added in the aqueous dispersion (B-9) made in synthesis example 26, silver concentration 5%, water/ethanol (1/1 is formed (w/w) Argent grain dispersion liquid).Using the K101 rods of No. 0 (4 μm of wet type thickness), in K-control coater (K101, RK Print Coat Instruments Ltd. manufacture) speed scale 10 under conditions of, by the dispersion liquid coating (rod paintings) gathering On imide membrane (Kapton EN150-C, 38 μ m-thicks, Du Pont-Toray Co., Ltd. manufacture).By the film in room temperature After lower drying, the sintering of 5 minutes is carried out at 250 DEG C, with the surface of scanning electron microscope viewing film, as a result, silver The covering rate of the polyimide surface that grain brings is for about 95%.Determine the resistance of silver-colored film coated surface, as a result, be 10⁷More than Ω's Resistance cannot thus be determined, and confirm that the film formed by Argent grain formed on Kapton is dielectric film.

(electroless copper operation)

Above-mentioned Argent grain is coated with Kapton as the test film of plating, pharmaceuticals industry strain formula in open country difficult to understand is used The plating reagent of commercial firm's manufacture carries out chemical plating.The operation of electroless copper is by via degreasing, washing, activation, washing, chemistry Plating, the flow chart of washing are carried out.The flowing water washed as 2 minutes is washed.

1. degreasing：Using degreasing agent (OPC190 Cleaner, Okuno Chemical Industries Co., Ltd. manufacture), at 60 DEG C of place Impregnated 5 minutes in reason liquid.

Chemically the coating side surface generally light red of the Argent grain of the test film that copper plating bath takes out, can confirm that good The chemical plating of copper has been carried out well.Test film carries out the baking of 60 minutes after washing, air-drying at 100 DEG C.By chemical plating The sheet resistance value of the copper film of formation is 0.04 Ω/, can be produced on the Kapton of 38 μ m-thicks of insulating properties base material The conductive material of the upper conductive layer with copper.The conductive layer of the copper being consequently formed carries out utilizing cellophane tape The result of the belt stripping test of (manufacture of Nichiban Co., Ltd.s), unconfirmed to stripping, adaptation is also good.

Embodiment 73

In embodiment 72, replace dispersion liquid (B-9) using aqueous dispersions (B-10~16), in addition, with embodiment 72 same operations, are produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks the electric conductivity material of the conductive layer with copper Material.The sheet resistance value of copper film is calculated as about 0.04 Ω/ with all material, and conductive layer carries out utilizing cellophane tape The result of the belt stripping test of (manufacture of Nichiban Co., Ltd.s), unconfirmed to stripping, adaptation is also good.

Embodiment 74

In embodiment 72, it is changed to dispersion liquid (B-17) to replace dispersion liquid (B-9), and form the second of Argent grain 5% Alcohol dispersion liquid, in addition, operation same with embodiment 72 is produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks The conductive material of the conductive layer with copper.The sheet resistance value of copper film is calculated as about 0.04 Ω/, conductive layer with all material The result using the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.s) is carried out, it is unconfirmed to stripping, it is close Conjunction property is also good.

Embodiment 75

Use obtained in embodiment 72~74, conductive layer with copper on the Kapton of 38 μ m-thicks Conductive material, operation same with embodiment 49, is electroplated (copper sulphate).The copper formed on Kapton after plating The average film thickness of layer is respectively 16 μm.The peel strength of the copper formed on Kapton is 9~10N/cm or so, display Go out good adaptation.

Embodiment 76

(formation of the non-conductive layer in insulating properties base material)

Addition ethanol in the aqueous dispersion (B-18) of the copper particle made in synthesis example 35, formation copper concentration 5%, water/ The copper particle dispersion of ethanol (1/1 (w/w)).Using the K101 rods of No. 0 (4 μm of wet type thickness), in K-control coater Under conditions of the speed scale 10 of (K101, RK Print Coat Instruments Ltd. manufactures), by dispersion liquid coating (rod painting) is on Kapton (Kapton EN150-C, 38 μ m-thicks, Du Pont-Toray Co., Ltd. manufacture).Should After film is dried at room temperature for, the sintering of 5 minutes is carried out at 250 DEG C, with the surface of scanning electron microscope viewing film, As a result, the covering rate of the polyimide surface that copper particle brings is for about 95%.It is 10 when determining the resistance of silver-colored film coated surface⁷Ω Resistance above, thus cannot determine, what confirmation was formed on Kapton is non-conductive by the granuloplastic film of copper Film.

(electroless copper operation)

Above-mentioned copper particle is coated with Kapton as the test film of plating, pharmaceuticals industry strain formula in open country difficult to understand is used The plating reagent (OIC COPPER) of commercial firm's manufacture, impregnates 20 minutes in the plating liquid of pH12.5 at 55 DEG C, carries out chemistry Plating.

Chemically the coating side surface generally light red of the copper particle of the test film that copper plating bath takes out, can confirm that good Carried out the chemical plating of copper.Test film carries out the baking of 60 minutes after washing, air-drying at 100 DEG C.By chemical plating shape Into copper film sheet resistance value be 0.04 Ω/, can be produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks The conductive material of the conductive layer with copper.The conductive layer of the copper being consequently formed is carried out using cellophane tape (Nichiban Co., Ltd. manufactures) belt stripping test result, unconfirmed to stripping, adaptation is also good.

Embodiment 77

In embodiment 76, dispersion liquid (B-18) is replaced using dispersion liquid (B-19), it is in addition, same with embodiment 76 Operation, carries out coating, the electroless copper of the copper particle on Kapton.The surface resistivity of copper plate is 0.04 Ω/, The conductive material of the conductive layer with copper can be produced on the Kapton of 38 μ m-thicks of insulating properties base material.Thus The conductive layer of the copper of formation carries out the knot of the belt stripping test using cellophane tape (Nichiban Co., Ltd. manufacture) Really, unconfirmed to stripping, adaptation is also good.

Embodiment 78

In embodiment 76, it is changed to dispersion liquid (B-20~24) and replaces dispersion liquid (B-18), in addition, with embodiment 76 same operations, carry out coating, the electroless copper of the copper particle on Kapton.The surface electricity of the copper plate of all films Resistance rate is 0.04~0.05 Ω/, can be produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks with copper The conductive material of conductive layer.When the conductive layer of the copper being consequently formed is any one, carry out utilizing cellophane tape The result of the belt stripping test of (manufacture of Nichiban Co., Ltd.s), unconfirmed to stripping, adaptation is also good.

Embodiment 79

In embodiment 76, the aqueous dispersion (B-25) of silver core-copper shell particle for being changed to be obtained in synthesis example 42 replaces Dispersion liquid (B-18), in addition, operation same with embodiment 76 carries out silver core-copper shell particle on Kapton Coating, electroless copper.The polyimide surface covering rate of silver core-copper shell particle is for about 80%, after being sintered at 250 DEG C, by surface It is still non-conductive that determination of resistivity is confirmed by silver core-granuloplastic film of copper shell.The surface electricity of the copper plate after chemical plating Resistance rate is 0.04 Ω/, can be produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks the conductive layer with copper Conductive material.The conductive layer of the copper being consequently formed be any one when, carry out using cellophane tape (Nichiban Co., Ltd. manufacture) belt stripping test result, unconfirmed to stripping, adaptation is also good.

Embodiment 80

In embodiment 79, it is changed to dispersion liquid (B-26~30) and replaces dispersion liquid (B-25), by decentralized medium composition not The dispersion liquid operation same with embodiment 79 for changing and the concentration of silver core-copper shell particle only being adjusted into 5%, carries out polyamides Coating, the electroless copper of the silver core-copper shell particle on imines film.In polyimide surface coating masking by silver core-copper shell After granuloplastic film is sintered at 250 DEG C, confirmation is determined by surface resistivity still all non-conductive.Plating after chemical plating The surface resistivity of layers of copper is 0.04~0.05 Ω/, can be produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks The conductive material of the upper conductive layer with copper.When the conductive layer of the copper being consequently formed is any one, carry out utilizing glassine paper The result of the belt stripping test of adhesive tape (manufacture of Nichiban Co., Ltd.s), unconfirmed to stripping, adaptation is also good.

Embodiment 81

Using it is being obtained in embodiment 76~80, the conductive layer with copper is led on the Kapton of 38 μ m-thicks Electric material, operation same with embodiment 49, is electroplated (copper sulphate).The layers of copper formed on Kapton after plating Average film thickness be respectively 16 μm.The peel strength of the copper formed on Kapton is 9~10N/cm or so, is shown Good adaptation.

Embodiment 82

In embodiment 1, embodiment 72, insulating properties base material is changed to the polyimides of following table by Kapton EN150-C Film, in addition, operation same with embodiment 1, embodiment 72 is coated with Argent grain on film, is formed comprising Argent grain After non-conductive layer, with embodiment 1,72 it is same operation, carry out chemical plating, as a result, for any one when can be in polyimides The conductive layer of the copper that surface resistivity is 0.04~0.05 Ω/ is formed on film.Carry out utilizing cellophane tape The result of the belt stripping test of (manufacture of Nichiban Co., Ltd.s), it is unstripped to confirm layers of copper, forms with sufficient The film of adaptation.

[table 11]

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

Using these conductive materials, operation same with embodiment 49 is electroplated (copper sulphate).It is sub- in polyamides after plating The average film thickness of the layers of copper formed on amine film is 16 μm.The peel strength of the copper formed on Kapton is 8~ 10N/cm or so, obtains sufficient peel strength.

Embodiment 83

In embodiment 1, embodiment 72, insulating properties base material is changed to solar strain formula meeting by Kapton EN150-C Expoxy glass plywood (thickness 3mm) of society's manufacture, it is in addition, same with embodiment 1, embodiment 72 to operate, in epoxy glass Coating dispersions on glass plywood, after forming the non-conductive layer containing Argent grain, with embodiment 1,72 same operations, are changed Learn plating, as a result, for any one when surface resistivity can be formed on expoxy glass plywood be 0.04~0.05 Ω/ The conductive layer of copper.The result using the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.s) is carried out, really Recognize that layers of copper is unstripped, form the copper film with sufficient adaptation.Use the conductive material, behaviour same with embodiment 49 Electroplated (copper sulphate), as a result, the average film thickness of the layers of copper formed on expoxy glass plywood after plating is 16 μm.

Embodiment 84

In embodiment 1, embodiment 72, insulating properties base material is changed to KURARAY by Kapton EN150-C VECSTAR CT-Z, in addition, operation same with embodiment 1, embodiment 72, the Coating dispersions on film, formation contains After the non-conductive layer of Argent grain, with embodiment 1,72 same operations, carry out chemical plating, as a result, for any one when can be The conductive layer of the copper that surface resistivity is 0.04~0.05 Ω/ is formed on VECSTAR CT-Z films.

Embodiment 85

(formation of the non-conductive layer in insulating properties base material)

In embodiment 1, the Argent grain dispersion liquid of silver concentration 5% is replaced using 0.5% Argent grain dispersion liquid, except this In addition, operate similarly to Example 1, in Kapton (Kapton EN150-C, 38 μ m-thicks, Du Pont-Toray Co., Ltd. manufacture) on be coated with (rod painting) Argent grain dispersion liquid, after drying at room temperature, carry out 210 DEG C, the sintering of 5 minutes, as a result, Surface covering rate is 23%.

(electroless copper operation)

Above-mentioned Argent grain is coated with Kapton as the test film of plating, using based on document (" Now for めっ I textbook " plating research association volume, daily magazine Industrial Co., Ltd (2011)) and the chemical plating fluid of making carries out chemical plating.Change Learn copper-plated operation is carried out by the flow chart via degreasing, washing, activation, washing, chemical plating, washing.Wash is 2 points The flowing water washing of clock.

3. chemical plating：Using foregoing " Now for めっ I textbook " following A P2 operations described in page 302, carry out 20 minutes Chemical plating.

AP2 operations

[table 12]

Copper sulphate	10g/L
		EDTA·2Na	30g/L
Formaldehyde (37%)	3mg/L
		Bipyridyl	It is some
Polyethylene glycol	It is some
		pH	12.2
Bath temperature	70℃

The coating side surface generally light red of the Argent grain of the test film for chemically being taken out in copper plating bath, can confirm that good The chemical plating of copper has been carried out well.Test film carries out the baking of 60 minutes after washing, air-drying at 100 DEG C.By chemical plating The sheet resistance value of the copper film of formation is 0.04 Ω/, can be produced on the insulating properties base material i.e. Kapton of 38 μ m-thicks The conductive material of the upper conductive layer with copper.The conductive layer of the copper being consequently formed carries out utilizing cellophane tape The result of the belt stripping test of (manufacture of Nichiban Co., Ltd.s), unconfirmed to stripping, adaptation is also good.

(plating)

Using it is thus obtained on polyimide with conductive layer conductive material, it is same with embodiment 49 operate into Row plating (copper sulphate).

The test film electroplated wipes moisture away after washing, then carries out heated-air drying, and 60 points are carried out at 120 DEG C The baking of clock.The average film thickness of the layers of copper formed on Kapton after plating is 16 μm, can be produced on 38 μ m-thicks The conductive material of the conductive layer with 16 μ m-thicks on Kapton.The stripping of the copper formed on Kapton Intensity is 8N/cm or so, shows good dhering strength.

Embodiment 86

(formation of the non-conductive layer in insulating properties base material)

Operate similarly to Example 1, by 5% Argent grain dispersion liquid coating (rod painting) in Kapton (Kapton EN100-C, 25 μ m-thicks, Du Pont-Toray Co., Ltd. manufacture) on.After the film is dried at room temperature for, surface is overturn And the back side, overleaf similarly operate silver coating coating fluid.After drying at room temperature, 210 DEG C, the sintering of 5 minutes are carried out.Silver is determined to apply The resistance on film surface, as a result, two sides is 10⁷The resistance of more than Ω, thus cannot determine, obtaining two sides has non-conductive layer Kapton.

The film is operated similarly to Example 1 carries out electroless copper treatment, can be produced on insulating properties base material i.e. 25 μm There is the conductive material of the conductive layer of copper on the two sides of thick Kapton.The conductive layer of the copper being consequently formed is carried out Using the result of the belt stripping test of cellophane tape (manufacture of Nichiban Co., Ltd.s), two sides is unconfirmed to stripping, Adaptation is also good.

Use the thus obtained conductive material on polyimides two sides with conductive layer, behaviour same with embodiment 49 Make, carry out the electro-coppering of 10 minutes, as a result, can be produced on the polyimides two sides of 25 μ m-thicks has the copper of 5-6 μ m-thicks respectively The conductive material of layer.

Embodiment 87

(there is the formation of the non-conductive layer in the insulating properties base material of through hole)

On Kapton (Kapton EN150-C, 38 μ m-thicks, the manufacture of Du Pont-Toray Co., Ltd.s), make The through hole of 6mm φ is formed with eyelet punch, in addition, operation same with embodiment 86, on the two sides of Kapton The non-conductive layer of silver is formed, electroless copper treatment is carried out.

The conductive layer of the copper being consequently formed carries out the adhesive tape stripping using cellophane tape (Nichiban Co., Ltd. manufacture) The result of separating test, two sides is unconfirmed to stripping, and adaptation is also good.Make the probe contact surface of electric tester and the back side two Face, can confirm to be powered, it is thus identified that surface and back side two sides are connected by through hole.

Industrial applicability

In the present invention, dividing containing the metal particle protected by the compound with specific atoms more than specified quantitative is used Dispersion liquid, conductive material is manufactured by the operation comprising certain working procedure, be therefore, it can not need vacuum equipment, is not used organic gluing High performance conductive material, the tellite that can be utilized in high-density installation field with low cost manufacture with connecing agent With substrate or printed circuit board (PCB).

Claims

1. a kind of manufacture method of conductive material, it is characterised in that with following operations：

(1) Coating dispersions (B) in insulating properties base material (A), form the operation of non-conductive layer (C), and the dispersion liquid (B) contains Have it is more than 0.5 mass % by with nitrogen-atoms, sulphur atom, phosphorus atoms or oxygen atom compound (b1) protection selected from by More than a kind of metal particle (b2) in the group of gold, silver, copper and platinum composition；

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

The compound (b1) is the compound (P1) with polyethyleneimine block and polyethylene glycol block, following (methyl) The Sulfide-containing Hindered organic compound (P3) that acrylic polymer (P2) or following formulas (1) are represented,

(methyl) acrylic polymer (P2) is made with polyglycol chain (methyl) esters of acrylic acid macromolecular list Body with have-OP (O) (OH)₂(methyl) acrylic ester monomer of the phosphate residue of expression is in the function represented with-SR Obtained from being polymerized in the presence of the chain-transferring agent of group, wherein, in-SR, R is the alkyl of carbon number 1~18, can have on phenyl ring The alkyl of the phenyl of substituted base or the carbon number 1~8 with following functional group,

The functional group be select free hydroxyl, the alkoxy of carbon number 1~18, the aralkyl oxy of carbon number 1~18, can be in phenyl ring The alkyl carbonyl epoxide and carbon number 1 of the upper phenoxy group with substitution base, carboxyl, the salt of carboxyl, 1 valency of carbon number 1~18 or multivalence The functional group of more than 1 in the group of the alkoxy carbonyl composition of~18 1 valency or multivalence,

X-(OCH₂CHR¹)_n-O-CH₂-CH(OH)-CH₂-S-Z (1)

In formula (1), X is C₁~C₈Alkyl, R¹It is hydrogen atom or methyl, n is the integer of the repeat number of expression 2~100, R¹Every It is independent in individual repeat unit, can be the same or different, Z is C₂~C₁₂Alkyl, pi-allyl, aryl, aralkyl ,- R²-OH、-R²-NHR³Or-R²-COR⁴The group of expression, wherein, R²It is C₂~C₄Alkylidene chain, R³It is hydrogen atom, C₂~C₄'s Acyl group, C₂~C₄Alkoxy carbonyl or can have C on aromatic rings₁~C₄Alkyl or C₁~C₈Alkoxy as taking The benzyloxycarbonyl of Dai Ji, R⁴It is hydroxyl, C₁~C₄Alkyl or C₁~C₈Alkoxy.

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

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

3. the manufacture method of conductive material according to claim 1, wherein, insulating properties base material (A) is by polyimides Base material obtained from the shaping of resin, liquid crystal polymer or glass epoxy resin.

4. the manufacture method of conductive material according to claim 3, it is characterised in that insulating properties base material (A) be film, The base material of thin slice or tabular.

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

6. the manufacture method of conductive material according to claim 1, it is characterised in that the number of the compound (b1) is equal Molecular weight is 3000~50000 scope.

7. the manufacture method of conductive material according to claim 1, wherein, the compound (b1) is wrapped in 1 molecule The atom of more than two kinds of nitrogen atom, sulphur atom, phosphorus atoms or oxygen atom.

8. the manufacture method of conductive material according to claim 1, wherein, the compound (b1) be with amino, The compound of carboxyl, hydroxyl, sulfydryl, phosphate, quaternary ammonium group, quaternary phosphines base, cyano group, ether, thioether group or disulfide group.

9. the manufacture method of conductive material according to claim 1, wherein, the average grain diameter of the metal particle is 1 The scope of~200nm.

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

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

The manufacture method of 12. conductive materials according to claim 1, wherein, the non-conductive layer (C) is in insulation With the metal particle layer of less than 5 layers of number of plies laminated metal particulate (b1) in property base material (A).

The manufacture method of 13. conductive materials according to claim 1, wherein, the resistance value of the non-conductive layer (C) It is 10⁷More than Ω.

The manufacture method of 14. conductive materials according to claim 1, it is characterised in that non-conductive layer (C) shape Into the two sides of the insulating properties base material (A) in film, thin slice or tabular.

15. a kind of conductive materials, it is characterised in that it is using the manufacture method any one of claim 1~14 Obtain.

16. conductive materials according to claim 15, it is use in printed circuit board laminated substrate.