CN104661818A

CN104661818A - Laminate, electroconductive pattern, and electric circuit

Info

Publication number: CN104661818A
Application number: CN201380050514.1A
Authority: CN
Inventors: 富士川亘; 齐藤公惠; 村川昭; 白发润
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2012-09-28
Filing date: 2013-09-18
Publication date: 2015-05-27
Anticipated expiration: 2033-09-18
Also published as: TWI548524B; JPWO2014050657A1; KR101721966B1; JP5569662B1; KR20150038105A; TW201412540A; CN104661818B; WO2014050657A1

Abstract

The present invention relates to a laminate characterized in having: a layer (I) comprising a support body containing a specific polyimide resin; a resin layer (II) for receiving a fluid containing an electroconductive substance (x); and an electroconductive layer (III) formed by the electroconductive substance (x). The present invention further relates to an electroconductive pattern and an electric circuit. This laminate has excellent adhesion between the layer comprising a support body and the resin layer for receiving an electroconductive substance and can maintain an excellent adhesion even when exposed to a high-temperature environment, and can therefore be used as a laminate for an electroconductive pattern or the like.

Description

Duplexer, conductive pattern and circuit

Technical field

The present invention relates to the duplexer of the conductive pattern in a kind of manufacture that can be used in electromagnetic wave shielding thing, integrated circuit or organic transistor etc. etc.

Background technology

In recent years, along with the high performance of e-machine, miniaturization, slimming, densification, slimming are also strongly required for its electronic circuit used, integrated circuit.

As the conductive pattern that can be used in above-mentioned electronic circuit etc., such as there will be a known the conductive pattern of following gained, namely, on the surface of supporting mass, coating waits electric conductivity ink liquid, the plating core agent burning till of conductive material containing silver, forms conductive material layer thus, then, plating process is carried out to the surface of above-mentioned conductive material layer, is provided with plating layer thus on the surface of above-mentioned conductive material layer (such as with reference to patent document 1.)。

But, above-mentioned conductive pattern due to the adaptation of above-mentioned supporting mass and above-mentioned conductive material layer abundant not, therefore above-mentioned conductive material is passed in time and comes off from above-mentioned supporting mass surface, thus there is the situation causing the broken string of the conductive pattern formed by above-mentioned conductive material, the reduction (rising of resistance value) of electric conductivity.

As the method for adaptation improving above-mentioned supporting mass and above-mentioned conductive material, such as there will be a known following method, namely, the black liquid of latex layer is being provided with by holding on base material on supporting mass surface, use electric conductivity ink liquid and utilize the method for regulation to draw pattern, making conductive pattern thus (with reference to patent document 2.)。

But, the conductive pattern utilizing said method to obtain still has at above-mentioned supporting mass and above-mentioned black liquid by the also insufficient situation of the adaptation this respect holding layer, therefore above-mentioned black liquid is passed in time by appearance layer and above-mentioned conductive material and comes off from the surface of above-mentioned supporting mass, there is the situation causing the broken string of the conductive pattern formed by above-mentioned conductive material, the reduction of electric conductivity.

In addition, for black liquid by holding layer from for the stripping on above-mentioned supporting mass surface, such as occur when being heated to 100 DEG C ~ about 200 DEG C in above-mentioned plating treatment process etc., abundant not in these heat resistances, therefore in above-mentioned conductive pattern, sometimes cannot to improve for the purpose of its intensity etc. and to implement plating process.

Prior art document

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2005-286158 publication

Patent document 2: Japanese Unexamined Patent Publication 2009-49124 publication

Summary of the invention

Invent problem to be solved

Problem to be solved by this invention is, the duplexer of a kind of conductive pattern etc. is provided, for described duplexer, the layer comprising supporting mass with by the excellent adhesion of resin bed holding conductive material, even and if possess the heat resistance of the level of the above-mentioned adaptation that also can maintain excellence when being exposed under hot environment.

For solving the method for problem

The present inventor etc. are studied to study above-mentioned problem, found that, by using specific supporting mass, thus can solve above-mentioned problem.

That is, the present invention relates to duplexer, conductive pattern and circuit, the feature of above-mentioned duplexer is, has layer (I), resin bed (II) and conductive layer (III),

Above-mentioned layer (I) comprises supporting mass (I1) or supporting mass (I2), the polyimide resin (i-1) of described supporting mass (I1) containing the structure had represented by following general formula (1) and there is the polyimide resin (i-2) of the structure represented by following general formula (2), the polyimide resin (i-3) of described supporting mass (I2) containing the structure represented by the structure had represented by following general formula (1) and following general formula (2)

Above-mentioned resin bed (II) contains the liquid of conductive material (x) by holding,

Above-mentioned conductive layer (III) is formed by above-mentioned conductive material (x).

R in general formula (1) ¹~ R ⁸represent hydrogen atom, halogen atom or organic group independently of one another.N represents 1 ~ 1, the integer of 000.

R in general formula (2) ⁹~ R ²²represent hydrogen atom, halogen atom or organic group independently of one another.M represents 1 ~ 1, the integer of 000.

The effect of invention

Even if duplexer of the present invention also can keep excellent adaptation when being exposed under hot environment, consequently, broken string can not be caused to wait and keep excellent electric conductivity, therefore such as can in the formation of conductive pattern or electronic circuit, form organic solar batteries or e-book terminal, organic EL, organic transistor, flexible circuit board, each layer of the RFID such as contactless IC card etc. or the formation of periphery distribution, the distribution of the electromagnetic wave shielding thing of plasma scope, integrated circuit, the manufactures of organic transistor etc. are generally known as in the frontier in printed electronic field and use.

Detailed description of the invention

Duplexer of the present invention is the duplexer at least with layer (I), resin bed (II) and conductive layer (III),

Above-mentioned conductive layer (III) is formed by above-mentioned conductive material (x),

Duplexer of the present invention such as goes in conductive pattern, circuit etc.

First, the layer (I) forming duplexer of the present invention is described.

The layer (I) forming duplexer of the present invention is the layer be made up of the supporting mass of supporting stack (I1) or supporting mass (I2).

As above-mentioned supporting mass, use the polyimide resin (i-1) containing the structure had represented by following general formula (1) and there is the supporting mass (I1) of polyimide resin (i-2) of the structure represented by following general formula (2) or the supporting mass (I2) of the polyimide resin (i-3) containing the structure represented by the structure had represented by following general formula (1) and following general formula (2).

Above-mentioned supporting mass (I1) is containing above-mentioned polyimide resin (i-1) and polyimide resin (i-2).

Above-mentioned polyimide resin (i-1) has the structure represented by above-mentioned general formula (1).

R in above-mentioned general formula (1) ¹~ R ⁸be hydrogen atom, hydroxyl, halogen atom or organic group independently of one another.As above-mentioned organic group, specifically, alkyl, aryl can be enumerated.From giving excellent adaptation, heat resistance, the aspect that can obtain is considered less expensively, above-mentioned R ¹~ R ⁸be preferably hydrogen atom.

M in above-mentioned general formula (1) is preferably 1 ~ 1, and the integer of 000 is more preferably the integer of 3 ~ 500, more preferably the integer of 50 ~ 500, is particularly preferably the integer of 100 ~ 500.

As above-mentioned polyimide resin (i-1), preferably the structure of its molecular end is amino.

Above-mentioned polyimide resin (i-1) such as can by making containing 4, polyamines and the tetrabasic carboxylic acid dihydrate containing pyromellitic dianhydride of 4 '-oxygen diphenylamines etc. react to manufacture polyamic acid (acid of Port リアミ Star Network), then, mix with catalyst etc. as required, carry out heating etc. and manufacture.

The reaction of above-mentioned polyamine and above-mentioned tetrabasic carboxylic acid dihydrate can utilize in the past known method to carry out.

When manufacturing above-mentioned polyimide resin (i-1), also can be used together 4, polyamines beyond 4 '-oxygen diphenylamines, the tetrabasic carboxylic acid dihydrate beyond pyromellitic dianhydride, but, the total amount of the raw material used in the manufacture relative to above-mentioned polyimide resin (i-1), preferably in the scope of total 95 quality % ~ 100 quality %, use 4,4 '-oxygen diphenylamines and pyromellitic dianhydride.

In addition, as using the polyamic acid obtained in aforesaid operations to manufacture the method for polyimide resin (i-1), the method for heating can be enumerated.

Above-mentioned heating is preferably carried out at 200 DEG C ~ 300 DEG C more than 150 DEG C, more preferably.

As the method manufacturing above-mentioned polyimide resin (i-1), specifically, JOURNAL OF POLYMER SCIENCE:PART A-2 VOL.6 can be enumerated, the method recorded in 953-960 (1968).

The polyimide resin (i-2) forming above-mentioned supporting mass (I1) has the structure represented by above-mentioned general formula (2).

R in above-mentioned general formula (2) ⁹~ R ²²be hydrogen atom, hydroxyl, halogen atom or organic group independently of one another.As above-mentioned organic group, specifically, alkyl, aryl can be enumerated.From the viewpoint of giving excellent adaptation, above-mentioned R ⁹~ R ²²be preferably hydrogen atom.

N in above-mentioned general formula (2) is preferably 1 ~ 1, and the integer of 000 is more preferably the integer of 3 ~ 500, more preferably the integer of 50 ~ 500, is particularly preferably the integer of 100 ~ 500.

As above-mentioned polyimide resin (i-2), preferably the structure of its molecular end is amino.

Above-mentioned polyimide resin (i-2) such as can by making containing 4, the polyamines of 4 '-oxygen diphenylamines etc. with containing 3,4,3 ', the tetrabasic carboxylic acid dihydrate reaction of 4 '-biphenyltetracarboxyacid acid dihydrate manufactures polyamic acid, then mix with catalyst etc. as required, carry out heating etc. and manufacture.

The reaction of above-mentioned polyamines and above-mentioned tetrabasic carboxylic acid dihydrate can utilize in the past known method to carry out.

When manufacturing above-mentioned polyimide resin (i-2), also can be used together 4, the polyamines beyond 4 '-oxygen diphenylamines, 3,4, tetrabasic carboxylic acid dihydrate beyond 3 ', 4 '-biphenyltetracarboxyacid acid dihydrate, but, the total amount of the raw material used in the manufacture relative to above-mentioned polyimide resin (i-2), preferably in the scope of total 95 quality % ~ 100 quality %, use 4,4 '-oxygen diphenylamines and 3,4,3 ', 4 '-biphenyltetracarboxyacid acid dihydrate.

In addition, as using the polyamic acid obtained in aforesaid operations to manufacture the method for polyimide resin (i-2), the method for heating can be enumerated.

As the method manufacturing above-mentioned polyimide resin (i-2), specifically can enumerate JOURNAL OF POLYMER SCIENCE:PART A-2 VOL.6, the method recorded in 953-960 (1968).

As the above-mentioned supporting mass (I1) forming above-mentioned layer (I), preferably use the supporting mass containing above-mentioned polyimide resin (i-1) and above-mentioned polyimide resin (i-2) with the ratio of [above-mentioned polyimide resin (i-1)/above-mentioned polyimide resin (i-2)]=5 ~ 95.

In addition, as the supporting mass (I2) of the layer (I) of formation duplexer of the present invention, the supporting mass of the polyimide resin (i-3) containing combination with the structure represented by following general formula (1) and the structure represented by following general formula (2) can be used.

As above-mentioned polyimide resin (i-3), can by make to go out illustrated in the material that can use in the manufacture of above-mentioned polyimide resin (i-1), above-mentioned polyimide resin (i-2), containing 4, the polyamines of 4 '-oxygen diphenylamines etc. with containing pyromellitic dianhydride or 3,4,3 ', the tetrabasic carboxylic acid dihydrate reaction of 4 '-biphenyltetracarboxyacid acid dihydrate, thus manufacture polyamic acid, then, mix with catalyst etc. as required, carry out heating etc. and manufacture.

When manufacturing above-mentioned polyimide resin (i-3), also can be used together 4, the polyamines beyond 4 '-oxygen diphenylamines, pyromellitic dianhydride and 3,4,3 ', tetrabasic carboxylic acid dihydrate beyond 4 '-biphenyltetracarboxyacid acid dihydrate, but, the total amount of the raw material used in the manufacture relative to above-mentioned polyimide resin (i-3), preferably in the scope of total 95 quality % ~ 100 quality %, use pyromellitic dianhydride and 3,4,3 ', 4 '-biphenyltetracarboxyacid acid dihydrate.

In addition, as using the polyamic acid obtained in aforesaid operations to manufacture the method for polyimide resin (i-3), the method for heating can be enumerated.

As above-mentioned supporting mass (I1) and above-mentioned supporting mass (I2), can use containing above-mentioned polyimide resin (i-1), above-mentioned polyimide resin (i-2), above-mentioned polyimide resin (i-3) and the supporting mass of various additives that uses as required.

As above-mentioned additive, from the viewpoint of improve comprise the above-mentioned supporting mass (I1) of polyimide film, above-mentioned supporting mass (I2) conveyance easness, prevent the adhesion of above-mentioned supporting mass (I1), above-mentioned supporting mass (I2), such as preferably use the inorganic filler such as silica, calcium phosphate.

As above-mentioned inorganic filler, from the viewpoint of the flatness on surface improving above-mentioned supporting mass, preferably to use in the scope of 0.5 quality % ~ 30 quality % relative to the quality of above-mentioned supporting mass (I1) or above-mentioned supporting mass (I2).In addition, the average grain diameter of above-mentioned inorganic filler is preferably 0.01 μm ~ 5 μm, is more preferably 0.01 μm ~ 0.5 μm.And above-mentioned average grain diameter refers to the value utilizing laser diffraction and scattering formula size distribution counter device to record.

As the method manufacturing above-mentioned supporting mass (I1), such as can enumerate following method, namely, using the polyamic acid of the precursor as above-mentioned polyimide resin (i-1), as the precursor of above-mentioned polyimide resin (i-2) polyamic acid and use as required solvent mixing, by additive mixing such as the solution of gained and the above-mentioned inorganic fillers that uses as required, the mixture of gained is carried out as required filter, deaeration, then be configured as film or sheet, and heat.

As the method manufacturing above-mentioned supporting mass (I2), following method can be enumerated, namely, by the polyamic acid of the precursor as above-mentioned polyimide resin (i-3) and use as required solvent mixing, by additive mixing such as the solution of gained and the above-mentioned inorganic fillers that uses as required, the mixture of gained is carried out as required filter, deaeration, be then configured as film or sheet, and heat.

As above-mentioned manufacturing process, such as, can enumerate and use T-shaped mould etc. to be extruded on cylinder by said mixture, and make it the method for curtain coating.

After above-mentioned curtain coating, such as, remove above-mentioned solvent by the heating temperatures 30 seconds ~ about 90 seconds at 80 DEG C ~ 150 DEG C, the formed products of above-mentioned film or sheet can be obtained thus.

By by above-mentioned formed products such as at the heating temperatures 30 seconds ~ about 200 seconds of 200 DEG C ~ 450 DEG C, the supporting mass containing polyimide resin can be manufactured thus.

The layer (I) comprising supporting mass (I1) or the supporting mass (I2) utilizing said method to obtain is preferably 1 μm ~ 5, and the thickness of about 000 μm, is more preferably the thickness of 1 μm ~ about 300 μm.When needing soft duplexer as above-mentioned duplexer, preferably use the duplexer of the thickness of 1 μm ~ about 200 μm.

Below, the resin bed (II) forming duplexer of the present invention is described.

Above-mentioned resin bed (II) is the layer that the hard to bear appearance of energy contains the liquid of the conductive material (x) forming conductive layer described later (III).Above-mentioned resin bed (II), when touching above-mentioned liquid, promptly absorbs solvent contained in above-mentioned liquid, and above-mentioned conductive material (x) is supported the surface in resin bed (II).Thus, the layer (I) that comprises above-mentioned supporting mass (I1) or supporting mass (I2) and resin bed (II), adaptation, heat resistance with the conductive layer (III) be made up of conductive material (x) can be increased substantially.

Above-mentioned resin bed (II) can be located at part or all of the surface of the layer (I) comprising above-mentioned supporting mass (I1) or supporting mass (I2), also can be located at its one or both sides.Such as, as above-mentioned duplexer, the whole mask that can also be used in the surface of the layer (I) comprising above-mentioned supporting mass (I1) or supporting mass (I2) has resin bed (II), and the required part only in this resin bed (II) has the duplexer of above-mentioned conductive layer (III).In addition, the duplexer being only provided with above-mentioned resin bed (II) in the surface of the layer (I) comprising above-mentioned supporting mass (I1) or supporting mass (I2) in the part arranging above-mentioned conductive layer (III) can also be used in.

Above-mentioned resin bed (II) although different according to the use of duplexer of the present invention etc., but is preferably set to the thickness of the scope of 10nm ~ 1000 μm usually.In addition, due to the adaptation of layer (I) and the above-mentioned conductive layer (III) comprising above-mentioned supporting mass (I1) or supporting mass (I2) can be improved further, therefore the thickness of above-mentioned resin bed (II) is more preferably the scope of 10nm ~ 300nm, more preferably the scope of 10nm ~ 100nm.

As above-mentioned resin bed (II), the resin bed utilizing the compound resin (II-1), melmac (II-2), polyurethane resin, vinylite, epoxy resin, imide resin, amide resin, phenolic resins, polyvinyl alcohol, polyvinylpyrrolidone etc. that are made up of polyurethane resin and acrylic resin to be formed can be used.Wherein, from the viewpoint of the duplexer manufacturing adaptation and excellent heat resistance, the layer that the compound resin (II-1) be made up of polyurethane resin and acrylic resin or melmac (II-2) are formed preferably is used.

Below, the conductive layer (III) forming duplexer of the present invention is described.

Above-mentioned conductive layer (III) is the layer be made up of contained conductive material (x) in liquid such as electric conductivity ink liquid, the agent of plating core etc.For above-mentioned conductive layer (III), such as if employ the situation of the plating core agent comprising silver as above-mentioned liquid, so be equivalent to the layer be made up of above-mentioned silver contained in the agent of above-mentioned plating core, be equivalent to the printing picture that is made up of above-mentioned silver or pattern.

Above-mentioned conductive layer (III) is preferably made up of above-mentioned conductive material (x), specifically, is preferably made up of silver.Above-mentioned conductive layer (III) is formed primarily of above-mentioned conductive material as previously mentioned, but also remainingly in above-mentioned conductive layer (III) can have solvent, additive etc. contained in above-mentioned liquid.

In addition, above-mentioned conductive layer (III) can be located at part or all of the surface of above-mentioned resin bed (II).Such as, as above-mentioned duplexer, part that can be only required in the surface of above-mentioned resin bed (II) arranges above-mentioned conductive layer (III).Specifically, as the conductive layer (III) of the required part be only arranged in the surface of above-mentioned resin bed (II), the layer by the wire formed with wire setting-out can be enumerated.The layer with wire is suitable for manufacturing conductive pattern, circuit etc. as the duplexer of above-mentioned conductive layer (III).

For the width (live width) of the layer of above-mentioned wire, from the viewpoint of the densification etc. realizing conductive pattern, be 0.01 μm ~ about 200 μm, be preferably 0.01 μm ~ about 150 μm.

The conductive layer (III) forming duplexer of the present invention can use the conductive layer of the thickness of the scope of 10nm ~ 10 μm.The coating weight etc. of liquid that the thickness of above-mentioned conductive layer (III) can be used in the formation of above-mentioned conductive layer (III) by control, that comprise conductive material (x) adjusts.When above-mentioned conductive layer (III) is for thin-line-shaped conductive layer, its thickness (highly) is preferably the scope of 10nm ~ 1 μm.

In addition, from the viewpoint of the surface of improving above-mentioned conductive layer (III) and the adaptation of plating layer (IV) that can arrange as required, part or all of the surface of preferred above-mentioned conductive layer (III) is oxidized.

Herein, above-mentioned oxidation to refer in above-mentioned conductive layer (III) contained conductive material (x) and oxygen bonding and forms the situation of oxide, and the situation that the valence mumber comprising above-mentioned conductive material (x) increases.

Thus, as the oxidized surface of above-mentioned conductive layer (III), such as if employ the situation of silver as conductive material (x) contained in above-mentioned conductive layer (III), so can use the surface comprising silver oxide or make by bondings such as above-mentioned silver and hydroxyls the surface that its valence mumber is formed from the material that 0 is increased to+1.

For above-mentioned conductive layer (III), as long as the surface contacted with above-mentioned plating layer (IV) is oxidized, but also together with above-mentioned surface, whole conductive materials contained in above-mentioned conductive layer (III) can be oxidized.

The resistance value on the oxidized surface of above-mentioned conductive layer (III) is preferably the scope of 0.1 Ω/ ~ 50 Ω/, from the viewpoint of what give with the adaptation of the excellence of above-mentioned plating layer (IV), the preferably scope of 0.2 Ω/ ~ 30 Ω/.

In addition, duplexer of the present invention also except above-mentioned layer (I), above-mentioned resin bed (II) and above-mentioned conductive layer (III), also can have plating layer (IV) as required.

Above-mentioned plating layer (IV) is the layer arranged for following object, namely, such as when being used for by above-mentioned duplexer in conductive pattern etc., can not cause broken string etc. in long-time, formation can maintain the high Wiring pattern of the reliability of good powered.

Above-mentioned plating layer (IV) such as preferably comprises the layer of the metals such as copper, nickel, chromium, cobalt, tin, is more preferably the plating layer comprising copper.

Above-mentioned plating layer (IV) can use the layer of the thickness of the scope of 1 μm ~ 50 μm.The thickness of above-mentioned plating layer (IV) can by controlling processing time in plating treatment process when forming above-mentioned plating layer (IV) or current density, the use amount etc. of plating additive adjusts.

Below, the manufacture method of duplexer of the present invention is described.

Duplexer of the present invention such as can be manufactured by following method, namely, part or all coating resin composition (R) on the surface of the above-mentioned supporting mass (I1) or supporting mass (I2) that form above-mentioned layer (I) also carries out drying and forms above-mentioned resin bed (II), then, by the liquid of part or all coating containing conductive material (x) on the surface at above-mentioned resin bed (II), and carry out burning till and forming above-mentioned conductive layer (III).When arranging above-mentioned plating layer (IV), carrying out plating process by part or all of the surface to above-mentioned conductive layer (III), thus the duplexer also possessing plating layer (IV) can be manufactured.

The method of above-mentioned resin bed (II) is formed as part or all of the surface at above-mentioned supporting mass (I1) or supporting mass (I2), can by above-mentioned resin combination (R) being coated on part or all of the surface of above-mentioned supporting mass (I1) or supporting mass (I2), and remove aqueous medium contained in above-mentioned resin combination (R) or organic solvent equal solvent and formed.

As the method on surface above-mentioned resin combination (R) being coated on above-mentioned supporting mass (I1) or supporting mass (I2), such as, can enumerate the methods such as intaglio plate mode, coating method, silk screen mode, roll coating model, rotary coating mode, spraying method.

Also can utilize the dry treatment methods such as plasma discharge facture, ultraviolet treatment such as Corona discharge Treatment method as required to the above-mentioned supporting mass (I1) of the above-mentioned resin combination of coating (R) or the surface of supporting mass (I2), employ water, the wet treatment method of acidity or alkaline liquid, organic solvent etc. to be to carry out surface treatment.

Behind the surface above-mentioned resin combination (R) being coated on above-mentioned supporting mass (I1) or supporting mass (I2), as the method for solvent contained in this coating layer of removing, such as usual way uses drying machine to make it dry, and above-mentioned solvent is volatilized.As baking temperature, as long as be set as above-mentioned solvent can being made to volatilize and the temperature of dysgenic scope can not being caused above-mentioned supporting mass (I1) or supporting mass (I2).

For above-mentioned resin combination (R) to the coating weight on above-mentioned supporting mass (I1) or supporting mass (I2), from the viewpoint of giving excellent adaptation and electric conductivity, preferably relative to the area of above-mentioned supporting mass (I1) or supporting mass (I2), be 0.01g/m ²~ 60g/m ²scope, if to consider in above-mentioned liquid absorbability and the manufacturing cost of contained solvent, be then particularly preferably 0.1g/m ²~ 10g/m ².

Operable resin combination (R) in manufacture as above-mentioned resin bed (II), can use the composition containing various resin and solvent.

As above-mentioned resin, such as, can use the compound resin (II-1), melmac (II-2), polyurethane resin, acrylic resin, epoxy resin, imide resin, amide resin, phenolic resins, polyvinyl alcohol, polyvinylpyrrolidone etc. that are made up of polyurethane resin and acrylic resin.

As above-mentioned resin, comprising the layer (I) of above-mentioned supporting mass (I1) or supporting mass (I2) and the adaptation of above-mentioned conductive layer (III) from the viewpoint of improving further, especially preferably using the compound resin (II-1) be made up of polyurethane resin and acrylic resin or melmac (II-2).

As above-mentioned resin combination (R), from the viewpoint of the easness etc. maintaining coating, preferred use and the composition of above-mentioned resin containing 10 quality % ~ 70 quality %s all relative to above-mentioned resin combination (R), more preferably uses the composition of the above-mentioned resin containing 10 quality % ~ 50 quality %.

In addition, as operable solvent in above-mentioned resin combination (R), various organic solvent, aqueous medium can be used.

As above-mentioned organic solvent, such as, can use toluene or ethyl acetate, MEK etc.In addition, as above-mentioned aqueous medium, organic solvent water can be enumerated, mixing with water and their mixture.

As the organic solvent mixed with water, such as, can enumerate methyl alcohol, ethanol, just and the alcohols such as isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve; The ketone such as acetone, MEK; The ployalkylene glycol classes such as ethylene glycol, diethylene glycol (DEG), propane diols; The alkyl ether of ployalkylene glycol; The lactams etc. such as METHYLPYRROLIDONE.

In addition, as the resin used in above-mentioned resin combination (R), from the viewpoint of the adaptation improved further with various above-mentioned supporting mass (I1) or supporting mass (I2), preferably use the resin with hydrophilic radical.As above-mentioned hydrophilic radical, such as, can enumerate anionic property group, cationic groups, the nonionic group such as carboxylic acid ester groups, sulfonate group that part or all are formed with neutralizations such as alkali compounds, be preferably anionic property group.

In addition, above-mentioned resin also can have the cross-linking functional group such as alkoxysilyl or silanol group, hydroxyl, amino, methylol, methylol amide base, methylolamide base, methylol as required.Thus, above-mentioned resin bed (II) both can form cross-linked structure before applied above-mentioned liquid, also after applied above-mentioned liquid, such as, can utilize the heating of firing process etc. and form cross-linked structure in addition.

As operable compound resin (II-1) in above-mentioned resin combination (R), polyurethane resin can be enumerated and acrylic resin forms composite resin particles and can be dispersed in the medium material of aqueous medium.

Above-mentioned composite resin particles specifically can enumerate the particle being built-in with part or all of aforesaid propylene acid resin in the resin particle that formed at above-mentioned polyurethane resin.Now, aforesaid propylene acid resin also can with multiple particle shape dispersion in above-mentioned polyurethane resin particle, in addition, the composite resin particles of the core-shell-type be made up of the aforesaid propylene acid resin as sandwich layer and the polyurethane resin with above-mentioned hydrophilic radical as shell is preferably formed.Particularly when forming conductive pattern, the composite resin particles of the above-mentioned core-shell-type of the surfactant that preferred use does not need use that electrical characteristics can be made to reduce etc.And, as above-mentioned composite resin particles, preferred aforesaid propylene acid resin is covered haply completely by above-mentioned polyurethane resin, but this is non-essential, also can in the scope not damaging effect of the present invention, a part for aforesaid propylene acid resin is present in the most external of above-mentioned composite resin particles.Above-mentioned polyurethane resin and aforesaid propylene acid resin also can form covalent bond, but preferably do not form key.

In addition, from the viewpoint of maintaining good dispersion stability, above-mentioned composite resin particles is preferably the average grain diameter of the scope of 5nm ~ 100nm.Said average grain diameter herein, also has and describes, refer to the average grain diameter based on volume reference utilizing dynamic light scattering method to record in embodiment described later.

As above-mentioned compound resin (II-1), preferably in the scope of [polyurethane resin/acrylic resin]=90/10 ~ 10/90, contain above-mentioned polyurethane resin and aforesaid propylene acid resin, more preferably contain in the scope of 70/30 ~ 10/90.

Operable polyurethane resin in manufacture as above-mentioned compound resin (II-1), can use the resin obtained by making the reactions such as various polyalcohol and PIC and the chain elongation agent that uses as required.

As above-mentioned polyalcohol, such as, can use PPG, PEPA, polyesterether polyols, polycarbonate polyol etc.

As above-mentioned PEPA, such as, the aliphatic polyester polyols that low-molecular-weight polyalcohol and polybasic carboxylic acid can be used to carry out esterification and obtain or aromatic polyester polyol, the cyclic ester compounds such as 6-caprolactone are made to carry out ring-opening polymerization and the polyester, their copolyester etc. that obtain.

As above-mentioned low-molecular-weight polyalcohol, such as, can make spent glycol, propane diols, 1,6-hexylene glycol, neopentyl glycol etc.

In addition, as above-mentioned polybasic carboxylic acid, such as, can use the aromatic polycarboxylic acids such as the aliphatic polycarboxylic acid such as butanedioic acid, adipic acid, decanedioic acid, dodecanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid and their acid anhydrides or ester formative derivative etc.

In addition, as above-mentioned PPG, such as, can use the one kind or two or more as initator of the compound of the active hydrogen atom with more than 2, make epoxyalkane addition polymerization and the material obtained.

As above-mentioned initator, such as can make spent glycol, diethylene glycol (DEG), triethylene glycol, propane diols, trimethylene, 1,3-butanediol, 1,4-butanediol, 1,6-hexylene glycol, neopentyl glycol, glycerine, trimethylolethane, trimethylolpropane etc., bisphenol-A, Bisphenol F, bisphenol b, bisphenol-A D etc.

In addition, as above-mentioned epoxyalkane, such as, can use oxirane, expoxy propane, epoxy butane, Styryl oxide, chloropropylene oxide, oxolane etc.

In addition, as above-mentioned polyesterether polyols, such as, can be used in the above-mentioned epoxyalkane of addition on above-mentioned initator and the PPG obtained and the polybasic carboxylic acid material that reacts and obtain.As above-mentioned initator or above-mentioned epoxyalkane, can use with as the identical material of the example gone out illustrated in operable material when manufacturing above-mentioned PPG.In addition, as above-mentioned polybasic carboxylic acid, can use with as the identical material of the example gone out illustrated in operable material when manufacturing above-mentioned PEPA.

In addition, as above-mentioned polycarbonate polyol, such as, can use carbonic ester and polyol reaction and the material obtained, phosgene and bisphenol-A etc. be reacted and the material obtained.

As above-mentioned carbonic ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate ester, diphenyl carbonate etc. can be used.

As can with the polyalcohol of above-mentioned carbonate reaction, such as can make spent glycol, diethylene glycol (DEG), triethylene glycol, 1,2-PD, 1,3-PD, dipropylene glycol, BDO, 1,3-BDO, 1,2-butanediol, 2,3-butanediol, 1,5-PD, 1,5-hexylene glycol, 2,5-hexylene glycol, 1,6-hexylene glycol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane, 1,12-dodecanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,3-hexylene glycol, 2-methyl isophthalic acid, ammediol, 2-methyl isophthalic acid, 8-ethohexadiol, 2-butyl-2-ethyl glycol, 2-methyl isophthalic acid, 8-ethohexadiol, neopentyl glycol, Isosorbide-5-Nitrae-cyclohexanediol, 1,4-CHDM, quinhydrones, resorcinol, bisphenol-A, bisphenol-f, 4, the dihydroxy compounds of the lower molecular weights such as 4 '-xenol, polyethylene glycol, polypropylene glycol, the PPGs such as polytetramethylene glycol, polyhexamethylene adipate ester, polyhexamethylene succinate, the PEPAs etc. such as polycaprolactone.

In addition, as above-mentioned polyalcohol, hydrophilic radical is imported from the viewpoint of in polyurethane resin, such as can use 2,2 '-dihydromethyl propionic acid, 2,2 '-dimethylolpropionic acid, 2,2 '-dihydroxymethyl butyric acid, 5-sulfoisophthalic acid, sulfo-terephthalic acid (TPA), 4-sulfo-phthalic acid, 5 [4-sulfo-phenoxy group] M-phthalic acid etc.

As above-mentioned PIC, such as can use 4,4 '-methyl diphenylene diisocyanate, 2, the aliphatic polymeric isocyanate such as PIC, hexamethylene diisocyanate, cyclohexane diisocyanate, IPDI, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate containing aromatic structure such as 4 '-methyl diphenylene diisocyanate, toluene di-isocyanate(TDI) or the PIC containing aliphatic ring structures.Especially the PIC containing aliphatic ring structures is preferably used.

In addition, as above-mentioned chain elongation agent, such as, the material that ethylenediamine, piperazine, IPD etc. are in the past known can be used.

In addition, operable acrylic resin in the manufacture as above-mentioned compound resin (II-1), can use various (methyl) acrylic monomer that will be representative with (methyl) methyl acrylate to be polymerized the resin obtained.

As above-mentioned (methyl) acrylic monomer, such as, can use (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate.

In the middle of above-mentioned, from the viewpoint of required by 0.01 μm ~ about 200 μm, the width that is preferably 0.01 μm ~ about the 150 μm fine rule (raising of fine rule) that forms when can not cause the conductive pattern oozing and be printed on spreading and sinking in and form electronic circuit etc., preferably use methyl methacrylate.

In addition, preferably together with above-mentioned methyl methacrylate, use and there is (methyl) alkyl acrylate that carbon number is the alkyl of 2 ~ 12, more preferably use and there is the alkyl acrylate that carbon number is the alkyl of 3 ~ 8, from the viewpoint of the printed article obtaining printing excellence, preferably use n-butyl acrylate.In addition, even if when employing electric conductivity ink liquid, the aspect of never oozing the conductive pattern of ground formation fine rule excellences such as spreading and sinking in is considered, also particularly preferably.

In addition, as above-mentioned (methyl) acrylic monomer, from importing the above-mentioned cross-linking functional group such as the amide groups of more than a kind be selected from methylol amide base and methylolamide base to above-mentioned acrylic resin, the aspect realizing the further raising of adaptation etc. is considered, can use (methyl) acrylic monomer containing cross-linking functional group.

As (methyl) acrylic monomer containing cross-linking functional group, from the viewpoint of the duplexer of conductive pattern etc. obtaining fine rule, excellent adhesion, preferably use N-n-butoxy methyl (methyl) acrylamide, N-isobutoxymethyl (methyl) acrylamide.

Above-mentioned compound resin (II-1) such as can be manufactured by following operation: the chain elongation agent reaction making above-mentioned polyalcohol, PIC and use as required, carries out moisture dispersion and manufactures the operation of the aqueous dispersion of polyurethane resin; And the polymerization of above-mentioned (methyl) acrylic monomer is manufactured the operation of acrylic resin in above-mentioned aqueous dispersion.

Specifically, by under the existence of solvent-free time or organic solvent or under the existence of (methyl) acrylic monomer isoreactivity diluent, make above-mentioned PIC and polyol reaction and obtain polyurethane resin, then, part or all of the hydrophilic radical had by above-mentioned polyurethane resin uses the neutralizations such as alkali compounds as required, react with chain elongation agent more as required, be scattered in aqueous medium, manufacture the aqueous dispersion of polyurethane resin thus.

Then, in the aqueous dispersion of the polyurethane resin obtained to utilizing aforesaid operations, supply above-mentioned (methyl) acrylic monomer, in above-mentioned polyurethane resin particle, make above-mentioned (methyl) acrylic monomer generation radical polymerization, manufacture acrylic resin.In addition, when carrying out the manufacture of above-mentioned polyurethane resin under the existence of (methyl) acrylic monomer, after the manufacture of above-mentioned polyurethane resin, supply polymerization initiator etc., make above-mentioned (methyl) acrylic monomer generation radical polymerization thus, manufacture acrylic resin.

Thus, can manufacture by aforesaid propylene acid resin built-in in above-mentioned polyurethane resin particle part or all and the composite resin particles obtained is scattered in the resin combination (R) in aqueous medium.

In addition, as above-mentioned resin combination (R), the composition containing polyurethane resin can be used.

As above-mentioned polyurethane resin, such as, can use the polyurethane resin with polyether structure, the polyurethane resin with polycarbonate structure, there is the polyurethane resin etc. of polyester construction.

These polyurethane resins can use the polyurethane resin obtained by following method, that is, the polyurethane resin carrying out reacting with the polyalcohol such as the identical polyalcohol recorded in the explanation of above-mentioned compound resin (II-1) or in the past known polycarbonate polyol and PIC as hereinbefore, chain elongation agent etc. and obtain is used.Now, by suitably selecting above-mentioned PPG, in the past known polycarbonate polyol or aliphatic polyester polyols etc. as above-mentioned polyalcohol, thus the above-mentioned polyurethane resin possessing required structure can be manufactured.

In addition, as operable vinylite in above-mentioned resin combination (R), (methyl) acrylic monomer recorded in the explanation of above-mentioned compound resin (II-1), the vinyl monomer generation radical polymerization comprising styrene etc. and the vinylite obtained can be used.

In addition, operable resin combination (R) in formation as above-mentioned resin bed (II), from the viewpoint of manufacturing the duplexer possessing excellent adaptation, heat resistance, preferably use the composition containing melmac (II-2).

As above-mentioned melmac (II-2), such as, melamine or benzoguanamine etc. can be used to have the amino-compound of triazine ring and formolite reaction and the hydroxymethylate obtained or alcoxylates.

As above-mentioned hydroxymethylate, such as, can use methoxyl group methylolated melamine resin, butylation methylolated melamine resin etc.

As above-mentioned alcoxylates, part or all can enumerating the methylol had by above-mentioned hydroxymethylate utilizes the end-blockings such as single methanol and the compound obtained, such as, can enumerate the alkoxylate melmacs such as methoxyl group methylolated melamine resin.

Above-mentioned alkoxylate melmac both can by above-mentioned to melamine or benzoguanamine etc. there is the amino-compound of triazine ring, above-mentioned formaldehyde, above-mentioned single methanol add once and make it reaction, also can make in advance above-mentioned there is triazine ring amino-compound and above-mentioned formolite reaction and obtain methylolated melamine compound, then make it to react with above-mentioned single methanol, use the resin of gained thus.

As above-mentioned alkoxylate melmac, the BECKAMINE M-3 of Dainippon Ink Chemicals specifically can be used.

As the number-average molecular weight of above-mentioned melmac (II-2), preferably use 100 ~ 10, the resin of 000, more preferably use the resin of 300 ~ 2,000.

Above-mentioned resin combination (R) also can as required suitably containing with crosslinking agent be representative, pH adjusting agent, epithelium form the known additives such as auxiliary agent, levelling agent, thickener, water-repelling agent, defoamer.

Above-mentioned crosslinking agent has defined the resin bed (II) of cross-linked structure before can being formed in the above-mentioned liquid of coating; Or the heating of such as firing process etc. can be utilized and form the resin bed (II) of cross-linked structure after the above-mentioned liquid of coating.

As above-mentioned crosslinking agent, such as can use meal chelate compounds, polyamine compounds, aziridine cpd, metal salt compound, isocyanate compound etc. can 25 DEG C ~ be less than the lower temperature of 100 DEG C under carry out reacting and form the thermal cross-linking agent of cross-linked structure; Be selected from compound of more than a kind in melamine based compound, epoxy compound, oxazoline compound, carbodiimide compound and blocked isocyanate compounds etc. can carry out reacting under the higher temperature more than 100 DEG C and the thermal cross-linking agent forming cross-linked structure; Various photocrosslinking agent.

Although above-mentioned crosslinking agent is different from kind etc., but preferred gross mass 100 mass parts relative to resin contained in above-mentioned silane coupling agent uses in the scope of 0.01 quality % ~ 60 quality % usually, more preferably use in the scope of 0.1 quality % ~ 10 quality %, when using in the scope of 0.1 quality % ~ 5 quality %, due to adaptation, excellent electric conductivity and the conductive pattern of above-mentioned excellent in te pins of durability can be formed, therefore preferably.

As mentioned above, by being utilized by above-mentioned resin combination (R) above-mentioned method to part or all coating etc. on the surface of above-mentioned supporting mass (I1) or supporting mass (I2), thus can obtain at the upper stacked material of above-mentioned resin bed (II) of above-mentioned layer (I).

Below, for by the liquid of part or all coating to the surface of above-mentioned resin bed (II) containing conductive material (x) and the method for carrying out burning till and forming conductive layer (III) be described.

Be coated with the method for above-mentioned liquid as the surface to above-mentioned resin bed (II), such as, can enumerate ink jet printing method, reversal printing method, silk screen print method, flexographic printing process, spin-coating method, spraying process, stick coating method, mould painting method, slot coated method, rolling method, dip coating etc.

Wherein, when thin-line-shaped above-mentioned conductive layer (III) of 0.01 μm ~ about 100 μm required when using above-mentioned liquid to form the densification realizing electronic circuit etc., preferably utilize ink jet printing method, reversal printing method to be coated with above-mentioned liquid.

As above-mentioned ink jet printing method, the device being referred to as ink-jet printer generally can be used.Specifically, Konica Minolta EB100, XY100 (Konica Minolta IJ Co., Ltd. system), Diamatix Materials Printer DMP-3000, Diamatix Materials PrinterDMP-2831 (Fuji Photo Film Co., Ltd.'s system) etc. can be enumerated.

In addition, as reversal printing method, there will be a known letterpress reverse printing method, intaglio plate reversal printing method etc., such as, following method can be enumerated, namely, above-mentioned liquid is coated with on the surface of various blanket, the version making it to highlight with non-setting-out portion contacts, the liquid corresponding with above-mentioned non-setting-out portion is optionally transferred to the surface of above-mentioned version, above-mentioned pattern is formed thus on the surface of above-mentioned blanket etc., then, above-mentioned pattern is transferred to the surface of the layer (I) comprising above-mentioned supporting mass (I1) or supporting mass (I2) or the surface of above-mentioned resin bed (II).

Burning till of carrying out after utilizing said method to be coated with above-mentioned liquid is carried out for following object, that is, by closely sealed joint between the conductive materials (x) such as metal contained in above-mentioned liquid, form conductive layer (II) thus.Above-mentioned burning till preferably carries out 2 minutes ~ about 200 minutes in the scope of 80 DEG C ~ 300 DEG C.Above-mentioned burning till also can be carried out in an atmosphere, from the viewpoint of the oxidation preventing above-mentioned metal, also can carry out part or all of firing process under reducing atmosphere.

In addition, above-mentioned firing process such as can use that baking oven, hot air type drying oven, infrared drying stove, laser irradiate, light burns till (photosintering), optical pulse irradiation, microwave etc. and carry out.

The liquid used in formation as above-mentioned conductive layer (III), be containing the liquid of above-mentioned conductive material (x) with the solvent used as required, additive, the liquid that generally can use in electric conductivity ink liquid, the agent of plating core can be enumerated.

As above-mentioned conductive material (x), transition metal or its compound can be used.Especially preferably ionic transition metal is used, the transition metal such as such as preferably copper, silver, gold, nickel, palladium, platinum, cobalt, at use copper, silver, Jin Dengshi, the conductive pattern that resistance is low owing to being formed, corrosion resistance is strong, therefore be more preferably, preferably use silver further.

In addition, when above-mentioned liquid is used in the agent of plating core, as above-mentioned conductive material (x), can use more than a kind, headed by the metallic comprising foregoing transition metal, the oxide of above-mentioned transition metal or covered the material etc. on surface by organic matter.

The oxide of above-mentioned transition metal is generally the state of torpescence (insulation), but such as metal can be exposed by using the reducing agents such as dimethyl amino borane to carry out processing, and gives active (electric conductivity).

In addition, as the metal being covered surface by above-mentioned organic matter, the material being built-in with metal in the resin particle (organic matter) utilizing emulsion polymerization etc. to be formed can be enumerated.The state of their normally torpescence (insulation), but such as metal can be exposed by using the above-mentioned organic matters of removing such as laser, give active (electric conductivity).

As above-mentioned conductive material (x), preferred use has the granular conductive material of the average grain diameter of about 1nm ~ 100nm, when use has the conductive material of the average grain diameter of 1nm ~ 50nm, compared with the situation that there is the conductive material (x) of the average grain diameter of micron level with use, fine conductive pattern can be formed, the resistance value after burning till can be reduced further, be therefore more preferably.And above-mentioned " average grain diameter " above-mentioned conductive material (x) is diluted with dispersion good solvent, utilizes the bulk averaged value that dynamic light scattering method records.Microtrac Inc. Nanotrac UPA-150 can be used in this mensuration.

Preferred use, relative to the material of total amount containing above-mentioned conductive material (x) in the scope of 5 quality % ~ 90 quality % of the liquid used in the present invention, more preferably uses in the scope of 10 quality % ~ 60 quality %.

In addition, consider from viewpoints such as the easnesses that raising is coated with, above-mentioned liquid is preferably containing solvent.As above-mentioned solvent, can with an organic solvent, aqueous medium.

As above-mentioned solvent, such as, headed by the aqueous mediums such as distilled water or ion exchange water, pure water, ultra-pure water, the organic solvents such as alcohol, ether, ester and ketone can be used.

As above-mentioned alcohol, such as methyl alcohol can be used, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, enanthol, hexanol, octanol, nonyl alcohol, decyl alcohol, tip-nip, dodecanol, tridecanol, tetradecanol, pentadecanol, octadecanol, allyl alcohol, cyclohexanol, terpinol, terpineol, dihydro-terpineol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3 third glycol monomethyl ethers, propylene glycol monopropyl ether, dipropylene glycol list propyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, 3 third ethylene glycol monobutyl ethers etc.

In addition, in above-mentioned liquid, also together with above-mentioned conductive material (x), solvent etc., such as, can make spent glycol or diethylene glycol (DEG), 1,3-BDO, isoprene etc.

As above-mentioned liquid, the viscosity preferably utilizing Brookfield viscometer to record at 25 DEG C is 0.1mPas ~ 500,000mPas, is preferably 0.5mPas ~ 10, the liquid of the aqueous or viscous liquid of 000mPas.When utilizing method coating (printing) the above-mentioned liquids such as above-mentioned ink jet printing method, letterpress reverse printing, preferably use the liquid of the scope that its viscosity is 5mPas ~ 20mPas.

Also can to passing through the above-mentioned liquid of coating and part or all enforcement oxidation processes on the surface of the conductive layer (III) burning till and formed.Specifically, also the plasma discharge process such as sided corona treatment can be implemented to the surface of above-mentioned conductive layer (III).

Above-mentioned plasma discharge process is not particularly limited, such as, be process that the vacuum plasma discharge facture such as glow discharge facture and arc discharge facture utilizing the atmospheric pressure plasma discharge factures such as Corona discharge Treatment method, vacuum Huo Minus to depress to carry out is carried out.

As above-mentioned atmospheric pressure plasma discharge facture, it is the method for carrying out plasma discharge process under oxygen concentration is the atmosphere of 0.1 quality % ~ 25 about quality %.In the present invention, from the viewpoint of giving excellent adaptation, especially preferably to adopt in the scope of preferably 10 quality % ~ 22 quality %, being more preferably the Corona discharge Treatment method that (oxygen concentration is about 21 quality %) in air carries out above-mentioned plasma discharge process.

In addition, also containing when carrying out above-mentioned atmospheric pressure plasma discharge facture under the environment of inactive gas while containing above-mentioned oxygen, that can not cause surplus on the surface of above-mentioned conductive layer (III) gives more excellent adaptation concavo-convexly, therefore preferably.As above-mentioned inactive gas, argon gas, nitrogen etc. can be used.

When utilizing above-mentioned atmospheric pressure plasma discharge facture to process, such as, can use the atmospheric pressure plasma jet treatment device (AP-T01) etc. of Sekisui Chemical Co., Ltd.

When utilizing above-mentioned atmospheric pressure plasma discharge facture to process, as the flow of the gases such as air, preferably carry out in the scope of 5 liters/min ~ 50 liters/min.In addition, as power output, be preferably the scope of 50W ~ 500W.In addition, the time utilizing plasma to carry out processing is preferably the scope of 1 second ~ 500 seconds.

As above-mentioned atmospheric pressure plasma discharge facture, specifically, preferably above-mentioned Corona discharge Treatment method is adopted.When adopting above-mentioned Corona discharge Treatment method, such as, can use the corona surface modified gneiss device (TEC-4AX) etc. of Kasuga Electric K. K..

When utilizing above-mentioned Corona discharge Treatment method process, as power output, preferably carry out in the scope of 5W ~ 300W.In addition, the time of carrying out Corona discharge Treatment is preferably the scope of 0.5 second ~ 600 seconds.

The plasma discharge process of above-mentioned Corona discharge Treatment etc. preferably can not carried out under the surface of above-mentioned layer (II) forms the condition of concavo-convex degree because of this process.

Preferably plating process is implemented to the surface of the conductive layer utilizing said method to be formed (III).Above-mentioned plating process both can be carried out the oxidized surface of conductive layer (III), also can carry out not having the surface of oxidized conductive layer (III) in addition.

As above-mentioned plating facture, such as, can enumerate the wet type plating such as the dry type such as sputtering method or vacuum vapour deposition plating, electroless plating method, galvanoplastic or these plating are combined method of more than two kinds.

The plating layer (IV) utilizing above-mentioned plating facture to be formed has excellent adaptation relative to the surface of above-mentioned conductive layer (III).Especially the plating layer (IV) utilizing galvanoplastic to be formed, relative to the surface of above-mentioned conductive layer (III), can embody adaptation excellent especially.

As above-mentioned dry type plating treatment process, sputtering method, vacuum vapour deposition etc. can be used.Above-mentioned sputtering method is following method, namely, import inactive gas (mainly argon gas) in a vacuum, material applying anion is formed to plating layer (IV) and produces glow discharge, then, by above-mentioned inactive gas atomizing/ionizing, gas ion is beaten at high speed intensely surface that above-mentioned plating layer (IV) forms material, make formation plating layer (IV) form the atom of material or molecule ejects and is attached to the surface of above-mentioned conductive layer (III) fiercely, form plating layer (III) thus.

Form material as above-mentioned plating layer (IV), chromium (Cr), copper (Cu), titanium (Ti), silver (Ag), platinum (Pt), gold (Au), nickel-chromium (Ni-Cr), SUS, copper-zinc (Cu-Zn), ITO, SiO can be used ₂, TiO ₂, Nb ₂o ₅, ZnO etc.

When utilizing above-mentioned sputtering method to carry out plating process, such as, magnetic control sputtering device etc. can be used.

In addition, above-mentioned vacuum vapour deposition is following method, namely, in a vacuum, heating forms various metal or the metal oxide of material as plating layer (IV), make their meltings, evaporation, distillation, make above-mentioned metallic atom or molecule attached on the surface of above-mentioned conductive layer (IV), form plating layer (IV) thus.

As the formation material of plating layer (IV) operable in above-mentioned vacuum vapour deposition, such as, can use aluminium (Al), silver (Ag), gold (Au), titanium (Ti), nickel (Ni), copper (Cu), chromium (Cr), tin (Sn), indium (In), SiO ₂, ZrO ₂, Al ₂o ₃, TiO ₂deng.

In addition, the electroless plating facture that can use as above-mentioned plating facture is following method, namely, such as by making electroless plating liquid contact the conductive material such as palladium, silver forming above-mentioned conductive layer (III), thus the metals such as copper contained in above-mentioned electroless plating liquid are separated out, form the electroless plating coating (tunicle) formed by metal epithelium.

As above-mentioned electroless plating liquid, such as, can use the solution containing the conductive material comprising the metals such as copper, nickel, chromium, cobalt, tin, reducing agent and aqueous medium or organic solvent equal solvent.

As above-mentioned reducing agent, such as, can use dimethyl amino borane, ortho phosphorous acid, inferior sodium phosphate, dimethyamine borane, hydrazine, formaldehyde, sodium borohydride, phenols etc.

In addition, as above-mentioned electroless plating liquid, also the monocarboxylic acid such as acetic acid, formic acid can be contained as required; The dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid; The hydroxycarboxylic acids such as malic acid, lactic acid, glycolic, gluconic acid, citric acid; The amino acid such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, glutamic acid; The complexing agent of the amine such as soluble-salt (sodium salt, sylvite, ammonium salt etc.), ethylenediamine, diethylenetriamines, trien of the organic acids such as the aminopolycarboxylic acid such as iminodiacetic acid, NTA, EDDA, ethylenediamine tetra-acetic acid, diethylene-triamine pentaacetic acid, these organic acids etc.

The temperature of above-mentioned electroless plating liquid when using above-mentioned electroless plating liquid is preferably the scope of 20 DEG C ~ 98 DEG C.

In addition, the electroplating processes method that can use as above-mentioned plating facture is following method, namely, such as, the conductive material making plating solution contacts form above-mentioned conductive layer (III), or be energized under the state utilizing the surface of the above-mentioned electroless plating coating (tunicle) without electrolytic treatments formation, make the metals such as copper contained in above-mentioned electroplate liquid at the conductive material of the above-mentioned conductive layer of the formation being arranged at negative pole (III) thus or utilize the surface of the above-mentioned electroless plating coating (tunicle) without electrolytic treatments formation to separate out, form plating tunicle (metal tunicle).

As above-mentioned electroplate liquid, the solution containing the metals such as copper, nickel, chromium, cobalt, tin, their sulfide etc., sulfuric acid etc. and aqueous medium can be used.Specifically, the solution etc. containing copper sulphate, sulfuric acid and aqueous medium can be used.

The temperature of above-mentioned electroplate liquid when using above-mentioned electroplate liquid is preferably the scope of 20 DEG C ~ 98 DEG C.

In above-mentioned electroplating processes method, due to the material not using toxicity high, good operability, therefore preferably utilizes galvanoplastic to form the layer comprising copper.

The duplexer utilizing said method to obtain can use as conductive pattern.Specifically, go for the formation of the electronic circuit employing silver-colored black liquid etc., form the formation of each layer of organic solar batteries or e-book terminal, organic EL, organic transistor, flexible circuit board, RFID etc. or periphery distribution, manufacture the distribution etc. of the electromagnetic wave shielding thing of plasma scope time conductive pattern, be more specifically the formation of circuit substrate.

When above-mentioned duplexer is used in conductive pattern, can by with to be formed needed for position corresponding to pattern form, coating can form the liquid of above-mentioned conductive layer (III) and burn till etc., thus manufactures the conductive pattern possessing required pattern.

In addition, above-mentioned conductive pattern such as can utilize the photoetching-etching methods such as subtractive process, semi-additive process, fully-additive process to manufacture.

Above-mentioned subtractive process is following method, namely, on the plating layer (IV) of the formation manufactured in advance duplexer of the present invention, form the etching resist layer of the shape corresponding with required pattern form, then, the plating layer (IV) of the part eliminated utilizing development treatment by above-mentioned resist and conductive layer (III) liquid dissolve removing, form required pattern thus.As above-mentioned liquid, the liquid containing copper chloride, iron chloride etc. can be used.

Above-mentioned semi-additive process is following method, namely, manufacture possesses the layer (I) comprising above-mentioned supporting mass (I1) or supporting mass (I2), the duplexer of above-mentioned resin bed (II) and above-mentioned conductive layer (III), then, by carrying out plasma discharge process to its surface as required by the surface oxidation of conductive layer (III), then this through oxidation surface, form the plating resist layer of the shape corresponding with required pattern as required, then, after utilizing galvanoplastic or electroless plating method to define plating layer (IV), above-mentioned plating resist layer and the above-mentioned conductive layer (III) contacted with it are dissolved in the middle removings such as liquid, form required pattern thus.

In addition, above-mentioned fully-additive process is following method, namely, on the layer (I) comprising above-mentioned supporting mass (I1) or supporting mass (I2), resin bed (II) is set, after utilizing ink-jet method or reversal printing method to print the pattern of above-mentioned conductive layer (III), as required plasma discharge process is carried out to the surface of above-mentioned conductive layer (III), form pattern thus, then, utilize galvanoplastic or electroless plating method to form plating layer (IV) on the oxidized surface of above-mentioned conductive layer (III), form required pattern thus.

The conductive pattern utilizing said method to obtain can not cause the stripping etc. of each interlayer, the level of the powered that can remain good can be given, quite excellent durability, therefore the formation employing circuit formation substrate used in the electronic circuit or integrated circuit etc. of silver-colored black liquid etc. is gone for, form organic solar batteries or e-book terminal, organic EL, organic transistor, flexible circuit board, each layer of RFID etc. or the formation of periphery distribution, in the middle of the distribution of the electromagnetic wave shielding thing of plasma scope etc., the purposes of special requirement durability.Particularly, the conductive pattern implementing above-mentioned plating process can not cause broken string etc. in long-time, the Wiring pattern that the reliability of the powered that can remain good is high can be formed, therefore such as generally may be used for being referred to as copper-clad laminated board (CCL:Copper Clad Laminate), flexible circuit board (FPC), tape automated bonding (TAB), covering in the purposes of brilliant film (COF) and printed wiring board (PWB) etc.

Embodiment

Below, the present invention is described in detail to utilize embodiment.

[preparation of supporting mass (F-1)]

With molar ratio computing with 50/50 ratio prepare pyromellitic dianhydride and 4,4 '-oxygen diphenylamines, by them at N, N " be polymerized in-dimethylacetylamide, obtain the polyamic acid solution (A-1) that nonvolatile component is 20 quality % thus.

In addition, with molar ratio computing with 50/50 ratio prepare 3,4,3 ', 4 '-biphenyltetracarboxyacid acid dihydrate and 4,4 '-oxygen diphenylamines, by them at N, be polymerized in N '-dimethyl acetamide, obtain the polyamic acid solution (A-2) that nonvolatile component is 20 quality % thus.

Then, above-mentioned polyamic acid solution (A-1) is mixed to make the mode of (quality of polyamic acid contained in above-mentioned polyamic acid solution (A-1))/(quality of polyamic acid contained in above-mentioned polyamic acid solution (A-2))=35/65 with above-mentioned polyamic acid solution (A-2), and the average grain diameter mixing 0.2 quality % is the silicon dioxide granule of 0.3 μm, obtains mixture thus.

Thereafter, by said mixture filter, deaeration process, it is extruded from T-shaped mould and curtain coating on cylinder.

By by the material of above-mentioned curtain coating gained at 100 DEG C dry 60 seconds, thus produce the film containing above-mentioned polyamic acid and above-mentioned silica.

By above-mentioned film after cylinder stripping, 250 DEG C of dryings 60 seconds, then 300 DEG C of dryings 60 seconds, thereafter 400 DEG C of dryings 75 seconds, obtain the supporting mass (F-1) formed by polyimide film thus.The thickness of above-mentioned supporting mass is 40 μm.

[preparation of supporting mass (F-2)]

With molar ratio computing with 50/50/100 ratio prepare pyromellitic dianhydride, 4,4 '-oxygen diphenylamines, 3,4,3 ', 4 '-biphenyltetracarboxyacid acid dihydrate and 4,4 '-oxygen diphenylamines, by them at N, be polymerized in N '-dimethyl acetamide, obtain the polyamic acid solution that nonvolatile component is 20 quality % thus.And then the average grain diameter of mixing 0.2 % by weight is that the silicon dioxide granule of 0.3 μm obtains mixture.

By by the material of above-mentioned curtain coating gained 100 DEG C of dryings 60 seconds, thus produce the film containing above-mentioned polyamic acid and above-mentioned silica.

By above-mentioned film after cylinder stripping, 250 DEG C of dryings 60 seconds, then 300 DEG C of dryings 60 seconds, thereafter 400 DEG C of dryings 75 seconds, obtain the supporting mass (F-2) formed by polyimide film thus.The thickness of above-mentioned supporting mass is 39 μm.

[preparation of supporting mass (F-3)]

Substitute above-mentioned polyamic acid solution (A-1) and above-mentioned polyamic acid (A-2), and employ by with molar ratio computing with 50/50 ratio prepare 3,4,3 ', 4 '-biphenyltetracarboxyacid acid dihydrate and 1, the polymerization of mixtures of 4-diaminobenzene and the polyamic acid that obtains, in addition, utilize the method identical with the preparation method of above-mentioned supporting mass (F-1) to produce the supporting mass (F-3) formed by polyimide film.The thickness of above-mentioned supporting mass is 49 μm.

[preparation of supporting mass (F-4)]

Substitute above-mentioned polyamic acid solution (A-1) and above-mentioned polyamic acid (A-2), and employ by with molar ratio computing with 50/50 the pyrophosphoric acid acid anhydride and 4 for preparing of ratio, the polymerization of mixtures of 4 '-oxygen diphenylamines and the polyamic acid obtained, and, to substitute above-mentioned average grain diameter be average grain diameter that the silica of 0.2 μm employs 0.05 quality % is the calcium phosphate of 1 μm, in addition, the method identical with the preparation method of above-mentioned supporting mass (F-1) is utilized to produce the supporting mass (F-4) formed by polyimide film.The thickness of above-mentioned supporting mass is 50 μm.

[preparation of resin combination (R-1)]

Possess thermometer, nitrogen ingress pipe, agitator the displacement of carrying out nitrogen container in, PEPA is made (to make 1, the PEPA that 4-cyclohexanedimethanol, neopentyl glycol and adipic acid react and obtain) 100 mass parts, 2,2-dihydromethyl propionic acid 17.6 mass parts, 1,4-cyclohexanedimethanol 21.7 mass parts, dicyclohexyl methyl hydride diisocyanate 106.2 mass parts are reacted in the mixed solvent of MEK 178 mass parts, obtain the organic solvent solution in molecular end with the carbamate prepolymer of NCO thus.

Then, by adding triethylamine 13.3 mass parts in the organic solvent solution to above-mentioned polyurethane resin, thus part or all neutralization of the carboxyl that above-mentioned polyurethane resin is had, then add water 380 mass parts and stir fully, obtain the aqueous liquid dispersion of polyurethane resin thus.

Then, by adding ethylenediamine solution 8.8 mass parts of 25 quality % and stir in above-mentioned aqueous liquid dispersion, and make emboliform polyurethane resin generation chain elongation, then by carrying out aging desolventizing, thus the aqueous liquid dispersion of the polyurethane resin (r-1) that solid component concentration is 30 quality % is obtained.The weight average molecular weight of above-mentioned polyurethane resin (r-1) is 53,000.

Then, to possessing aqueous dispersion 100 mass parts of polyurethane resin (r-1) adding deionized water 140 mass parts, utilize aforesaid operations to obtain in the reaction vessel of mixer, backflow cooling tube, nitrogen ingress pipe, thermometer, monomer mixture dropping dropping funel, polymerization catalyst dropping dropping funel, while being blown into nitrogen, be warmed up to 80 DEG C.

In the reaction vessel being warmed up to 80 DEG C, under agitation, temperature in reaction vessel is remained while 80 ± 2 DEG C, from each dropping funel, dripped with 120 minutes the monomer mixture and ammonium persulfate aqueous solution (concentration: 0.5 quality %) 20 mass parts that are made up of methyl methacrylate 60 mass parts, n-butyl acrylate 30 mass parts, N-n-butoxy methyl acrylamide 10 mass parts, and be polymerized.

After dropping terminates, stir 60 minutes at the same temperature, obtain the aqueous dispersion be made up of the shell of above-mentioned polyurethane resin (r-1) and the sandwich layer of polyvinyl thus.

Temperature in above-mentioned reaction vessel is cooled to 40 DEG C, then, is, after the mode of 20.0 quality % uses deionized water, with 200 order filter-cloth filterings, obtain resin combination (R-1) thus to make nonvolatile component.

[preparation of resin combination (R-2)]

To in the reaction flask possessing reflux condenser, thermometer, mixer, in formalin 600 mass parts (content of formaldehyde: 222 mass parts (7.4mol), methanol content: 42 mass parts (1.31mol)) containing the formaldehyde of 37 quality % and the methyl alcohol of 7 quality %, add water 200 mass parts and methyl alcohol 350 mass parts (10.92mol).25 quality % sodium hydrate aqueous solutions are added in this aqueous solution, after pH is adjusted to 10, add melamine 310 mass parts (2.46mol), liquid temperature is elevated to 85 DEG C, make it methylolation (primary first-order equation) (reaction time: 1 hour).

Thereafter, add formic acid and after pH is adjusted to 7, be cooled to 60 DEG C, making it etherification reaction (secondary response).At gonorrhoea temperature 40 DEG C, add 25 quality % sodium hydrate aqueous solutions and pH is adjusted to 9, stopping etherification reaction (reaction time: 1 hour).Under the decompression of temperature 50 C, remove remaining methyl alcohol (separating methanol time: 4 hours), obtain the resin combination (R-2) containing melmac that nonvolatile component is 80 quality %.

And, the assay method of above-mentioned gonorrhoea temperature is described as follows.Gather resin 1g, the hot water of this resin with the 100ml being adjusted to the temperature of specifying is mixed.Now, by resin, the highest temperature be insoluble in hot water when there is gonorrhoea is set to gonorrhoea temperature.

[preparation of electric conductivity ink liquid]

Electric conductivity ink liquid 1 has been prepared by disperseing the silver particles of average grain diameter 30nm in the mixed solvent of ethylene glycol 45 mass parts and ion exchange water 55 mass parts.

[embodiment 1]

To the surface of above-mentioned supporting mass (F-1), TEC-4AX (the corona surface modified gneiss device of Kasuga Electric K. K., gas: air (oxygen concentration about 21 quality %), gap: 1.5mm, power output: 100W, processing time: 2 seconds) is used to carry out Corona discharge Treatment.

Thereafter, on the surface of above-mentioned supporting mass, spin coater is used to be that the mode of 0.1 μm is coated with above-mentioned resin combination (R-1) to make its dry film thickness, then, use air drier under the condition of 80 DEG C dry 5 minutes, obtain the stacked resin bed (II) on the surface of the layer comprising above-mentioned supporting mass (I) thus and the duplexer that obtains.

Then, on the surface of above-mentioned resin bed (II), utilize spin-coating method to be coated with above-mentioned electric conductivity ink liquid, then, burn till 3 minutes at 250 DEG C, produce the conductive layer (III) (thick 0.1 μm) formed by above-mentioned silver thus.Method described later is utilized to determine the sheet resistance of above-mentioned conductive layer (III), consequently 2 Ω/.

Then, to the surface of above-mentioned conductive layer (III), TEC-4AX (the corona surface modified gneiss device of Kasuga Electric K. K., gas: air (oxygen concentration about 21 quality %), gap: 1.5mm, power output: 100W, processing time: 2 seconds) is used to carry out Corona discharge Treatment.The sheet resistance of the above-mentioned conductive layer (III) before Corona discharge Treatment is 2 Ω/, and the sheet resistance of having carried out the conductive layer (III) of Corona discharge Treatment increases to 5 Ω/.In addition, use above-mentioned identical x-ray photoelectron analytical equipment to analyze its surface, consequently, the peak representing that the silver of the above-mentioned conductive layer of formation (III) is oxidized can be confirmed.

Then, be negative electrode by the oxidized surface set of above-mentioned conductive layer (III), phosphorous copper is set as anode, use electroplate liquid containing copper sulphate with current density 2A/dm ²carry out plating in 15 minutes, thus the stacked copper plating layer of thick 8 μm on the surface of above-mentioned conductive layer (III).As above-mentioned electroplate liquid, employ copper sulphate 70g/ liter, sulfuric acid 200g/ liter, chlorion 50mg/ liter, Toplucina SF (polishing material of Okuno Chemical Industries Co., Ltd.) 5g/ liter.

Utilize above method, obtain the duplexer (L-1) being laminated with the layer (I), resin bed (II), above-mentioned conductive layer (III) and the above-mentioned plating layer (IV) that comprise above-mentioned supporting mass.

[embodiment 2]

Substitute above-mentioned resin combination (R-1) and employ resin combination (R-2), in addition, utilize the method identical with embodiment 1, obtain being laminated with the duplexer (L-2) of layer (I), resin bed (II), above-mentioned conductive layer (III) and the above-mentioned plating layer (IV) comprising above-mentioned supporting mass.

[embodiment 3]

Substitute above-mentioned supporting mass (F-1) and employ supporting mass (F-2), and substitute above-mentioned resin combination (R-1) and employ the mixture containing resin combination (R-1) and resin combination (R-2) with the ratio of 50/50 (solid constituent), in addition, utilize the method identical with embodiment 1, obtain being laminated with the duplexer (L-3) of layer (I), resin bed (II), above-mentioned conductive layer (III) and the above-mentioned plating layer (IV) comprising above-mentioned supporting mass.

[comparative example 1]

Substitute above-mentioned supporting mass (F-1) and employ supporting mass (F-3), in addition, utilize the method identical with embodiment 1, obtain being laminated with the duplexer (L '-1) of layer (I), resin bed (II), above-mentioned conductive layer (III) and the above-mentioned plating layer (IV) comprising above-mentioned supporting mass.

[comparative example 2]

Substitute above-mentioned supporting mass (F-1) and employ supporting mass (F-4), utilize the method identical with embodiment 1 in addition, obtain being laminated with the duplexer (L '-2) of layer (I), resin bed (II), above-mentioned conductive layer (III) and the above-mentioned plating layer (IV) comprising above-mentioned supporting mass

< adaptation: based on the evaluation > of disbonded test

The peel strength of the duplexer utilizing aforesaid operations to obtain measures to utilize carries out according to the method for IPC-TM-650, NUMBER2.4.9.Wire widths used in mensuration is 1mm, and its angle peeled off is set to 90 °.And the thickness that there is above-mentioned plating layer is thicker, then peel strength demonstrates the tendency of higher value, and the mensuration of peel strength in the present invention implements using measured value during now general plating layer 8 μm as benchmark.

< heat resistance: the evaluation based on disbonded test (the temperature 150 DEG C) > after heat resistant test

Utilize dry 168 hours of the duplexer being set as that the drying machine of 150 DEG C will utilize aforesaid operations to obtain.Except using above-mentioned dried duplexer, utilize and determine peel strength with above-mentioned < based on the method that the method recorded in the evaluation > of disbonded test is identical.

< humidity resistance: the evaluation based on disbonded test (temperature 135 DEG C and the humidity 85%) > after hot resistance test

The duplexer obtained utilizing aforesaid operations puts into the HAST exerciser 168 hours being set as temperature 135 DEG C and humidity 85%.Except using the duplexer after above-mentioned hot resistance test, utilize and determine peel strength with above-mentioned < based on the method that the method recorded in the evaluation > of disbonded test is identical.

[table 1]

Claims

1. a duplexer, is characterized in that,

There is layer (I), resin bed (II) and conductive layer (III),

Described layer (I) comprises supporting mass (I1) or supporting mass (I2), the polyimide resin (i-1) of described supporting mass (I1) containing the structure had represented by following general formula (1) and there is the polyimide resin (i-2) of the structure represented by following general formula (2), the polyimide resin (i-3) of described supporting mass (I2) containing the structure represented by the structure had represented by following general formula (1) and following general formula (2)

Described resin bed (II) contains the liquid of conductive material (x) by holding,

Described conductive layer (III) is formed by above-mentioned conductive material (x),

R in general formula (1) ¹~ R ⁸represent hydrogen atom, halogen atom or organic group independently of one another, n represents 1 ~ 1, the integer of 000,

R in general formula (2) ⁹~ R ²²represent hydrogen atom, halogen atom or organic group independently of one another, m represents 1 ~ 1, the integer of 000.

2. duplexer according to claim 1, wherein,

The described layer (I) comprising supporting mass is also the silicon dioxide microparticle of 0.01 μm ~ 1 μm containing average grain diameter.

3. duplexer according to claim 1, wherein,

Described resin bed (II) is the compound resin (II-1) or melmac (II-2) that are made up of polyurethane resin and acrylic resin.

4. duplexer according to claim 1, wherein,

In part or all of the surface of described conductive layer (III), there is plating layer (IV).

5. duplexer according to claim 4, wherein,

Part or all of described conductive layer (III) is made up of oxidized silver.

6. duplexer according to claim 4, wherein,

Described plating layer (IV) utilizes copper electroplating method to be formed.

7. a conductive pattern, it comprises duplexer above-mentioned any one of claim 1 ~ 6.

8. a circuit, it has duplexer above-mentioned any one of claim 1 ~ 6.