CN106663504A - Method for producing conductive coating film, and conductive coating film - Google Patents
Method for producing conductive coating film, and conductive coating film Download PDFInfo
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- CN106663504A CN106663504A CN201580035526.6A CN201580035526A CN106663504A CN 106663504 A CN106663504 A CN 106663504A CN 201580035526 A CN201580035526 A CN 201580035526A CN 106663504 A CN106663504 A CN 106663504A
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- conductive coating
- copper
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- copper powders
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention discloses a method for producing a conductive coating film, and a conductive coating film. The purpose of the present invention is to provide a conductive coating film which is provided on an insulating substrate using a copper paste and which exhibits not only excellent electrical conductivity but also improved adhesion to the insulating substrate. The conductive coating film according to the present invention is produced by: arranging, on an insulating substrate, a resin layer that contains a heterocyclic compound containing nitrogen in a heterocyclic ring and/or a hydrazide compound; forming a copper powder-containing coating film on the resin layer using a copper paste; and subsequently subjecting the coating film to a heat treatment in a non-oxidizing gas atmosphere.
Description
Technical field
The present invention relates to the manufacture method and profit with the conductive coating of the cementability and excellent electric conductivity of insulated substrate
With conductive coating obtained from the manufacture method.
Background technology
In recent years, conducting channel has rapidly carried out densification.At present, to being bonded in for forming conducting channel
Metal covering that Copper Foil on insulated substrate is etched and is patterned corrosion (substractive) method, operation length and multiple
It is miscellaneous, and produce substantial amounts of discarded object.Therefore, replace metal covering etch and contain conductive used in the formation of conducting channel
The print process and rubbing method of the conductive paste of grain is of concern.
From from the aspect of electric conductivity and ageing stability, silver is usually used as the metal that conductive particle is used.However, silver-colored
It is not only expensive, and stock number is few, and there is a problem of betiding the Ion transfer between the circuit under high-temperature high-humidity.As
Replace silver for the metal of conductive particle, copper can be enumerated.However, copper powders easily form oxide layer in particle surface, exist
Shortcoming as making electric conductivity be deteriorated because of oxide layer.In addition, particle is less, the adverse effect of oxide layer is more notable.Therefore, it is
The oxide layer of copper powders is reduced, needs under the reducing atmosphere of hydrogen etc. carry out reduction treatment with the temperature more than 300 DEG C,
Or be sintered at a higher temperature.Although electric conductivity can be made close to block copper by sintering processes, can
The insulated substrate for using is defined to the high material of heat resistance of ceramics, glass etc..
As polymer-type conductive paste, it is known to using macromolecular compound as adhesive resin conductive paste.Polymer
Type conductive paste can guarantee the fixation of conductive particle and cementability with base material using adhesive resin, but due to adhesive tree
Fat hinders the contact between conductive particle, thus makes electric conductivity be deteriorated.However, when reducing the adhesive resin ratio of conductive paste,
Reduction with the adaptation of base material or the reduction of cohesiveness of layer containing copper powders etc. would generally occur.
In addition, as the copper cream of conductive particle, due to the carrying out of the oxidation of copper particle surface, not only holding with regard to using copper powders
Easily there is the deterioration of electric conductivity, even and if oxide layer is reduced, in the process carried out at a high temperature of more than 100 DEG C, also can
Because of the decomposition of the adhesive resin near the oxide layer of copper particle surface and because of the stress produced by Volume Changes caused by oxidation
Deng, and it is susceptible to the reduction of adaptation.That is, because of the carrying out aoxidized in copper cream the problem that produces except electric conductivity deterioration with
Also there is the reduction of adaptation sometimes outward.
In the prior art, it was also proposed that for improving the side of the electric conductivity of the film obtained by polymer-type conductive paste
Case.For example, Patent Document 1 discloses, by using the metal particle of below particle diameter 100nm, can be with far below block
The temperature of the fusing point of metal is sintered, and obtains the metallic film of excellent electric conductivity.In addition, patent document 2 discloses that to using
The film that metal powder cream is formed carries out overheated steam process.Patent document 3 discloses that the polymer containing sulphonate-base
As the metal particle dispersion of adhesive.Patent document 4 discloses that and obtained by implementing plating after overheated steam is processed
To metallic film.
However, the electric conductivity of the film obtained by the conductive paste containing copper powders and cementability are expected further to improve,
It is also insufficient.In the conducting that the sintering using copper powders is carried out, often sintering is more carried out, and shrinkage stress more increases,
Adaptation is more reduced, in addition, the thickness of conductive coating is bigger, shrinkage stress is bigger, and adaptation is more reduced.In addition, overheated
In steam treatment, treatment temperature is higher, and the performance of electric conductivity is better, but presence is reduced so with the cementability of insulated substrate
Tendency.In addition, good dividing can be obtained using the polymer containing sulphonate-base as the metal particle dispersion of adhesive
Dissipate, but sulphonate-base is strong to the absorption affinity of metal particle, it is a large amount of containing the tendency that sometimes, there is the sintering for reducing metal particle.
As by the technology of resinous insulated substrate and conductive layer bonding, Patent Document 5 discloses, by using
The organic compound comprising nitrogen processes Copper Foil to improve the cementability with base plate resin in heterocycle.In patent document 6
In disclose, Copper Foil is processed by using the heterocyclic compound with mercapto improve the cementability with resin film.
Patent Document 7 discloses, improved using the adhesion durability of the Copper Foil of aromatic series diacyl hydrazide process.In addition, in patent
Disclose in document 8, after corona treatment is implemented to polyimide resin layer, by using amino-compound article on plasma
Body process face is processed, and improves the cementability with metal.
However, in the process using heterocyclic compound or the copper surface of hydrazide compound, the sintering effect of heating is not enough,
The performance of electric conductivity is deteriorated, or, there is a problem of making characteristic changing etc. because of the cleaning of process layer.In addition, by containing copper
In the case that the conductive paste of powder obtains film, it is impossible to the prior enforcement of conductive layer is processed as Copper Foil.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 03-034211 publication
Patent document 2:Japan internationality discloses No. 2010/095672
Patent document 3:Japanese Unexamined Patent Publication 2010-132967 publications
Patent document 4:Japanese Unexamined Patent Publication 2011-60653 publications
Patent document 5:Japanese Unexamined Patent Application 61-266241 publication
Patent document 6:Japanese Unexamined Patent Application 64-53495 publication
Patent document 7:Japanese Unexamined Patent Publication 08-311658 publication
Patent document 8:International Publication 2008/018399
The content of the invention
Invent problem to be solved
The present invention problem be:There is provided and use the cream containing copper powders, electric conductivity is good and closely sealed on insulated substrate
The manufacture method of the conductive coating of excellent in te pins of durability.
Method for solving problem
The present inventor is studied intensively to solve above-mentioned problem, as a result completes the present invention.I.e., originally
Invention is as described below.
(1) a kind of manufacture method of conductive coating, it is characterised in that:Arrange to contain on insulated substrate and wrap in heterocycle
Nitrogenous heterocyclic compound and/or the resin bed of hydrazide compound, are formed containing copper powders on the resin layer using copper cream
After film, implement to heat in non-oxidizing atmosphere.
(2) manufacture method of the conductive coating as described in (1), wherein, above-mentioned copper cream contains copper powders, adhesive resin
And solvent, the ratio of the copper powders in total nonvolatile component of the copper cream is more than 94 weight %.
(3) manufacture method of the conductive coating as described in (1) or (2), wherein, the adhesive tree contained by above-mentioned copper cream
Fat contains the polymer comprising sulphonate-base or carboxylate group.
(4) manufacture method of the conductive coating as any one of (1)~(3), wherein, above-mentioned heating exists
Carry out for more than 200 DEG C.
(5) manufacture method of the conductive coating as any one of (1)~(4), wherein, above-mentioned heating is used
Overheated steam.
(6) manufacture method of the conductive coating as any one of (1)~(5), wherein, implementing to heat
Afterwards, plating is further carried out.
(7) a kind of conductive coating of the manufacture method manufacture utilized any one of (1)~(6).
Invention effect
The manufacture method of the conductive coating of the present invention includes following operation:Across containing miscellaneous comprising nitrogen in heterocycle
The resin bed of cycle compound and/or hydrazide compound, use on insulated substrate with copper powders and adhesive resin for mainly into
The copper cream for dividing is formed after film, implements to heat in non-oxidizing atmosphere.By implementing heating in non-oxidizing atmosphere
Process, the oxide for not only making copper powders surface reduce, the sintering of generation copper powders, and above-mentioned specific compound is to containing
The absorption progress of the film of copper powders, improves the adaptation of the film containing copper powders and insulated substrate.Therefore, by containing
The resin bed of specific compound is pre-set on insulated substrate, can pass through the increase for heating and obtaining adaptation.
As a result, the conductive coating of adaptation with insulated substrate and excellent electric conductivity can be obtained.
Furthermore, using the present invention, when preserving above-mentioned conductive coating for a long time at high temperature, it is also possible to prevent because of gold
The oxidation of metal particles and the change of crystalline state etc. conductive coating interface produce stress and caused closing force drop
It is low.
In addition, in the present invention, by the copper powders containing ratio in raising copper cream, it is also possible to further improve film
Electric conductivity.Film is formed using the high copper cream of copper powders containing ratio across above-mentioned resin bed on substrate, and implements heating
Process, it is hereby achieved that the adaptation and the conductive coating of excellent electric conductivity with insulated substrate.
Specific embodiment
Copper cream used in the present invention is, with copper powders and adhesive resin as main component, to be scattered in solvent and obtained
Arrive.
Copper powders are the metallic particles with copper as main component, or the ratio of copper is copper conjunction more than 80 weight %
Gold, the surface of the copper powders can also be with silver covering.Silver both can be to be completely covered, or make to the covering of the copper powders
The covering that a part of copper exposes.In addition, copper powders can also have the oxidation of the degree for not damaging electric conductivity in its particle surface
Cover layer.The shape of copper powders can use the arbitrary shape of substantially spherical, dendroid, flake etc..As copper powders or copper
Alloy powder, it is possible to use wet type copper powder, electrolytic copper powder, atomized copper powder, vapour phase reduction copper powder etc..
The preferred average grain diameter of copper powders used in the present invention is 0.01~20 μm.The average grain diameter of copper powders is more than 20 μm
When, fine Wiring pattern is formed in insulative substrate will become difficult.In addition, when average grain diameter is less than 0.01 μm, because
The deformation for fusing between particulate during heating and occurring can become big, reduce with the adaptation of insulated substrate.Copper powders it is average
The scope that more preferably 0.02 μm~15 μm of particle diameter, more preferably 0.04~4 μm, be even more preferably 0.05~2 μm.It is flat
The measure of particle diameter utilizes following method:Swept with transmission electron microscope, field emission type transmission electron microscope, field emission type
Any one particle diameter to 100 particles retouched in electron microscope is measured, and obtains mean value.Copper powder used in the present invention
As long as last average grain diameter is 0.01~20 μm, it is also possible to be used in mixed way the two or more copper powders of different-grain diameter.Particularly
In serigraphy with copper cream, from giving from the aspect of the distinctive flow behavior of the purposes, it is desirable to 0.05~0.5 μm of fine powder
With the mixing of 1~10 μm of micron order powder.
Solvent of the solvent that copper cream used in the present invention is used selected from dissolving adhesive resin.Both can be to organise
Compound, or water.Solvent except with addition to making the effect that copper powders are scattered in copper cream, also with adjustment dispersion
The effect of viscosity.As the example of organic solvent, alcohol, ether, ketone, ester, aromatic hydrocarbon, acid amides etc. can be enumerated.
As the adhesive resin that the copper cream used in the present invention is used, polyester, polyurethane, poly- carbonic acid can be enumerated
The resin of ester, polyethers, polyamide, polyamidoimide, polyimides or acrylic acid etc..Examine in terms of the stability of copper powders
Consider, preferred resin has ester bond, amino-formate bond, amido link, ehter bond, imide bond etc. in main chain.
The ratio of each composition of the copper cream used in the present invention is 5~400 relative to the weight portion preferred solvent of copper powders 100
Weight portion, adhesive resin are the scope of 0.5~20 weight portion.Adhesive resin amount in copper cream is relative to the weight of copper powders 100
When amount part is less than 0.5 weight portion, the reduction with the adaptation of insulated substrate is notable, thus not preferred.On the other hand, more than 20 weights
During amount part, the touch opportunity between copper powders is reduced, thus cannot ensure electric conductivity.Adhesive resin is more preferably 1~6 weight
Part, more preferably 2~5 weight portions.
In addition, in copper cream used in the present invention, (copper powders contain the ratio of the copper powders in preferably total nonvolatile component
Have ratio) it is more than 94 weight %, more than more preferably 96 weight %.Wherein, so-called nonvolatile component, refers in copper cream and volatilizees
Composition beyond the solvent of property, is copper powders, adhesive resin, filler, curing agent, dispersant etc..It is total non-volatile by making
The ratio of the copper powders in composition becomes many, it is possible to increase electric conductivity.The ratio of the copper powders in total nonvolatile component is less than 94 weights
During amount %, the raising of electric conductivity is not sufficiently effective.The upper limit of the ratio of the copper powders in total nonvolatile component is because of the bonding for being used
Agent resin and different, preferably 99 weight %, more preferably 98 weight %.
When the ratio of the copper powders in making total nonvolatile component becomes many, in order to give play to viscous with a small amount of adhesive resin
Function required for mixture resin, the higher the better for the molecular weight of adhesive resin.It is desired according to the species of adhesive resin
Molecular weight is different, and with regard to polyester, polyurethane or Merlon, number-average molecular weight is more than 10,000, it is desirable to for more than 20,000.From dispersion
From the aspect of viscosity of body etc., the upper limit of the molecular weight of adhesive resin is 500,000 or so.
In order to show good electric conductivity, copper powders need to keep good dispersity in copper cream.In order to a small amount of
Adhesive resin given play to function required for adhesive resin, as adhesive resin, it is desirable to containing comprising sulphonate-base,
Carboxylate group etc. has the polymer of the functional group of adsorption capacity to metal.
Situation containing sulphonate-base represents by the sulfur content in adhesive resin, the sulfur content in preferred adhesive resin
For 0.05~3 weight %, more preferably 0.1~1 weight %.For carboxylate group, as the carboxylic acid group of script, preferably per 1 ton
Adhesive resin contains 30~500 moles, more preferably 50~200 moles.
As needed, curing agent can also be coordinated in the copper cream used in the present invention.As consolidating that the present invention can be used
Agent, can enumerate phenolic resin, amino resins, isocyanate compound, epoxy resin, oxetane compound, Malaysia
Imide compound etc..The scope of 1~50 weight % of the preferred adhesive resin of usage amount of curing agent, more preferably 1~20 weight
The scope of amount %.
Copper cream used in the present invention can coordinate dispersant.As dispersant, stearic acid, oleic acid, Pork and beans can be enumerated
Higher fatty acids, fatty acid amide, fatty acid metal salts, phosphate, sulphonic acid ester of cool acid etc. etc..The usage amount of dispersant is preferred
For the scope of 0.1~10 weight % of adhesive resin.
Then, the manufacture method of copper cream is described.
Method as copper cream is obtained, can adopt the usual way being scattered in powder in liquid.For example, can be by
After the mixture mixing be made up of copper powders and binder resin solution and solvent additional as needed, using ultrasonic wave
Method, mixer method, three-roller method, ball mill method etc. implement dispersion.Multiple combinations in these process for dispersing can also be carried out point
Dissipate.These decentralized processings can be carried out at room temperature, in order to reduce the viscosity of dispersion, it is also possible to heated and carried out.
As the insulated substrate used in the present invention, the material of the temperature heated using tolerance.For example, can enumerate
Polyimides system resins piece or film, ceramics, glass or expoxy glass laminated plate etc., it is desirable to polyimides system resins piece or film.
As polyimides system resins, the solvable polyimide resin of polyimide precursor resin, solvent, polyamides can be enumerated
Amine imide resin.Polyimides system resins can be polymerized using usual way.For example, tetracarboxylic dianhydride and diamines is made to exist
The method for obtaining polyimide precursor solution is reacted in solution, under low temperature;Tetracarboxylic dianhydride and diamines is set to react in the solution
To the method for the polyimide solution of solvent soluble;Using isocyanates as raw material method;Using acyl chlorides as raw material
Method etc..
As the polyimide film or piece of insulated substrate, when using polyimide precursor resin, it is possible to use to precursor
Resin solution carries out carrying out after film by wet, at a higher temperature the usual way of imidization reaction and obtains.With regard to solvent
Solvable polyimide resin, polyamide-imide resin, due to imidizate in the solution, therefore can utilize wet type system
Film carries out piece or membranization.
Insulated substrate can carry out the surface treatment of Corona discharge Treatment, corona treatment, alkali process etc..
In the present invention, arrange on insulated substrate containing the heterocyclic compound comprising nitrogen and/or hydrazides in heterocycle
The resin bed of compound, forms the film containing copper powders using copper cream on the resin layer.As the resin that resin bed is used,
Selected from the resin excellent in adhesion with insulated substrate, for example, can enumerate polyester, polyurethane, Merlon, polyethers, polyamides
Amine, polyamidoimide, polyimides or acrylic acid etc..Examine in terms of the heat resistance of resin bed and the cementability of insulated substrate
Consider, it is desirable to which resin has ester bond, imide bond, amido link etc. in main chain.From the heat resistance of resin bed and gluing for insulated substrate
From the aspect of connecing property, it is also desirable to contain curing agent in resin bed.As curing agent, can enumerate phenolic resin, amino resins,
Isocyanate compound, epoxy resin, oxetane compound, maleimide compound etc..The usage amount of curing agent is excellent
Elect the scope of 1~50 weight % of weight resin as.
In the present invention, containing the heterocyclic compound comprising nitrogen in heterocycle in the resin bed being arranged on insulated substrate
And/or hydrazide compound.The heterocyclic compound comprising nitrogen and hydrazide compound are sometimes used as the anti-of Copper Foil and copper powder in heterocycle
Rust agent, but in the present invention, these compounds can give play to firmly close with the film containing copper powders by heating
Conjunction property.Heterocyclic compound comprising nitrogen and hydrazide compound are high to the compatibility of copper, and copper surface is adsorbed in securely.In order that depositing
It is in the resin bed excellent in adhesion with insulated substrate, the heterocyclic compound comprising nitrogen, hydrazide compound are adsorbed in copper
Surface, needs to supply energy, and most-often used is to heat.
As the heterocyclic compound comprising nitrogen in heterocycle, for example, can also enumerate pyridine, oxazoles, isoquinolin, indoles, thiophene
Azoles, imidazoles, benzimidazole, bipyridyl, pyrazoles, benzothiazole, pyrimidine, purine, triazole, BTA, benzoguanamine etc. or
Their constitutional isomer.These compounds can have alkyl, phenyl, phenolic group, carboxyl, amino, hydroxyl, mercapto, fragrance
The substituent of ring etc..In addition, these compounds can also be with aromatic rings or heterocyclic condensation.In these compounds, it is desirable to be miaow
Azole compounds, BTA based compound.
Hydrazide compound is the compound of the structure being condensed with carboxylic acid with hydrazine or derivatives thereof, for example, can enumerate
Condensation product of salicylic acid hydrazides, isophthalic dihydrazide, salicylic acid hydrazides and dodecanedicarboxylic acid etc..
The resin bed on insulated substrate is arranged in the present invention preferably with respect to the weight portion of resin 100 with 1~30 weight portion
Scope contain in heterocycle comprising nitrogen heterocyclic compound and/or hydrazide compound.Relative to the weight portion of resin 100, miscellaneous
When the heterocyclic compound comprising nitrogen and/or hydrazide compound are less than 1 weight portion in ring, do not observe and the layer containing copper powders
The raising of adaptation, relative to the weight portion of resin 100, the heterocyclic compound comprising nitrogen and/or hydrazide compound are super in heterocycle
When crossing 30 weight portion, the reduction of the physical property of resin bed is can be observed sometimes.
When forming resin bed on insulated substrate, it is possible to use by it is resin-coated or used when being printed in film or piece one
As method.For example, silk screen print method, dip coating, spraying process, spin-coating method, rolling method, die coating method, ink-jet method, relief printing plate can be enumerated
Print process, woodburytype etc..By using heating or decompression etc., solvent is made from the film formed using printing or coating
Middle evaporation, can form resin bed.Resin bed can be arranged on insulated substrate with entire surface, it is also possible to which part is arranged, at least
It is arranged at the part to form conductive coating.
With regard to the resin containing the heterocyclic compound comprising nitrogen and/or hydrazide compound in heterocycle formed in the present invention
Layer, it is desirable to which its thickness is less than 5 μm, it is therefore highly desirable that for less than 2 μm.In addition, the lower limit of the thickness of the resin bed is 0.01 μm.Tree
When the thickness of lipid layer is more than 5 μm, due to sintering warpage of copper powders of generation etc. in heating, sometimes adaptation can be reduced,
When thickness is less than 0.01 μm, due to decomposition of adhesive resin for occurring because of heating etc., the reduction of adaptation can become big.
The method that copper cream used in the present invention forms conductive coating on insulated substrate across resin bed is said
It is bright.Wherein, conductive coating can be the entire surface ground pattern such as the film that is arranged on insulated substrate, or conducting channel
Thing.In addition, conductive coating can be arranged at a face of insulated substrate, it is also possible to be arranged at two faces.
The copper cream using liquid, form the film containing copper powders across resin bed on insulated substrate when, can be with
Using the conventional method that copper cream is coated with or is used when being printed in film or piece.For example, silk screen print method, dip-coating can be enumerated
Method, spraying process, spin-coating method, rolling method, die coating method, ink-jet method, toppan printing, woodburytype etc..By using heating or
Person's decompression etc., makes solvent evaporate from the film formed using printing or coating, can form the film containing copper powders.It is logical
Often, in the case of using copper cream, the film containing copper powders in the stage is ratio resistance more than 1 Ω cm, it is impossible to obtained
Obtain as the electric conductivity required for conducting channel.
The thickness of the film containing copper powders mainly determines by required electric conductivity, preferably makes the solvent contained by copper cream
Dried thickness obtained from evaporation is 0.05 μm~100 μm.When the thickness of the film containing copper powders is less than 0.05 μm, i.e.,
Make to implement to heat under non-oxidizing atmosphere, there is also can not obtain the possibility of sufficient electric conductivity, more than 100 μm
When, there is dissolvent residual in film, there is the solvent of the residual bumping in overheated steam process,
In this case, sometimes in film coated surface generation defect.The thickness of the film containing copper powders is more preferably 0.1 μm~50
μm。
In the case where the polyimides system resins used as insulated substrate are used, can be molten in polyimide precursor
The temporary transient dry product of the temporary transient dry product of liquid or polyimide solution or polyamideimide solution is formed after resin bed, complete
Into drying.Alternatively, it is also possible to the copper coated cream before completing to be dried, drying is completed afterwards.By molten by polyimides system precursor
Liquid or polyimides system solution remain coating resin layer and copper on the temporary transient dry product of the state of the solvent of 10~30 weight %
Cream simultaneously completes drying, and polyimides system resins become with the bonding and resin bed of resin bed with the bonding of the film containing copper powders
Firmly.The solvent of polyimides system precursor solution and polyimides system solution is usually used acid amides series solvent.Acid amides series solvent by
It is poor in drying property, it is therefore desirable to baking temperature to be improved to more than 150 DEG C.Now, due to aoxidizing in copper powders, because
This is heated under anaerobic state as inactive gas or overheated steam of the hope in nitrogen etc..
In the present invention, by heating the heterocyclic compound comprising nitrogen, the hydrazides chemical combination that make to be present in resin bed
Thing is adsorbed in copper particle surface, and the closing force of insulated substrate and conductive layer is thus improved via resin bed.Containing above-mentioned in copper cream
During compound, the sintering because hindering the copper particle in heating causes the reduction of electric conductivity and the coating strength of conductive layer
Reduce, but in the present invention, be present in resin bed by making above-claimed cpd, the conductive layer of the high electric conductivity of display can be made
It is closely sealed with insulated substrate.Optimal heating condition changes because of many factors, as factor, for example, can enumerate institute
The mode of heating that uses glass transition temperature, molecular weight, degree of crystallinity, the degree of cross linking relevant with resin etc. and heterocyclic compound
Compatibility of relevant fusing point, molecular weight and resin etc. with hydrazide compound.
Wherein, in the manufacture method of the present invention, so-called " heating " as necessary condition is referred in order that copper powder
The oxide reduction on last surface, cause the sintering of copper powders, improve the film containing copper powders and insulated substrate adaptation and
The process for carrying out.It is thus impossible to the simple heating (such as dried process etc.) for obtaining such effect is not included.
With regard to heating, because copper is easily aoxidized at high temperature, it is therefore necessary in reducing atmosphere state or anaerobic state
Deng non-oxidizing atmosphere under heated.Heating used in the present invention can be set forth in the reduction comprising hydrogen, formic acid
The heating carried out under atmosphere or overheated steam are processed.From the efficiency of heating surface, security, economy and the electric conductivity for obtaining
Deng from the aspect of, it is therefore highly desirable that overheated steam process.So-called overheated steam is processed, refer to using with air phase specific heat capacity,
Used as the process of the thermal source being heat-treated, so-called overheated steam is to enter saturated steam to the big overheated steam of specific heat
One step heats and improves the vapor of temperature.
With regard to heating condition, the target, copper powders characteristic or adhesive resin according to electric conductivity, most suitable scope is not
Together.In addition, heterocyclic compound, the type and quantity of hydrazide compound comprising nitrogen in heterocycle in resin bed, pass through
The temperature for heating and embodying adaptation is also different.Wish heat temperature be more than 200 DEG C, preferably 250 DEG C with
On, more preferably more than 300 DEG C.In addition, the temperature for heating is preferably the glass transition of the resin that resin bed is used
Temperature is included more than the heterocyclic compound of nitrogen and/or the fusing point or sublimation point of hydrazide compound in heterocycle.Heat
Ceiling temperature is different because of the material for being used.Heating treatment time is 10 seconds~10 minutes, preferably 20 seconds~5 minutes.Close
In overheated steam process, its efficiency of heating surface is good, during process required for the reduction of the oxide that can shorten copper powders surface
Between, can suppress the reduction of adaptation occurred because of the process under high temperature, thus particularly preferably.
The present invention conductive coating after above-mentioned heating, in order to improve electric conductivity, in addition, further for raising
Corrosion resistance, abrasion performance, soldering resistance etc., adjustment hardness etc., can carry out plating.Plating can enter in accordance with known methods
OK, can enumerate plating, electroless plating, displacement plating, as coating metal, can enumerate copper, nickel, gold, silver, palladium, tin or with
These metals are alloy of main body etc..Carry out under alkalescence or acidity or at high temperature, but the conduction of the present invention when being plated with
Property film it is excellent in adhesion with insulated substrate, therefore the damage produced because of plating less or confirm less than.
Embodiment
In order to the present invention will be described in more detail, embodiment is exemplified below, but the present invention does not receive any limit of embodiment
It is fixed.Wherein, described in embodiment measure and it is measured as follows or manufactures using material.
Resistance:Using the low-resistivity meter Loresta GP and ASP probe assay resistance values of Mitsubishi Chemical Ind.Measure
Resistance value be sheet resistance, specific insulation is the thickness of sheet resistance and the conductive layer (layer containing copper powders) for determining sample
The product of degree.
Fitness test 1:
(preliminary evaluation) implements 10 μm of copper sulphate electro-coppering to conductive coating, after one day, in 20 DEG C of temperature of the measurement, draws
Stretch under conditions of speed 100mm/ minute, the 180 degree peel strength of coating is measured.Wherein, the pre-treatment of plating is used
" DP-320Clean (the DP-320 ク リ ー Application) " of pharmaceuticals industry company system in open country difficult to understand is carried out.
Situation about being evaluated adaptation in (Evaluation of Heat Tolerance) and above-mentioned preliminary evaluation equally implements plating, and determining will
Implement adaptation of the conductive coating after plating after 150 DEG C of heat resistant tests for placing 1 week.
Fitness test 2:Cellophane tape (cellophane tape) is bonded on conductive coating, it is quick to peel off.
A:It is not peeling-off on conductive coating.
B:It was observed that peel off, but stripping is less than the 20% of cellophane tape bond site.
C:It was observed that peeling off, peel off as more than the 20% of cellophane tape bond site.
The copper powders for being used:
Copper powders 1:In water, copper sulphate (II) aqueous solution is adjusted to pH12.5 using NaOH, use anhydrous Portugal
Grape sugar is reduced to after cuprous oxide, and recycling hydrazine hydrate reduction is copper powders.Observed using transmission electron microscope, confirmed as
The spherical particle of 0.15 μm of average grain diameter.
Copper powders 2:It is copper powders using hydrazine hydrate reduction in cuprous oxide is suspended in containing tartaric water.Profit
Observed with transmission electron microscope, confirm as the spherical particle of 1.8 μm of average grain diameter.
Copper powders 3:Be with silver amount be calculated as the ratio of 10 weight % to atomized copper powder implement it is silver-plated after 5 μm of average grain diameter
Particle.
Polyimide film with resin bed:
AC-1~8,16:With the match ratio described in table 1, to polyamidoimide, (HR- of company system spins in Japan
The phenolic resin varnish type epoxy resin " 152 " of the Mitsubishi Chemical Ind as curing agent 11NN) is added in solution, is urged as solidification
The triphenylphosphine (TPP) of agent, the tetrahydrofuran as retarder thinner of 2 times of amounts of polyamideimide solution and conduct
The 2- phenylimidazoles of additive, l, 2,3 triazole, the benzotriazole derivatives " JF-832 " of north of the city chemical company,
The benzotriazole derivatives " TT-LYK " of north of the city chemical company, the hydrazides based compound " CDA-6 " of Adeka company systems,
The hydrazides of phthalic acid two.Become in the way of in the of 0.5 μm by dried thickness, said composition is coated into the poly- of Kaneka company systems
On acid imide film " 25 μm of Apical NPI thickness ", with 200 DEG C drying-heat treatment in 5 minutes is carried out.
AC-9~13,17,18:With the match ratio described in table 1, to by copolymer polyester resin, (company system is spun by Japan
RV-290 MEK/toluene (1/1 weight ratio) solution) and the thermosetting phenolic resin (Resitop of Qun Rong chemical companies
PL-2407), in the composition constituted as the p-methyl benzenesulfonic acid (p-TS) of catalysts, the 2- as additive is added
Phenylimidazole, the benzotriazole derivatives " BT-3700 " of north of the city chemical company and " TT-LYK ", the acyl of Adeka company systems
Hydrazine based compound " CDA-10 ".Become in the way of in the of 0.5 μm by dried thickness, said composition is coated into Kaneka companies
On the polyimide film " 25 μm of Apical NPI thickness " of system, with 200 DEG C drying-heat treatment in 5 minutes is carried out.
AC-14:It is same with AC-1, but do not add additive, obtain the polyimide film with resin bed.
AC-15:It is same with AC-9, but do not add additive, obtain the polyimide film with resin bed.
[table 1]
Adhesive resin:
·Vylon270:The copolyester of company system spins in Japan
·Vylon290:The copolyester of company system spins in Japan
Polyester 1-1~2-2:To possessing in thermometer, agitator, the reaction vessel of Li Bixi (Liebig) condenser pipe
Load 140 parts of dimethyl terephthalate (DMT), 8.9 parts of Sodium Dimethyl Isophthalate-5-sulfonate, 122 parts of 1,3- propane diols,
0.1 part of 82 parts of Hydroxypivalyl hydroxypivalate (Hydroxypivalyl hydroxypivalate) and butyl titanate,
Heat 180 minutes at 150~230 DEG C, after carrying out ester exchange, add 50.5 parts of decanedioic acid, at 200~220 DEG C 60 minutes are carried out
Esterification.Reaction system is warming up to into 270 degree with 30 minutes, system is lentamente reduced pressure, become after 10 minutes
0.3mmHg.React 80 minutes under this condition, obtain polyester resin.The analysis result of resulting resin is represented in table 2
In.Same operation obtains the polyester described in table 2.With regard to polyester 1-2 and 1-3, constitute identical with polyester 1-1, but molecular weight
It is different.With regard to polyester 2-1 and 2-2, constitute similar with polyester 1-1, but without sulphonate-base.
[table 2]
Breviary symbol in table is as described below:
T:Terephthalic acid (TPA);Seb:Decanedioic acid;SIA:5-sodium sulfo isophthalate;
1,3-PG:1,3- propane diols;HPN:Hydroxypivalyl hydroxypivalate
Embodiment 1:
The composition of following mixing ratios is loaded into sand mill, is disperseed 1 hour with 800rpm.Medium actionradius
The zirconium oxide bead of 0.2mm.Become in the way of in the of 2 μm by dried thickness, coated resulting copper cream using coating machine attached
Have on the resin bed of polyimide film (AC-1) of resin bed, with 100 DEG C 5 minutes heated-air dryings are carried out, obtain containing copper powders
Film.
Dispersion liquid is constituted
2 minutes overheated steams are carried out to the resulting film containing copper powders with 330 DEG C to process.Heated using steam
Device (" the DHF Super-Hi10 " of the first high frequency industrial group) as the generating means of overheated steam, with 10kg/
Overheated steam is supplied heat-treatment furnace by hour.The evaluation result of resulting conductive coating is shown in Table 3 below.
Embodiment 2~8:
Using the polyimide film with resin bed described in table 3 as insulated substrate, in addition, with embodiment 1
Same operation obtains conductive coating.The evaluation result of resulting conductive coating is shown in Table 3 below.
Embodiment 9~14:
The composition of following mixing ratios is loaded into sand mill, is disperseed 1 hour with 800rpm.Medium actionradius
The zirconium oxide bead of 0.2mm.Become in the way of in the of 2 μm by dried thickness, coated resulting copper cream using coating machine attached
Have on the resin bed of polyimide film (AC-9) of resin bed, with 100 DEG C 5 minutes heated-air dryings are carried out, obtain containing copper powders
Film.
Dispersion liquid is constituted
2 minutes overheated steams are carried out to the resulting film containing copper powders with 300 DEG C to process.Heated using steam
Device (" the DHF Super-Hi10 " of the first high frequency industrial group) as the generating means of overheated steam, with 10kg/
Overheated steam is supplied heat-treatment furnace by hour.The evaluation result of resulting conductive coating is shown in Table 3 below.Wherein,
In embodiment 10~14, using the polyimide film with resin bed described in table 3 as insulated substrate, as shown in table 3,
Change overheated steam treatment conditions.
[table 3]
Comparative example 1:
Using the polyimide film " 25 μm of Apical NPI thickness " without resin-coated Kaneka company systems as absolutely
Edge substrate, in addition, operation similarly to Example 1 obtains conductive coating.The evaluation of resulting conductive coating is tied
Fruit is shown in Table 4 below.
Comparative example 2:
Using AC-14 as insulated substrate, in addition, operation similarly to Example 1 obtains conductive coating.By institute
The evaluation result of the conductive coating for obtaining is shown in Table 4 below.
Comparative example 3:
Using AC-15 as insulated substrate, in addition, operation similarly to Example 9 obtains conductive coating.By institute
The evaluation result of the conductive coating for obtaining is shown in Table 4 below.
Comparative example 4:
The polyimide film " 25 μm of Apical NPI thickness " of Kaneka company systems is immersed in into 2- phenylimidazoles under room temperature
5% tetrahydrofuran solution 100ml in after 5 minutes, after sinking to above-mentioned dipping portion 5 minutes in the tetrahydrofuran of 1L, under room temperature
It is allowed to drying.Using the polyimide film as insulated substrate, in addition, conductive coating is obtained similarly to Example 1.Will
The evaluation result of resulting conductive coating is shown in Table 4 below.
Comparative example 5,6:
It is same with comparative example 2, but, in the copper cream for being used with 1 weight of the nonvolatile component of copper cream in comparative example 5
Amount % addition 2- phenylimidazoles, are added in the copper cream for being used in comparative example 6 with 1 weight % of the nonvolatile component of copper cream
Plus the benzotriazole derivatives " JF-832 " of north of the city chemical company, in addition, same operation obtains conductive coating.Will
The evaluation result of resulting conductive coating is shown in Table 4 below.
Comparative example 7,8:
It is same with comparative example 3, but, in the copper cream for being used with 1 weight of the nonvolatile component of copper cream in comparative example 7
Amount % adds the hydrazides based compound " CDA-6 " of Adeka company systems, in the copper cream for being used with copper cream in comparative example 8
3 weight % of nonvolatile component add the hydrazides based compound " CDA-6 " of Adeka company systems, in addition, equally operate
To conductive coating.The evaluation result of resulting conductive coating is shown in Table 4 below.
Comparative example 9,10:
It is same with comparative example 3, but, city is added with 1 weight % of the nonvolatile component of copper cream in the copper cream for being used
The benzotriazole derivatives " BT-3700 " of northern chemical company, in comparative example 10, as shown in table 4, change overheated steam
Treatment conditions, in addition, same operation obtains conductive coating.The evaluation result of the conductive coating for obtaining is represented in table
In 4.
Comparative example 11:
Using the electroless copper plating bath " OPC Copper T " of pharmaceuticals industry company system in open country difficult to understand with 60 DEG C of works to embodiment 1
Obtained by the midway of sequence, sheet resistance is 106The overheated steam before processing of Ω/more than with the painting containing copper powders
The polyimide film of film carries out 10 minutes platings, gives electric conductivity.Sheet resistance now is 0.2 Ω/.In order to further right
Adaptation and heat resistance are evaluated, and carry out copper plating.Evaluation result is shown in Table 4 below.
[table 4]
Embodiment 15~18:
In the baking furnace of hydrogen 0.1L/ minutes and the mixed-gas atmosphere of nitrogen 1L/ minutes, with the condition shown in table 5 to reality
Obtained by the midway of the operation for applying example 1, overheated steam before processing the polyimide film with the film containing copper powders
Heated, formed conductive coating.The evaluation result of resulting conductive coating is shown in Table 5 below.
Embodiment 19,20:
In the baking furnace of hydrogen 0.1L/ minutes and the mixed-gas atmosphere of nitrogen 1L/ minutes, with the condition shown in table 5 to reality
Obtained by the midway of the operation for applying example 11, overheated steam before processing the polyimide film with the film containing copper powders
Heated, formed conductive coating.The evaluation result of resulting conductive coating is shown in Table 5 below.
Comparative example 12:
In the baking furnace of hydrogen 0.1L/ minutes and the mixed-gas atmosphere of nitrogen 1L/ minutes, with the conditions correlation shown in table 5
The polyimide film with the film containing copper powders of obtained by compared with the midway of the operation of example 2, overheated steam before processing
Heated, formed conductive coating.The evaluation result of resulting conductive coating is shown in Table 5 below.
Comparative example 13:
In the baking furnace of hydrogen 0.1L/ minutes and the mixed-gas atmosphere of nitrogen 1L/ minutes, with the conditions correlation shown in table 5
The polyimide film with the film containing copper powders of obtained by compared with the midway of the operation of example 3, overheated steam before processing
Heated, formed conductive coating.The evaluation result of resulting conductive coating is shown in Table 5 below.
[table 5]
Embodiment 21:
Using the electroless copper plating bath " ATS Addcopper IW " of pharmaceuticals industry company system in open country difficult to understand with 40 DEG C to embodiment 1
In the polyimide film for carrying out conducting that obtains carry out 5 minutes platings, improve electric conductivity.
By the plating of 5 minutes, sheet resistance was reduced to 0.0028 Ω/ from 0.055 Ω/, and electric conductivity is improved.In plating
Cellophane tape is bonded in surface application, it is completely not peeling-off when carrying out the belt stripping test of quick stripping.
Comparative example 14:
Using the electroless copper plating bath " ATS Addcopper IW " of pharmaceuticals industry company system in open country difficult to understand with 40 DEG C to embodiment 1
Operation midway obtained by, the polyimide film with the film containing copper powders of overheated steam before processing carry out 5
Minute plating, shows electric conductivity.By the plating of 5 minutes, sheet resistance was from 106Ω/more than is reduced to 0.81 Ω/, leads
Electrically improve, but in plating surface application bonding cellophane tape, when carrying out the belt stripping test of quick stripping, entire surface there occurs stripping
From.
Embodiment 22:
Using the epoxy glass fabric of 200 μm of Dong Shinko companies (NITTO SHINKO CORPORATION) system of thickness
Prepreg (EPOXY GLASS CLOTH PREPREG) " EGL-7 " as insulated substrate, using it is Chong Die with fluororesin film and with
200 DEG C carried out being heating and curing for 1 hour obtained from epoxy glass fabric as mold release film.Become 0.5 μm with dried thickness
Mode, the polyimide film " AC-1 " being coated with insulated substrate with resin bed using wire bar (wire bar) made
Solution, with 200 DEG C of dry solidifications 5 minutes.Become in the way of in the of 2 μm by dried thickness, be coated with same as Example 1
Copper cream, with 100 DEG C 5 minutes heated-air dryings are carried out, and obtain the film containing copper powders.Carry out superheated water similarly to Example 1 again
Steam treated, obtains conductive coating.Conductive coating is evaluated similarly to Example 1.Sheet resistance be 0.068 Ω/
, the initial value of fitness test 1 is 11.1N/cm, is 10.1N/cm after heat resistant test.
Embodiment 23~25:
The composition of following mixing ratios is loaded into sand mill, is disperseed 1 hour with 800rpm.Medium actionradius
The zirconium oxide bead of 0.2mm.The copper cream for obtaining is coated the polyimide film (AC-16) with resin bed using coating machine
On resin bed, dried thickness is adjusted, be allowed to respectively become the value described in table 6, with 100 DEG C 10 minutes hot air dryings are carried out
It is dry, obtain the film containing copper powders.
Dispersion liquid is constituted
2 minutes overheated steams are carried out to the resulting film containing copper powders with 330 DEG C to process.Heated using steam
Device (" the DHF Super-Hi10 " of the first high frequency industrial group) as the generating means of overheated steam, with 10kg/
Overheated steam is supplied heat-treatment furnace by hour.The evaluation result of resulting conductive coating is shown in Table 6 below.
Embodiment 26~28:
The composition of following mixing ratios is loaded into sand mill, is disperseed 1 hour with 800rpm.Medium actionradius
The zirconium oxide bead of 0.2mm.The copper cream for obtaining is coated into polyimide film with resin bed (AC-16,3) using coating machine
Resin bed on, adjust dried thickness, be allowed to respectively become the value described in table 6, carry out 10 minutes hot air dryings with 100 DEG C
It is dry, obtain the film containing copper powders.
Dispersion liquid is constituted
2 minutes overheated steams are carried out to the resulting film containing copper powders with 330 DEG C to process.Heated using steam
Device (" the DHF Super-Hi10 " of the first high frequency industrial group) as the generating means of overheated steam, with 10kg/
Overheated steam is supplied heat-treatment furnace by hour.The evaluation result of resulting conductive coating is shown in Table 6 below.
Embodiment 29,30:
In the baking furnace of hydrogen 0.1L/ minutes and the mixed-gas atmosphere of nitrogen 1L/ minutes, with the condition shown in table 6 to reality
Obtained by the midway of the operation for applying example 27, overheated steam before processing the polyimide film with the film containing copper powders
Heated, formed conductive coating.The evaluation result of resulting conductive coating is shown in Table 6 below.
[table 6]
Embodiment 31:
After with composition mixing of the mixer by following mixing ratios, using Exact Technologies company systems
Three-roller " M-50 " is disperseed.The copper cream for obtaining is coated the polyimide film (AC- with resin bed using coating machine
16) on resin bed, dried thickness is adjusted, makes 20 μm, with 100 DEG C 15 minutes heated-air dryings are carried out, contained
There is the film of copper powders.
Dispersion liquid is constituted
2 minutes overheated steams are carried out to the resulting film containing copper powders with 340 DEG C to process.Heated using steam
Device (" the DHF Super-Hi10 " of the first high frequency industrial group) as the generating means of overheated steam, with 10kg/
Overheated steam is supplied heat-treatment furnace by hour.The evaluation result of resulting conductive coating is shown in Table 7 below.
Embodiment 32~42:
It is same with embodiment 31, but, adhesive resin is used described in table 7 in embodiment 32~35 and 39~42
Polyester, embodiment 38 and embodiment 41 with copper cream in total nonvolatile component in the ratio of copper powders become the side of 99 weight %
Formula is changed to the composition described in table 7, and in addition, same operation obtains conductive coating.By resulting conductive coating
Evaluation result be shown in Table 7 below.
[table 7]
Comparative example 15:
Using the polyimide film " 25 μm of Apical NPI thickness " without resin-coated Kaneka company systems as absolutely
Edge substrate, in addition, with the equally operation of embodiment 31 conductive coating is obtained.The evaluation of resulting conductive coating is tied
Fruit is shown in Table 8 below.
Comparative example 16,17:
Using AC-14 as insulated substrate, the polyester 1-3 used in comparative example 17 as adhesive resin, except this with
Outward, conductive coating is obtained with the equally operation of embodiment 31.The evaluation result of resulting conductive coating is represented in table 8
In.
Comparative example 18,19:
Using AC-15 as insulated substrate, the polyester 2-1 used in comparative example 19 as adhesive resin, except this with
Outward, conductive coating is obtained with the equally operation of embodiment 31.The evaluation result of the conductive coating for obtaining is shown in Table 8 below.
[table 8]
Embodiment 43:
Using 200 μm of thickness day east Shinko company systems epoxy glass fabric prepreg (EPOXY GLASS CLOTH
PREPREG) " EGL-7 " used as insulated substrate, using it is Chong Die with fluororesin film and with 200 DEG C carried out being heating and curing for 1 hour and
The epoxy glass fabric for obtaining is used as mold release film.Become in the way of in the of 0.5 μm, using wire bar in insulated substrate by dried thickness
Solution used in polyimide film " AC-16 " of the upper coating with resin bed, with 200 DEG C of dry solidifications 5 minutes.With dry
Thickness after dry becomes 20 μm of mode, coating and the identical copper cream of embodiment 31, and with 100 DEG C 15 minutes heated-air dryings are carried out,
Obtain the film containing copper powders.Again overheated steam process is equally carried out with embodiment 31, obtain conductive coating.It is resulting
The specific insulation of conductive coating be 6.8 μ Ω cm, the result of fitness test 2 after overheated steam before processing
For " A ".
Comparative example 20:
As insulated substrate, using without 200 μm of resin-coated thickness day east Shinko company systems expoxy glass
Cloth prepreg (EPOXY GLASS CLOTH PREPREG) " EGL-7 ", in addition, is led with the equally operation of embodiment 43
Electrical film.The specific insulation of resulting conductive coating is 6.8 μ Ω cm, and the result of fitness test 2 is in superheated water
It is before and after steam treated " C ".
Industrial applicability
The conductive coating obtained in the present invention has across containing the heterocyclic compound comprising nitrogen and/or acyl in heterocycle
The resin bed of hydrazine compound is stacked in the structure on insulated substrate, implements to heat in non-oxidizing atmosphere, thus not only
Excellent electric conductivity, and also improve with the adaptation of insulated substrate.These conductive coatings can be used in metal/resin lamination
Metal foil film formation material, metal wiring material, conductive material of body, electromagnetic shielding metallic film etc. etc..
Claims (7)
1. a kind of manufacture method of conductive coating, it is characterised in that:
Resin bed containing the heterocyclic compound comprising nitrogen and/or hydrazide compound in heterocycle is set on insulated substrate,
Formed after the film containing copper powders using copper cream on the resin bed, implement to heat in non-oxidizing atmosphere.
2. the manufacture method of conductive coating as claimed in claim 1, it is characterised in that:
The copper cream contains copper powders, adhesive resin and solvent, the ratio of the copper powders in total nonvolatile component of the copper cream
More than 94 weight %.
3. the manufacture method of conductive coating as claimed in claim 1 or 2, it is characterised in that:
Adhesive resin contained by the copper cream contains the polymer comprising sulphonate-base or carboxylate group.
4. the manufacture method of the conductive coating as any one of claims 1 to 3, it is characterised in that:
The heating is carried out more than 200 DEG C.
5. the manufacture method of the conductive coating as any one of Claims 1 to 4, it is characterised in that:
The heating uses overheated steam.
6. the manufacture method of the conductive coating as any one of Claims 1 to 5, it is characterised in that:
After implementing to heat, plating is further carried out.
7. the conductive coating that the manufacture method any one of a kind of utilization claim 1~6 is manufactured.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1822749A (en) * | 2004-11-30 | 2006-08-23 | 新日铁化学株式会社 | Copper-clad laminated sheet |
CN102037157A (en) * | 2008-03-21 | 2011-04-27 | 恩索恩公司 | Adhesion promotion of metal to laminate with a multi-functional compound |
CN102102000A (en) * | 2010-12-30 | 2011-06-22 | 上海南亚覆铜箔板有限公司 | Adhesive of medium glass transition temperature epoxy glass cloth-based copper-clad laminate suitable for lead-free process |
CN102326213A (en) * | 2009-02-18 | 2012-01-18 | 东洋纺织株式会社 | Metal thin film production method and metal thin film |
CN102634167A (en) * | 2011-02-10 | 2012-08-15 | 台光电子材料股份有限公司 | Resin composition |
JP2013237881A (en) * | 2012-05-11 | 2013-11-28 | Ishihara Chem Co Ltd | Electroless copper plating method |
CN103732704A (en) * | 2011-05-18 | 2014-04-16 | 户田工业株式会社 | Method for manufacturing conductive coating film and conductive coating film |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5053495A (en) | 1973-09-12 | 1975-05-12 | ||
JPS61266241A (en) | 1985-05-21 | 1986-11-25 | 株式会社日立製作所 | Surface treating method of copper |
JP2561537B2 (en) | 1989-03-30 | 1996-12-11 | 真空冶金株式会社 | Metal paste and manufacturing method thereof |
JPH08311658A (en) | 1995-05-17 | 1996-11-26 | Nippon Parkerizing Co Ltd | Composition for surface treatment of copper based metallic material |
WO2008018399A1 (en) | 2006-08-10 | 2008-02-14 | Nippon Steel Chemical Co., Ltd. | Process for surface modification of polyimide resin layers and process for production of metal-clad laminates |
JP5453789B2 (en) | 2008-12-04 | 2014-03-26 | 東洋紡株式会社 | Metal fine particle dispersion, method for producing metal thin film, and metal thin film |
JP5564866B2 (en) | 2009-09-11 | 2014-08-06 | 東洋紡株式会社 | Metal thin film manufacturing method and metal thin film |
-
2015
- 2015-07-06 KR KR1020177000010A patent/KR20170032275A/en unknown
- 2015-07-06 JP JP2016534375A patent/JP6547748B2/en active Active
- 2015-07-06 CN CN201580035526.6A patent/CN106663504A/en active Pending
- 2015-07-06 WO PCT/JP2015/069413 patent/WO2016009873A1/en active Application Filing
- 2015-07-09 TW TW104122325A patent/TW201612917A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1822749A (en) * | 2004-11-30 | 2006-08-23 | 新日铁化学株式会社 | Copper-clad laminated sheet |
CN102037157A (en) * | 2008-03-21 | 2011-04-27 | 恩索恩公司 | Adhesion promotion of metal to laminate with a multi-functional compound |
CN102326213A (en) * | 2009-02-18 | 2012-01-18 | 东洋纺织株式会社 | Metal thin film production method and metal thin film |
CN102102000A (en) * | 2010-12-30 | 2011-06-22 | 上海南亚覆铜箔板有限公司 | Adhesive of medium glass transition temperature epoxy glass cloth-based copper-clad laminate suitable for lead-free process |
CN102634167A (en) * | 2011-02-10 | 2012-08-15 | 台光电子材料股份有限公司 | Resin composition |
CN103732704A (en) * | 2011-05-18 | 2014-04-16 | 户田工业株式会社 | Method for manufacturing conductive coating film and conductive coating film |
JP2013237881A (en) * | 2012-05-11 | 2013-11-28 | Ishihara Chem Co Ltd | Electroless copper plating method |
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KR20170032275A (en) | 2017-03-22 |
WO2016009873A1 (en) | 2016-01-21 |
JPWO2016009873A1 (en) | 2017-05-25 |
JP6547748B2 (en) | 2019-07-24 |
TW201612917A (en) | 2016-04-01 |
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