CN105612585B - Electrocondution slurry, conductive coating, galvanic circle, electric conductivity laminate and touch-screen - Google Patents
Electrocondution slurry, conductive coating, galvanic circle, electric conductivity laminate and touch-screen Download PDFInfo
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- CN105612585B CN105612585B CN201480052717.9A CN201480052717A CN105612585B CN 105612585 B CN105612585 B CN 105612585B CN 201480052717 A CN201480052717 A CN 201480052717A CN 105612585 B CN105612585 B CN 105612585B
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- electrocondution slurry
- thermoplastic resin
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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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1275—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
Abstract
The problem of the present invention is, there is provided a kind of electrocondution slurry, it has less than 50 μm of fine rule printing, and the cohesive of the ito film in the conductive pattern with being formed by less than 150 DEG C of low temperature process is excellent, can also realize environmental reliability, high-durability.The electrocondution slurry is characterised by, it is at least to contain thermoplastic resin (A), thermoplastic resin (B), curing agent (C), the electrocondution slurry of electroconductive powder (D) and organic solvent (E), thermoplastic resin (A) is relative to thermoplastic resin (B), weight ratio is below 4.0 times, thermoplastic resin (A) is weight average molecular weight 10, more than 000 and the polyurethane resin and/or polyester resin of 10~150 DEG C of glass transition temperature, further, thermoplastic resin (B) is PEPA and/or PPG, number-average molecular weight is 500~6, 000.
Description
Technical field
The present invention relates to electrocondution slurry and its use, is related to the excellent conduction of fine rule printability in further detail
Slurry, the galvanic circle formed using the electrocondution slurry, conductive coating, the conductive coating lamination over transparent conductive layer
Electric conductivity laminate and the touch-screen using the electric conductivity laminate.
Background technology
The transparent touch-sensitive panel to be operated is contacted with picture by finger or special pen etc., it is in ATM, auto navigation
System, game machine, the automatic machine at station, duplicator, the explanation terminal in museum and information terminal of convenience store etc. are extensive
Purposes in used, gradually popularization.Transparent touch-sensitive panel, it is such that switch is overlapped to form by transparent two panels conductive membrane
And form.As the transparent conducting film of transparent touch-sensitive panel, generally have makes indium oxide tin film by vapour deposition method or sputtering method
(hereinafter sometimes referred to simply as ito film) is attached on the base materials such as polyester film, glass, and the thin of pattern is formed by etching the ito film
Film.
Touch-screen has various ways, and representational mode has resistive film mode and capacitive way.In recent years, along with intelligence
The popularization of mobile phone or tablet PC and the capacitive way to get most of the attention, it is characterised by by sensing relative to resistive film mode
Finger or special pen and plate contact and caused electric discharge phenomena etc. and determine the mode of position contacted on panel, Ke Yiduo
Point touch-control.In order to carry out multi-point touch with high-resolution, compared with conventional resistive film mode, it is necessary to form multiple circuits are matched somebody with somebody
Line.Further, in recent years, because the picture of display becomes much larger, and the requirement in commodity design, to making to be configured with electricity
The demand that the architrave portion of pole circuit connection is narrower increases, based on such background, it is desirable to multiple distribution electrodes are formed with high density,
Also the high graph thinning of circuit layout is more required.
In order to form multiple electrodes circuit connection to high-density, thin distribution is preferably placed at short intervals.As in order to
The technique for realizing above-mentioned purpose, photoetching technique method is for example there are, but had including process is miscellaneous, multiple skills including cost standpoint
Art problem.In addition, by above-mentioned photoetching technique method and the conducting channel that is formed, because only being formed by metals such as aluminium or copper,
In the presence of relative to bending etc. physical impact it is weaker the problem of.In addition, in photoetching technique method, it is main according to used in its use environment
Stream base material is glass, but is requiring touch-screen light-weighted today, has the shortcomings that selectivity of base material is by limitation.
On the other hand, the base material of print process is selectively excellent, can be eclipsed in such as glass, ito film, ITO a part
Conductive pattern is formed on the various base materials such as the etching-film at quarter, PET film, polyimide film.Further, print process has into we
The advantages of in terms of face and device simple, if electrocondution slurry can be used in print process and form fine rule, can have greatly excellent
Point.Further, since adhesive resin is used in electrocondution slurry as the binding agent with base material, in physical impact sides such as reply bendings
Mask is advantageous.However, in print process, in order that forming thin conductive pattern with electrocondution slurry, it is necessary to the fine rule of electrocondution slurry
Adaptability.
Required line width in the circuit layout of resistive film mode, width (the hereinafter referred to as L/ of line width and line spacing
S it is enough if forming thicker conductive pattern more than 200 μm (200/200 μm)) to be respectively mostly, but because of electric capacity
The popularization of the touch-screen of mode, L/S is further required at 50/50 μm below 100/100 μm to L/S requirements in recent years
Following occasion, the requirement for fine rule adaptability also further improve.
Therefore, people, which have done, a variety of are related to low cost and are not in grinding for the conductive pattern forming method of harmful waste water etc.
Study carefully.Wherein, intaglio plate flexographic printing process is electrocondution slurry to be filled in the galley with female pattern, the conductive paste of filling
Expect after there is the printing of silicon rubber sheet material to be received with cloth on surface, electrocondution slurry is transferred to from the printing with cloth printed
On base material, the method printing and form electrode pattern, because it can form fine conductive pattern in high precision, so as photoetching skill
The method of substitution of art method and attracted attention.
As the method that conductive pattern is formed using intaglio plate flexographic printing process, previously known oriented by glass substrate shape
Into transfer printing body transfer conductive ink and manufacture the method for film (referring for example to patent document 1).But, it is contemplated that so
Conventional art be applied to the glass substrate that can sinter at high temperature, the problem of such be present：It is more difficult to be suitable for use with designing
The conductive ink and use crossed are arranged at the touch-screen of the ito film in PET film etc..
As described above, can accurately form fine rule in intaglio plate flexographic printing process, but energy-saving from manufacturing procedure,
Or from the aspect of the heat resistance of film base material, it is desirable to the heat treatment step under low temperature, more require the heat of the relatively low temperature below 150 DEG C
Processing is lower to embody Physical properties of coating film.Further, along with the miniaturization of touch-screen in recent years, widely using, the ring used
Border, the frequency used relatively also became varied in the past, so for forming the environmental reliability of electrode and the requirement of durability
Also more and more higher.
Prior art literature
Patent document
【Patent document 1】No. 5088063 publication of patent
The content of the invention
Invent problem to be solved
Completed under the background of problem of the present invention in such conventional art.That is, it is an object of the invention to provide one kind
Electrocondution slurry, it has less than 50 μm of fine rule printing, and the conductive pattern with being formed by less than 150 DEG C of low temperature process
In ito film cohesive it is excellent, can further realize environmental reliability, high-durability.
The means to solve the problem
The present inventor has made intensive studies to reach such purpose, as a result finds by containing in electrocondution slurry
Two or more number-average molecular weight different thermoplastic adhesive's resin and curing agent, the fine rule print of intaglio plate hectographic printing can be assigned
Brush, and it is excellent with the cohesive of ito film in the conductive pattern of the low temperature process formation by less than 150 DEG C, further may be used
To keep environmental reliability, high-durability.
That is, the present invention is made up of following technical scheme.
(1) a kind of electrocondution slurry, it is characterised in that be at least containing thermoplastic resin (A), thermoplastic resin (B), solidification
The electrocondution slurry of agent (C), electroconductive powder (D) and organic solvent (E), thermoplastic resin (A) is relative to thermoplastic resin
(B), for weight ratio below 4.0 times, thermoplastic resin (A) is weight average molecular weight 10, more than 000 and glass transition temperature -10
~150 DEG C of polyurethane resin and/or polyester resin, further, thermoplastic resin (B) are noncrystal polyalcohol, and number is divided equally
Son amount is 500~6,000.
(2) electrocondution slurry as described in (1), it is characterised in that the average grain diameter (D50) of electroconductive powder (D) is at least 7
Below μm.
(3) electrocondution slurry as described in (1)~(2), it is characterised in that thermoplastic resin (B) be PEPA and/or
PPG, and/or polycarbonate polyol.
(4) electrocondution slurry as described in any one of (1)~(3), it is characterised in that 130 DEG C, the heat treatment of 30 minutes
In, the acid number of fixedness organic principle is 20~500eq/ton.
(5) electrocondution slurry as described in any one of (1)~(4), it is characterised in that curing agent (C) is isocyanation esterification
Compound, and curing agent (C) meets following condition relative to the combined amount of thermoplastic resin (B)：Relative to thermoplastic resin (B)
Hydroxyl, the NCO of curing agent (C) is 20~200 moles of %.
(6) electrocondution slurry as described in any one of (1)~(5), it is characterised in that the boiling point of organic solvent (E) is 100
More than DEG C, and it is below 25 weight % relative to the weight percent of electrocondution slurry total weight.
(7) electrocondution slurry as described in any one of (1)~(6), it is characterised in that electroconductive powder (D) mainly by
Silver is formed.
(8) electrocondution slurry as described in any one of (1)~(7), it is characterised in that (will be led for intaglio plate hectographic printing
Plasma-based material is filled in the galley with female pattern, and the electrocondution slurry of filling is through having the print of silicon rubber sheet material on surface
After brush is received with cloth, electrocondution slurry is transferred on printing base from the printing with cloth, prints and forms electrode pattern
Method).
(9) a kind of printed article, being (will through intaglio plate hectographic printing by the electrocondution slurry described in any one of (1)~(7)
Electrocondution slurry is filled in the galley with female pattern, and the electrocondution slurry of filling is through having the print of silicon rubber sheet material on surface
After brush is received with cloth, electrocondution slurry is transferred on printing base from the printing with cloth, prints and forms electrode pattern
Method) obtained from conductive coating through dry and/or solidification and obtain.
(10) printed article as described in (9), the spacing of line width/line is less than 100 μm.
(11) a kind of electric conductivity laminate, it is the printed article lamination over transparent conductive layer recorded by (9)~(10)
Form.
(12) a kind of touch-screen, the electric conductivity laminated plates that described (11) are recorded are it used.
The effect of invention
The electrocondution slurry of the present invention, by using the different thermoplastic adhesive's resin of at least two kinds of number-average molecular weights and admittedly
Agent, the fine rule intaglio plate hectographic printing of electrocondution slurry can be assigned, and be led with what is formed by less than 150 DEG C of low temperature process
The cohesive of ito film is excellent in electrical pattern, can further have environmental reliability, high-durability concurrently.
Embodiment
Hereinafter, the electrocondution slurry of embodiments of the present invention is illustrated.
The electrocondution slurry of present embodiment, be at least containing thermoplastic resin (A), thermoplastic resin (B), curing agent (C),
The electrocondution slurry of electroconductive powder (D) and organic solvent (E), thermoplastic resin (A) is relative to thermoplastic resin (B), weight
Than below 4.0 times, thermoplastic resin (A) is weight average molecular weight 10, more than 000 and glass transition temperature is -10~150 DEG C
Polyurethane resin or polyester resin, further, thermoplastic resin (B) is noncrystal polyalcohol, number-average molecular weight is 500~
6,000.
There is different numbers to divide equally for thermoplastic resin (A), thermoplastic resin (B) used in the electrocondution slurry of the present invention
Son amount, thermoplastic resin (A) is relative to thermoplastic resin (B), and weight ratio is below 4.0 times.It is equal using such 2 kinds of different numbers
When the thermoplastic resin of molecular weight is as adhesive resin, in gpc analysis, molecular weight distribution curve turns into peaks more than double mountains
Situation is more.Because the summit of the molecular weight distribution of each thermoplastic resin is different.As a result, molecular weight distribution is compared with use
Broadened during single resin.That is, compared with single resin, adhesive resin overall weight average molecular weight Mw and number-average molecular weight Mn's
Become big than (Mw/Mn), this is advantageous to realize environmental stability, high-durability and printing simultaneously.
In addition, the electrocondution slurry of the present invention, as long as not damage to the environment stability, durability and printing, can mix 3 kinds
Resin above.
The species of thermoplastic resin (A) is not particularly limited, preferably polyurethane resin, polyester resin.As thermoplastic
Property resin (A), by using these resins, in the solidification after electrocondution slurry applies or prints, it can be ensured that film it is resistance to
Long property, high conductivity is further embodied by the mutual distance of the electroconductive powders such as the metal dust inside the film that furthers.
When thermoplastic resin (A) is polyester resin, aromatic dicarboxylic acid is 20 moles of more than % preferably in all acid composition,
More preferably 35 moles of more than %, further preferably 50 moles of more than %.If less than 20 moles % of aromatic dicarboxylic acid, then have
The possibility of the reductions such as coating strength reduction, the durability such as low temperature resistance to bend(ing), heat resistance or moisture-proof or resistance to sudden heating.
The preferred upper limit of aromatic dicarboxylic acid is 100 moles of %.
As the aromatic dicarboxylic acid being copolymerized in polyester resin, terephthalic acid (TPA), M-phthalic acid, O-phthalic for example there are
Acid, 2,6- naphthalene dicarboxylic acids etc..Wherein, from the aspect of physical property and solvent solubility, preferably be combined terephthalic acid (TPA) and
Phthalic acid.
In addition, as the other dicarboxylic acids being copolymerized in polyester, for example there are succinic acid, glutaric acid, adipic acid, decanedioic acid,
The aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, azelaic acid, the binary acid of carbon number 12~28, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,
3- cyclohexane dicarboxylic acids, 1,2- cyclohexane dicarboxylic acids, 4- methyl hexahydrophthalic acid anhydride, 3- methyl hexahydrophthalic acid anhydride, 2-
Methyl hexahydrophthalic acid anhydride, dicarboxyl hydrogenated bisphenol A, dicarboxyl A Hydrogenated Bisphenol A S, dimeric dibasic acid, hydrogenated dimer acids, hydrogenated naphthalene two
The hydroxycarboxylic acids such as the alicyclic dicarboxylic acids such as carboxylic acid, tricyclodecane-dicarboxylic acid, hydroxybenzoic acid, lactic acid, from the aspect of moisture-proof
It is preferred that decanedioic acid, adipic acid, azelaic acid, 1,4-CHDM.
In addition, in the range of the content of the invention is not damaged, the polynary carboxylic such as trimellitic anhydride, benzenetetrahydride can be used together
The unsaturated dicarboxylics such as acid, fumaric acid and the dicarboxylic acids containing the Sulfonic acid metal base such as 5- sulfo isophthalate sodium salts.This
Outside, after polyester resin polymerization, acid number can be assigned by acid anhydrides such as rear addition trimellitic anhydride, phthalate anhydrides.
The diol component being copolymerized in polyester resin, known glycol as shown below can be used.Such as, it is ethylene glycol, new
Pentanediol, 1,3-PD, 2- methyl isophthalic acids, ammediol, BDO, NPG, 2- methyl-
1,3-PD, BDO, 2,2- diethyl -1,3-PD, 2- butyl -2- ethyls -1,3-PD, 1,3- fourths two
Alcohol, 1,5-PD, 1,6- hexylene glycols, 3- methyl isophthalic acids, 5- pentanediols, 2- methyl isophthalic acids, 5- pentanediols, 1,9- nonanediols, 1,10-
The aklylene glycols such as decanediol, 1,4-CHDM, 1,3-CHDM, 1,2-CHDM, the three ring last of the ten Heavenly stems
The polyethers system such as alicyclic diol, diethylene glycol (DEG), polyethylene glycol, the polytetramethylene glycols such as alkane glycol, dimer dihydric alcohol dihydric alcohol etc..This
Outside, can also and with the alkylene oxide adduct of bisphenol-A, the alkylene oxide adduct of Bisphenol F or trimethylolethane, trihydroxy methyl third
The polyalcohols such as alkane, glycerine, pentaerythrite, polyglycereol.
As polyester resin, it is contemplated that cohesive, bendability and solvent solubility etc., preferably without fusing point (display
For noncrystal property).Do not shown when described no fusing point is and determined with differential scanning calorimeter (DSC) herein clearly
Melting peakss.
When thermoplastic resin (A) is polyurethane resin, mix noncrystal property polyalcohol and polyisocyanate compounds and
The chain extender being added as needed on, synthesized by known method.Polyurethane resin, because can polymerize in the solution, institute
With with being easier to obtain the feature of the product of HMW than polyester resin.As the preference of noncrystal property polyalcohol, lift
Example has (methyl) acrylic polyol, PCDL, polybutadiene polyol, PEPA or PPG
Deng.In view of cohesive, resistance to bend(ing), durability, more preferably PCDL, PPG, PEPA, from
Further preferred PEPA from the aspect of the free degree of MOLECULE DESIGN.
When the noncrystal property polyalcohol that thermoplastic resin (A) uses when being polyurethane resin is PEPA, preferably
Composition is identical with the polyester resin, but its molecular weight preferably 1, more than 000, the upper limit preferably 20, less than 000, more preferably 10,
Less than 000.
During synthesis of polyurethane resin, in the compound used as chain extender, the compound preferably with hydroxyl and amino,
It can be the compound with one of which group or with two kinds of groups.As specifically into point example, for example there are dihydroxy
Methylbutanoic acid, dihydromethyl propionic acid, and 1,2-PD, 1,2- butanediols, 1,3-BDO, 2,3-butanediol, 2,2- bis-
Methyl isophthalic acid, ammediol, 3- methyl isophthalic acids, 5- pentanediols, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyls -1,3- hexylene glycol,
2,2- dimethyl -3- hydroxypropyls -2 ', 2 '-dimethyl -3 '-hydroxy propionate, 2- normal-butyls -2- ethyls -1,3-PD, 3-
Ethyl -1,5-PD, 3- propyl group -1,5-PD, 2,2- diethyl -1,3-PD, 3- octyl groups -1,5-PD, 3-
(such as Uniqema is international public for phenyl -1,5-PD, 2,5- dimethyl -3- sodium sulfo groups -2,5- hexylene glycol, dimer dihydric alcohol
Department PRIPOOL-2033 processed) etc. have in 1 molecule the compounds of 2 hydroxyls, trimethylolethane, trimethylolpropane, glycerine,
Have in the molecule of the polyalcohols such as pentaerythrite, polyglycereol, MEA, diethanol amine, triethanolamine etc. 1 more than 1 hydroxyl with
The amino alcohol of amino, ethylenediamine, 1,6- hexane diamines, 1,8- octanediamines, 1,9- nonane diamines, 1,10- decanediammes, 1,
The aliphatic diamines such as 11- hendecanes diamines, 1,12- dodecamethylene diamines or m-xylene diamine, 4,4 '-diamino-diphenyl first
There is 2 amino in 1 molecules such as the aromatic diamines such as alkane, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether
Compound.These compounds can be used alone, and several can also above be used in combination, all has no problem.
The polyisocyanate compounds used during synthesis of polyurethane resin, have no particular limits, optimization aromatic, fat
Race, alicyclic diisocyanate etc..For example, for example there are 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, to first
Phenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, m-benzene diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenyl
Diisocyanate, 2,6- naphthalene diisocyanates, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate, 4, the isocyanic acid of 4 '-hexichol two
Ester, 4,4 '-diisocyanate diphenyl ether, 1,5- naphthalene diisocyanates, m xylene diisocyanate, isophorone diisocyanate
Ester, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI) etc..
The number-average molecular weight (Mn (A)) of thermoplastic resin (A) is 10,000~70,000, more preferably 10,000~40,
000, further preferably 10,000~30,000 scope.When Mn (A) is too low, examined in terms of durability, environmental stability
Consider, not preferably.On the other hand, when Mn (A) is too high, the cohesiveness increase of resin, durability etc. improve, but intaglio plate hectographic printing
In fine rule printing adaptability be remarkably decreased.
The glass transition temperature of preferred thermoplastic resin (A) is more than -10 DEG C, more preferably more than 0 DEG C.Glass transition
When temperature is too low, resin softens under high temperature, so have the anxiety of the reliability decrease of the conductive membrane formed by lotion, in addition,
Because viscosity induces case hardness and reduced, have manufacturing process and/or using when be transferred to contact object side containing paste composition and
Produce the anxiety of the reliability decrease of conductive membrane.On the other hand, the glass transition temperature of thermoplastic resin (A), it is contemplated that
Printing, cohesive, dissolubility, lotion viscosity and printing etc., preferably less than 150 DEG C, more preferably less than 120 DEG C, further
Preferably less than 100 DEG C of ground.
In the present invention, contain carboxyl in the SOLID ORGANIC composition of electrocondution slurry, preferably the carboxyl amount (acid number) is to provide
In the range of amount.As preferred embodiment, thermoplastic resin (A) preferably has the acid number of particular range.As thermoplasticity
Resin (A), by using the resin of the acid number with specific scope, it can significantly increase thin relative to the electric conductivity of formation
The cohesive of film base material.The acid number of thermoplastic resin (A), more preferably preferably 20~500eq/ton, 30~350eq/ton.Thermoplastic
When the acid number of property resin (A) is too low, the conductive membrane of formation and the cohesive of base material have the tendency of reduction.On the other hand, it is hot
When the acid number of plastic resin (A) is too high, the water imbibition of the conductive membrane of formation uprises, and has and promotees because of the catalyst action of carboxyl
Enter the possibility of the hydrolysis of thermoplastic resin, the tendency for also causing the reliability of conductive membrane to reduce.
In addition, the diatomic alcohol compounds with carboxyl can also be added in electrocondution slurry.As an example, it for example there are dihydroxy first
Amine salt of the dimethylolalkanoic acids such as base propionic acid, dimethylolpropionic acid and these dimethylolalkanoic acids etc..Have by adding these
The diatomic alcohol compounds of carboxyl, easily carboxyl can be imported in the film after solidification, the bonding with ito film may be improved
Property.In addition, the diatomic alcohol compounds with carboxyl, preferably with 130 DEG C, the heat treatment of 30 minutes, fixedness organic principle
Acid number be 20~500eq/ton mode add, more preferably 30~350eq/ton.
The species of thermoplastic resin (B) is not particularly limited, having in preferably 1 molecule can be with more than 2 isocyanic acid
The noncrystal property polyalcohol of ester group reaction.As an example, PEPA, PPG, polycarbonate polyol be for example there are
Alcohol, from the aspect of the free degree of MOLECULE DESIGN, more preferably PEPA.Divided equally by mixing ratio thermoplastic resin (A) number
Son measures lower thermoplastic resin (B), can improve when carrying out intaglio plate hectographic printing electrocondution slurry from siloxanes cloth to film on
Transferability, significantly improve fine rule printing.
In addition, preferable dicarboxylic acid component when using PEPA as thermoplastic resin (B), for example there are terephthaldehyde
Acid, M-phthalic acid, phthalic acid, 2,6- naphthalene dicarboxylic acids, succinic acid, glutaric acid, adipic acid, decanedioic acid, dodecane dicarboxyl
The aliphatic dicarboxylic acids such as acid, azelaic acid, the binary acid of carbon number 12~28, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,3- hexamethylenes two
Carboxylic acid, 1,2- cyclohexane dicarboxylic acids, 4- methyl hexahydrophthalic acid anhydride, 3- methyl hexahydrophthalic acid anhydride, 2- methyl hexahydrobenzenes
Dicarboxylic acid anhydride, dicarboxyl hydrogenated bisphenol A, dicarboxyl A Hydrogenated Bisphenol A S, dimeric dibasic acid, hydrogenated dimer acids, hydrogenation naphthalene dicarboxylic acids, three rings
The hydroxycarboxylic acids such as the alicyclic dicarboxylic acids such as decane dicarboxylic acid, hydroxybenzoic acid, lactic acid.These can be used alone, can also two
It is used in combination more than kind.In addition, wherein, it is contemplated that in terms of physical property and solvent solubility, preferably and with terephthalic acid (TPA), isophthalic two
Formic acid.
In addition, in the range of the content of the invention is not damaged, the polynary carboxylic such as trimellitic anhydride, benzenetetrahydride can be used together
The unsaturated dicarboxylics such as acid, fumaric acid and the dicarboxylic acids containing the Sulfonic acid metal base such as 5- sulfo isophthalate sodium salts.This
Outside, after PEPA polymerization, acid number can be assigned by acid anhydrides such as rear addition trimellitic anhydride, phthalate anhydrides.
Further, using diol component during PEPA, known glycol as shown below can be used.Example
Such as, ethylene glycol, neopentyl glycol, 1,3-PD, 2- methyl isophthalic acids, ammediol, BDO, 2,2- diethyl -1,3- third
Glycol, 2- methyl isophthalic acids, ammediol, BDO, 2,2- diethyl -1,3-PD, 2- butyl -2- ethyls -1,3- third
Glycol, 1,3-BDO, 1,5-PD, 1,6- hexylene glycols, 3- methyl isophthalic acids, 5- pentanediols, 2- methyl isophthalic acids, 5- pentanediols, 1,
The aklylene glycols such as 9- nonanediols, 1,10- decanediols, 1,4-CHDM, 1,3-CHDM, 1,2- hexamethylenes
The polyethers systems such as alicyclic diol, diethylene glycol (DEG), polyethylene glycol, the polytetramethylene glycols such as dimethanol, tristane glycol, dimer dihydric alcohol
Dihydric alcohol etc..Further, it is also possible to and with the alkylene oxide adduct of bisphenol-A, the alkylene oxide adduct of Bisphenol F or trihydroxy methyl second
The polyalcohols such as alkane, trimethylolpropane, glycerine, pentaerythrite, polyglycereol.Further, citing is as used 6-caprolactone conduct
Polycaprolactone polyol class obtained from polyalcohol ring-opening polymerisation.They may be used alone, two or more kinds can also be used.
When thermoplastic resin (B) is polyether polyols alcohols, comprising the polyalcohol such as in glycerine or propane diols it is alone or its
In mixture, polyether polyols alcohols obtained from the oxyalkylene such as independent addition ethylene oxide, propylene oxide or addition its mixture,
Polyethers obtained from polyfunctional compound's reaction of polybutadiene alcohols, further oxyalkylene and ethylenediamine, ethanolamines etc. is more
First alcohols and, so-called polymer polyol alcohols etc. obtained from these polyethers polymerize as medium and acrylamide etc..
When thermoplastic resin (B) is polycarbonate polyol class, it for example there are containing from one kind or two or more straight-chain
The repeat unit of aliphatic dihydroxy alcohol as the PCDL of Component units, containing from one kind or two or more alicyclic ring
The repeat unit of formula dihydric alcohol as Component units PCDL or contain the repetition from both dihydric alcohols
PCDL of the unit as Component units.As specific constituent, as straight-chain aliphatic dihydroxy alcohol, lift
Example have 1,6- hexylene glycols, 1,5-PD, BDO, 3- methyl isophthalic acids, 5- pentanediols etc., as ester ring type dihydric alcohol, lift
Example has 1,4-CHDM etc..
The number-average molecular weight preferably 500~6 of thermoplastic resin (B), 000, more preferably 500~4,000.Number-average molecular weight mistake
When low, the viscosity of electrocondution slurry, fine rule printing adaptability declines, so not preferred.On the other hand, number-average molecular weight is too high
When, the viscosity of electrocondution slurry is uprised, and the fine rule printing adaptability in intaglio plate hectographic printing is remarkably decreased.In addition, thermoplastic resin
(B) improved for the cohesive of ito film, it is possible to which there is the acid number in particular range.
Thermoplastic resin (A) is necessary below 4.0 times relative to thermoplastic resin (B), weight ratio, more preferably 3.5 times
Hereinafter, further preferably less than 3.0 times.Weight than it is too high when, the viscosity of electrocondution slurry uprises, thin in intaglio plate hectographic printing
Line printing adaptability is remarkably decreased.
In the electrocondution slurry of the present invention, not to the polyurethane series resin outside the thermoplastic resin of above-mentioned record, polyester
Resin, epoxy resin, phenolic resin, acrylic resin, styrene-acrylic resins, SB, polyphenyl
Ethene, polyamide, polyamide-imide resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer resins, ethene-
Vinyl acetate copolymerized resin, polyvinyl butyral resin, cellulose and modified cellulose class and be used as any restrictions.
The species of curing agent (C) to that can be reacted with the adhesive resin of the present invention is not particularly limited, it is contemplated that bonding
The particularly preferred isocyanate compound such as property, resistance to bend(ing), curability.Further, as these isocyanate compounds, make
If product with NCO block, storage stability improves, it is advantageous to.As consolidating outside isocyanate compound
Agent, it for example there are the amino resins such as methylated melamine, butylated melamines, benzoguanamine, urea resin, acid
The known compounds such as acid anhydride, imidazoles, epoxy resin, phenolic resin.In these curing agent, it can be used together according to its species and select
Known catalyst or accelerator.The mixing ratio of thermoplastic resin (B) and curing agent (C), relative to thermoplastic resin (B)
Hydroxyl, can be preferably 20~200 moles of % with the functional group of the hydroxyl reaction of curing agent (C), more preferably 50~150 rub
You are %, further preferably 75~125 moles of %.
Can be aromatic series or fat as the example for the isocyanate compound that can be mixed into the electrocondution slurry of the present invention
PIC more than fat (cyclo) aliphatic diisocyanates, trivalent etc., can be any one of low molecular compound, high-molecular compound.
It for example there are the aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocynate
The aromatic diisocyanates such as ester, methyl diphenylene diisocyanate, XDI, hydrogenated diphenyl methane two are different
Alicyclic two isocyanide such as cyanate, hydrogenated xylene diisocyanate, dimer acid diisocyanate, IPDI
Acid esters or 3 amount bodies of these isocyanate compounds and these isocyanate compounds containing excess quantity and such as second two
Low point of alcohol, propane diols, trimethylolpropane, glycerine, D-sorbite, ethylenediamine, MEA, diethanol amine, triethanolamine etc.
Sub- active dydrogen compounds or various polyester polyols alcohols, polyether polyols alcohols, polyamide-based high molecular reactive hydride etc. are anti-
The compound containing terminal isocyanate group that should be obtained.In addition, the block agent as NCO, citing such as phenol,
The phenols such as benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol, cresols, xylenols, resorcinol, nitrophenols, chlorophenol, acetoxime, first
Chloro- 2- propyl alcohol of the alcohols such as the oximes such as base ethyl ketoxime, cyclohexanone oxime, methanol, ethanol, propyl alcohol, butanol, chlorethanol, 1,3- bis- etc.
The tertiary alcohols such as halogenated alcohols, the tert-butyl alcohol, tert-pentyl alcohol, epsilon-caprolactams, δ-valerolactam, butyrolactam, azetidinone etc.
The pyrazoles such as lactams, 3,5- dimethyl pyrazoles, other aspects also have aromatic amine, acid imide, pentanedione, second
Ethyl sodio acetoacetic ester, malonic acid ethyl ester isoreactivity methylene compound, thio-alcohol, imines, imidazoles, urea class, diarylide
Compound class, sodium hydrogensulfite etc..Wherein, it is contemplated that the particularly preferred oximes of curability, pyrazoles, active methylene group class, imidazoles,
Amine.
Electroconductive powder (D) in the electrocondution slurry of present embodiment is used for the conduction for assigning the conductive pattern formed
Property.
As the electroconductive powder (D) in the present invention, preferably precious metal powder, the preferably copper such as silver powder, bronze, platinum powder, palladium powder
The common metals such as powder, nickel powder, aluminium powder, brass powder (base metal) powder.In addition, the inorganic matter shape such as common metal or silica
Into different particles with the precious metal electroplatings such as silver into the common metal powder that forms of the precious metal alloys such as plating powder, silver.In addition, make
For the electroconductive powder (D) in the present invention, the electric conductivity of the nonmetallic formation such as the carbon system fillers such as carbon black, graphite powder can also be used
Powder.The content of carbon black and/or graphite powder during as containing carbon black, graphite powder, can relative to the mass parts of metal dust 100
To mix below 25 mass parts, further preferably below 11 mass parts.These electroconductive powders, can be used alone, and also may be used
To be used in combination.Wherein, from be readily obtained show high conductivity film this point consider, particularly preferably individually silver powder or with
Electroconductive powder based on silver powder.
It is not particularly limited for the shape of electroconductive powder (D), as the example of preferable shape, can enumerates known
Sheet (phosphorus sheet), spherical, dendroid (dendron shape), 1 particle described in Japanese Patent Laid-Open 9-306240 publications
Aggegation is shape (aggegation powder) of 3-dimensional state etc..Wherein, preferably sheet, spherical, aggegation powder, can be used alone, can also be simultaneously
With.
It is not particularly limited for the particle diameter of electroconductive powder (D), from the aspect of it can assign fine rule adaptability, preferably
Electroconductive powder of the center-diameter (D50) below 7 μm.When being more than 7 μm of electroconductive powder using center-diameter, the fine rule of formation
Shape deteriorates, it is possible to causes to be in contact between fine rule and produce short circuit.
Make the resistivity of the conductive coating of electrocondution slurry body solidification, examined in terms of it can obtain excellent conducting channel
Consider, preferably 5.0 × 10-2Hereinafter, more preferably 5.0 × 10-3Hereinafter, further preferably 5.0 × 10-4Below.
In the electrocondution slurry of the present invention, following inorganic matters can be added.As inorganic matter, carborundum, boron carbide, carbonization
Titanium, zirconium carbide, hafnium carbide, vanadium carbide, ramet, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond phosphinylidyne
The various carbide such as amine；The various borides such as the various nitride such as boron nitride, titanium nitride, zirconium nitride, zirconium boride；Titanium oxide (two
Titanium oxide), calcium oxide, magnesia, zinc oxide, cupric oxide, aluminum oxide, silica, the various oxides such as cataloid；
The various titanic acid compounds such as calcium titanate, magnesium titanate, strontium titanates；Molybdenum disulfide sulfides；The various fluorinations such as magnesium fluoride, fluorocarbons
Thing；The various metallic soaps such as aluminum stearate, calcium stearate, zinc stearate, magnesium stearate；In addition it is possible to use talcum, bentonite,
Talcum powder, calcium carbonate, bentonite, kaolin, glass fibre, mica etc..By adding these inorganic matters, print can be improved sometimes
Brush or heat resistance, further improve mechanical property or long durability.Wherein, in electrocondution slurry of the invention, from can be with
From the viewpoint of assigning printing, silica is convenient.That is, in the presence of silica, it can improve and contain silica
Filler between physical condensation power, be further advanced by hydrogen bond formation doubtful crosslinking and improve viscosity.The titanium dioxide used
In silicon, no matter its particle diameter or its hydrophily, hydrophobicity, can be used.
Further, it is also possible to using thixotropic agent, defoamer, fire retardant, tackifier, hydrolysis inhibitor, levelling agent, plasticizer,
Antioxidant, ultra-violet absorber, fire retardant, pigment, dyestuff.Further can suitably it make as resin decomposition inhibitor
With carbodiimides, epoxide etc..These can be used alone or are used in combination.
As the organic solvent (E) in the present invention, the boiling point under preferably 0.1013MPa is more than 100 DEG C, less than 350 DEG C.
More preferably more than 150 DEG C of boiling point, less than 330 DEG C.Further more than 180 DEG C of preferred boiling point, less than 320 DEG C.Organic solvent (E)
Boiling point it is too low when, lotion manufacturing process or during using lotion, has the composition specific volume for forming electrocondution slurry variable at solvent volatilization
The worry of change.On the other hand, when the boiling point of organic solvent is too high, it is desirable to the situation (such as less than 150 DEG C) of low temperature drying process
Under, solvent may be a large amount of remaining in film, there is the worry that the reliability for causing film reduces.
In addition, as organic solvent (E), thermoplastic resin (A), thermoplastic resin (B) and curing agent can be preferably dissolved
(C), and electroconductive powder (D) solvent scattered well can be made.For example there are for example, cyclohexanone, toluene, isophorone, γ-
Butyrolactone, phenmethylol, the SOLVESSO 100,150,200 of Exxon Chemical, propylene glycol methyl ether acetate, terpinol, second
Glycol monobutyl ether acetate, diamyl benzene, 3 penta benzene, n-dodecane alcohol, diethylene glycol (DEG), diethylene glycol monoethyl ether acetic acid esters, diethylene glycol (DEG) only son
Ether acetic acid ester, diethylene glycol dibutyl ether, diglycol monotertiary acetic acid esters, triethylene glycol diacetate esters, triethylene glycol, triethylene glycol list first
Ether, Triethylene glycol ethyl ether, triethylene glycol butyl ether, triethylene glycol butyl ether acetic acid esters, tetraethylene glycol, tetraethylene glycol diformazan
Ether, tetraethylene glycol monobutyl ether, tripropylene glycol, Tripropylene glycol monomethyl Ether, Tripropylene glycol monomethyl Ether acetic acid esters, tripropylene glycol monobutyl
Ether, Tri(propylene glycol)butyl ether,mixture of isomers acetic acid esters, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates, benzyl butyrate, Ergol
Deng.In addition, as petroleum hydro carbons, the AF solvents No. 4, No. 5, No. 6, No. 7 and No. 0 of Nippon Oil(Nippon Mitsubishi Oil) (strain) system are for example there are
Solvent H etc., two or more in these can be included as needed.
In electrocondution slurry can suitably containing such organic solvent, with the correspondingly viscosity such as printing.
As organic solvent (E) content, preferably below 25 parts by weight, enter relative to the parts by weight of lotion total weight 100
One step preferably below 20 parts by weight.During the too high levels of organic solvent (E), lotion viscosity reduces, under occurring when fine rule prints
Hang down.
In intaglio plate hectographic printing, during using such electrocondution slurry, in order to obtain good printing adaptability, its concentration,
With the measured value (25 of commercially available cone-plate type viscosimeter (for example, eastern machine industry (strain) system, RE-85 types, 3 ° of angle of taper, R14 etc.)
DEG C, start the measured value after rotation 180 seconds under rotating speed 2.5rpm), preferably 10~500Pas.During less than 10Pas, conductive paste
The ratio of organic solvent in material is excessive, and printed substrate is wired in electrocondution slurry printing with silicon rubber sheet material from surface
On transferability reduce, it is difficult to obtain good printed article.When on the other hand, more than 500Pas, it is difficult to be filled into galley
In, easily there is substrate spot (attachment of the lotion in non-image areas) in the scraping property deterioration of scraping blade in addition.Further electrocondution slurry
Tailed off from galley to printing with the reception amount of cloth, occur breaking on electrode pattern or wire drawing.More preferably 20~300dPas.
In addition, can suitably it be diluted during printing.
The electrocondution slurry of the present invention, preferably F values are 60~95%, more preferably 75~95%.F values, represent to include in lotion
Packing quality part relative to the mass parts of all solids composition 100 numerical value, with F values=(packing quality part/solid constituent matter
Amount part) × 100 represent.Described packing quality part refers to electroconductive powder (D) mass parts, solid constituent quality herein
Part is the mass parts of the composition outside solvent, contains electroconductive powder, adhesive resin, other curing agent or the addition of whole
Agent.When F values are less than 60%, it is impossible to obtain good electric conductivity, during more than 95%, there is the cohesive and/or electric conductivity with base material
The tendency that the hardness of film declines, and the reduction of printing is not avoided that.
The electrocondution slurry of the present invention is coated on base material or printing forms film, then, by will be included in film
Organic solvent (E) volatilization makes its drying, can form conductive membrane.
The process volatilized by entering to exercise organic solvent (E) under heating, curing reaction are carried out, dried conductive membrane
Electric conductivity or cohesive, case hardness it is good.It is preferably more than 80 DEG C, more preferably more than 100 DEG C of heating-up temperature, further excellent
Select more than 110 DEG C.In addition, from the aspect of the energy-conservation in the heat resistance and production process of the transparency conducting layer of bottom, heating
Preferably less than 150 DEG C of temperature, more preferably less than 135 DEG C, further preferably less than 130 DEG C.Preferably 5 minutes heat time with
On, more preferably more than 15 minutes, further preferably more than 25 minutes.When heat time was less than 5 minutes, conductive membrane is consolidated
Change deficiency, cohesive deficiency.
Base material coated by electrocondution slurry is not particularly limited, for example there are for example, makrolon, acrylic acid, polyamides are sub-
Amine, polyester etc..In addition, by setting transparency conducting layer between the base material and conductive film, lamination over transparent conductive layer
Conductive membrane, electric conductivity laminate can be obtained.The raw material of transparency conducting layer are not particularly limited, such as can be used
Conductive film of the indium oxide based on the ito film or nano wire that tin is that principal component is formed.In addition, transparency conducting layer is not
Substrate surface entirety is only formed at, the transparency conducting layer that a part of transparency conducting layer is eliminated by etching can also be used.
Using the electric conductivity laminate of the present invention, touch-screen can be manufactured.Touch-screen can be that resistive film mode can also
It is capacitive way.Although being applied to any touch-screen, this lotion is suitable for fine rule and formed, and it is advantageous to for capacitor square
In formula.
As the manufacture method of touch-screen, do not limit especially.For example, it can manufacture by the following method：In ITO
On the base material of the transparency conducting layer lamination such as film, after solidification, apply or print electrocondution slurry so as to form conductive return
Road, solidify the electrocondution slurry of coating or printing by heating, form electric conductivity laminate, the electric conductivity laminate that will be obtained
It is bonded with other electric conductivity laminates.
The electrocondution slurry of the present invention, be suitable for the circuit layout of touch-screen, in addition, electromagnetic wave shielding purposes,
The circuit of electronic unit is formed in the purposes such as the electric conductivity sticker of purposes, terminal and wire and can also used.Further,
It is suitable for the replacement as transparent and electrically conductive films such as the ito film with net-like pattern or ito glasses and by the material attracted attention
Printing in.
【Embodiment】
The present invention is described in further detail in embodiment exemplified below and comparative example.In addition, the invention is not limited in following
Embodiment.In addition, unless otherwise prescribed, " portion " expression " mass parts " in example, solid component concentration represents that organic solvent is complete
Nonvolatile component after full volatilization.
The evaluation of the evaluation of physical property and electrocondution slurry of polyester resin and polyurethane resin in the present invention, passes through following sides
Method is carried out.
1. number-average molecular weight
Sample resin, which is dissolved or is diluted in tetrahydrofuran, makes resin concentration for 0.5 weight % or so, with aperture 0.5
μm poly tetrafluoroethylene filter filtering, as GPC determination samples.Using tetrahydrofuran as mobile phase, (strain) Shimadzu is used
Made gel permeation chromatography (GPC) Prominence is made, is detected by Differential refractometer (in terms of RI), in chromatogram column temperature
30 DEG C, the GPC measure of resin samples is carried out under flow 1mL/ minutes.Use monodisperse polystyrene known to number-average molecular weight
Gpc measurement result, the conversion number-average molecular weight of the polystyrene of sample resins is obtained, as the equal molecule of number of sample resins
Measure (Mn), weight average molecular weight (Mw).Simply chromatographic column using shode × KF-802 of Showa Denko K. K, 804L,
806L。
2. glass transition temperature (Tg)
Sample resin 5mg is placed in aluminum sample disk and sealed, the difference made by using Seiko Instr Inc's (strain)
Show scanning calorimetry (DSC) DSC-220, be warming up to 200 DEG C with 20 DEG C/min of speed of programming rate, measure, obtain glass
The intersection point temperature of tangent line of the extended line of baseline below glass transition temperature with representing maximum inclination in transition portion.
3. acid number
0.2 gram of accurate weighing sample is dissolved in 20 milliliters of chloroform, is then dripped by using 0.01N potassium hydroxide (ethanol solution)
Location survey is determined.Indicator uses phenolphthalein solution.The unit of acid number is eq/ton, i.e. every 1 ton of sample equivalent.
5. the making of electric conductivity laminate test film
Electrocondution slurry is printed on to PET film (Japan's spinning for the annealed processing that thickness is 100 μm by silk screen print method
The COSMO shine A4300 of (strain) system) or ito film (tail vat industry (strain) system, KH150) on, form width 30mm, length
50mm pure color patterns, dry 30 minutes at 130 DEG C, electric conductivity laminate test film is used as using solidfied material.Painting during adjustment printing
Thickness degree makes thickness of dry film be 8~12 μm.
6. cohesive
Using electric conductivity laminate test film, according to JIS K-5400-5-6：1990, use セ ロ テ ー プ (registrars
Mark) (Nichiban (strain) manufactures) evaluated by disbonded test.The lattice of 10 lattice × 10 totally 100 grids are formed with 1mm intervals
Draw lattice, carry out cellophane tape stripping.Visual valuation is carried out to the extent of exfoliation of the film in ito film.Evaluation criterion is as follows.
○：It is not stripped completely.
△：A part is stripped.
×：More than 50% is stripped.
7. ratio resistance
The sheet resistance and thickness of the test film of electric conductivity laminate are determined, calculates ratio resistance.Thickness is to use thickness
SMD-565L ((strain) TECLOCK) is counted, the thickness of 3 cured coating films is determined using the thickness of PET film as zero point, uses it
Average value.Sheet resistance is to determine four test films using Loresta-GP MCP-T610 ((strain) Mitsubishi Chemical analytical technology system),
Use its average value.
8. pencil hardness
Electric conductivity laminate test film is placed on the SUS304 plates that thickness is 2mm, according to JIS K5600-5-4：
1999 measure pencil hardness.
9. the adaptation evaluation after hot and humid processing
Electric conductivity laminate test film is placed in 85 DEG C of -85%RH hot and humid groove, carries out 120hr processing.
In obtained test film, forming the lattice of 10 lattice × 10 with 1mm intervals, totally 100 grids draw lattice, carry out cellophane tape stripping.So
Afterwards, visual valuation is carried out to the extent of exfoliation of the film in ito film.Evaluation criterion is as follows.
○：It is not stripped completely.
△：A part is stripped.
×：More than 50% is stripped.
10. the evaluation of fine rule printing
It is recessed to prepare the nickel electroforming plane with 30 μm of line width, 20 μm of depth, multiple female patterns that spacing is 60 μm respectively
Version is as the galley used in intaglio plate hectographic printing, and PET film (society COSMO shine A4300 spin in Japan) is as printed
Base material.In addition, it is used as printing cloth using the silicone cloth that thickness is 0.6mm.First, on plane intaglio plate surface with a certain amount of confession
To electrocondution slurry, electrocondution slurry is embedded into the female pattern of plane intaglio plate using metal squeegee.Then, in siloxanes cloth
Make its rotation in the state of being crimped on plane intaglio plate, slided by making it on plane intaglio plate, the recessed of plane intaglio plate will be embedded in
Electrocondution slurry in shape pattern is received to siloxanes cloth surface.Finally, its rotation is made in the state of siloxanes cloth is crimped on PET film
Turn, by making it slide on a pet film, obtain the printed article on PET film surface with specific pattern.Using above-mentioned printed article,
L/S is determined using digit microscope VHX-2000 ((strain) Keyence systems), in addition, the observation of detail mode is carried out, by following
Judgment standard evaluates fine rule printing.
○：Do not break, without the short circuit (short) between fine rule.
×：Part broken string has short circuit (short) between fine rule.
11. the making of electrocondution slurry
Each composition is mixed with mixed proportion (mass ratio) shown in table 1,2, is kneaded, is implemented in three-roll grinder
The electrocondution slurry of example 1~7, comparative example 1~3.
【Table 1】
【Table 2】
Polyester 1：(strain) RV630 processed (number-average molecular weight 23,000, acid number 20eq/ton, 7 DEG C of glass transition temperature) spins in Japan
Polyester 2：(strain) GK390 processed (number-average molecular weight 18,000, acid number 80eq/ton, 7 DEG C of glass transition temperature) spins in Japan
Polyester 3：(strain) RV296 processed (number-average molecular weight 14,000, acid number 80eq/ton, 71 DEG C of glass transition temperature) spins in Japan
Polyurethane 4：(strain) UR-PS9 processed (number-average molecular weight 22,000, acid number 170eq/ton, glass transition spin in Japan
100 DEG C of temperature)
PEPA 1：(strain) KURARAY P-2013 (number-average molecular weight 2,000, acid number 3eq/ton, hydroxyl value
54.4KOHmg/g)
PEPA 2：(strain) KURARAY P-2030 (number-average molecular weight 2,000, acid number 4eq/ton, hydroxyl value
55.4KOHmg/g)
PEPA 3：(strain) KURARAY P-1030 (number-average molecular weight 1,000, acid number 3eq/ton, hydroxyl value
111.3KOHmg/g)
PEPA 4：(strain) KURARAY F-3010 (number-average molecular weight 3,000, acid number 5eq/ton, hydroxyl value
55.8KOHmg/g)
Blocked isocyanate 1：Baxenden societies Trixene BI7982 (the weight % of solid constituent rate 70, isocyanates
The weight % of theoretical value 10.2)
Blocked isocyanate 2：Baxenden societies Trixene BI 7992 (the weight % of solid constituent rate 70, isocyanates
The weight % of theoretical value 9.2)
Blocked isocyanate 3：Baxenden societies Trixene BI 7950 (the weight % of solid constituent rate 65, isocyanates
The weight % of theoretical value 7.4)
Silver powder 1：FUKUDA METAL paper tinsel powder industry (strain) AgC-251 (D50=1.8 μm, flake silver powder)
Silver powder 2：(strain) iron Japan SF30 (D50=1.0 μm, flake silver powder)
Silver powder 3：DOWA Hi-tech (strain) G-35 (D50=6.1 μm, aggegation silver powder)
Silver powder 4：DOWA Hi-tech (strain) Ag-2-1C (D50=1.1 μm, spherical silver powder)
Organic solvent 1：Diethylene glycol monoethyl ether acetate (217 DEG C of boiling point)
Organic solvent 2：Diethylene glycol monobutyl ether acetic acid esters (247 DEG C of boiling point)
Organic solvent 3：Tetraethyleneglycol dimethyl ether (276 DEG C of boiling point)
Organic solvent 4：Triethylene glycol butyl ether (278 DEG C of boiling point)
Organic solvent 5：Triethylene glycol diacetate esters (300 DEG C of boiling point)
Dispersant 1：BYK Japan (strain) Disperbyk2155 processed
Levelling agent 1：Common prosperity society chemistry (strain) MK Concha
12. evaluation result
The various evaluation results that embodiment 1~6, the electrocondution slurry of comparative example 1~3 are carried out are described in table 3,4.By table
3rd, 4 understand, the electrocondution slurry of embodiment 1~6, can have good printing and ITO cohesives concurrently.
【Table 3】
【Table 4】
Industrial applicability
The manufacture of the electrocondution slurry, the printed circuit board wiring that can be used for used in various e-machines etc. of the present invention.
Further, it is also possible to form conductive adhesive of application, terminal or wire etc. in the loop of electromagnetic wave shielding application, electronic component
Used in.
Claims (12)
1. a kind of electrocondution slurry, it is characterised in that be at least containing thermoplastic resin A, thermoplastic resin B, curing agent C, conduction
Property powder D and organic solvent E electrocondution slurry, thermoplastic resin A relative to thermoplastic resin B weight ratio below 4.0,
Thermoplastic resin A be weight average molecular weight more than 10,000 and the polyurethane resin of glass transition temperature -10~150 DEG C and/or
Polyester resin, further, thermoplastic resin B are noncrystal polyalcohol, and number-average molecular weight is 500~6,000.
2. electrocondution slurry according to claim 1, it is characterised in that electroconductive powder D average grain diameter D50 is at least 7 μ
Below m.
3. electrocondution slurry according to claim 1 or 2, it is characterised in that thermoplastic resin B be PEPA and/or
PPG, and/or polycarbonate polyol.
4. electrocondution slurry according to claim 1 or 2, it is characterised in that 130 DEG C, in the heat treatment of 30 minutes, non-volatile
The acid number of property organic principle is 20~500eq/ton.
5. electrocondution slurry according to claim 1 or 2, it is characterised in that curing agent C is isocyanate compound, and solid
Agent C meets following condition relative to thermoplastic resin B combined amount：Relative to thermoplastic resin B hydroxyl, curing agent C's
NCO is 20~200 moles of %.
6. electrocondution slurry according to claim 1 or 2, it is characterised in that organic solvent E boiling point more than 100 DEG C, and
Weight percent relative to electrocondution slurry total weight is below 25 weight %.
7. electrocondution slurry according to claim 1 or 2, it is characterised in that electroconductive powder D is mainly formed by silver.
8. electrocondution slurry according to claim 1 or 2, it is characterised in that for intaglio plate hectographic printing, the intaglio plate hectograph
Printing is that electrocondution slurry is filled in the galley with female pattern, and the electrocondution slurry of filling is through having silicon rubber on surface
After the printing rubber blanket of sheet material receives, electrocondution slurry is transferred on printing base from the printing rubber blanket, printed
And the method for forming electrode pattern.
9. a kind of printed article, it is through obtained from intaglio plate hectographic printing by the electrocondution slurry described in any one of claim 1~7
Conductive coating obtains through drying and/or solidifying, and the intaglio plate hectographic printing is that electrocondution slurry is filled in spill figure
In the galley of case, the electrocondution slurry of filling is after there is the printing rubber blanket of silicon rubber sheet material to receive on surface, by conduction
Slurry is transferred on printing base from the printing rubber blanket, the method printed and form electrode pattern.
10. printed article according to claim 9, line width and line spacing are respectively less than 100 μm.
It is that lamination forms over transparent conductive layer for printed article described in claim 9 or 10 11. a kind of electric conductivity laminate.
12. a kind of touch panel, it use the electric conductivity laminate described in claim 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013204073 | 2013-09-30 | ||
| JP2013-204073 | 2013-09-30 | ||
| PCT/JP2014/074994 WO2015046096A1 (en) | 2013-09-30 | 2014-09-22 | Electro-conductive paste, electro-conductive film, electro-conductive circuit, electro-conductive laminate, and touch panel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105612585A CN105612585A (en) | 2016-05-25 |
| CN105612585B true CN105612585B (en) | 2018-03-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480052717.9A Active CN105612585B (en) | 2013-09-30 | 2014-09-22 | Electrocondution slurry, conductive coating, galvanic circle, electric conductivity laminate and touch-screen |
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| JP (1) | JP6767089B2 (en) |
| CN (1) | CN105612585B (en) |
| TW (1) | TWI648748B (en) |
| WO (1) | WO2015046096A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6372689B2 (en) * | 2014-07-28 | 2018-08-15 | Dic株式会社 | Conductive paste and conductive pattern forming method |
| KR101810855B1 (en) | 2015-04-21 | 2017-12-20 | 도레이 카부시키가이샤 | Laminate member and touch panel |
| DE102015122034A1 (en) * | 2015-12-16 | 2017-06-22 | Ferro Gmbh | Thermoplastic screen printing paste |
| CN105702323B (en) * | 2016-03-15 | 2017-08-25 | 张家港瑞诺光电材料科技有限公司 | A kind of compliant conductive silver paste and preparation method |
| TWI732839B (en) * | 2016-03-29 | 2021-07-11 | 日商東洋紡股份有限公司 | Extensible conductive paste and manufacturing method of curved printed circuit board |
| WO2018029750A1 (en) * | 2016-08-08 | 2018-02-15 | 東レ株式会社 | Laminated member and touch panel |
| KR20180024827A (en) * | 2016-08-31 | 2018-03-08 | 주식회사 동진쎄미켐 | Conductive composition and conductive laminate using the same |
| CN109716448B (en) * | 2016-09-16 | 2021-04-09 | 株式会社则武 | Silver paste for resin substrate, electronic component comprising same, and method for producing same |
| TWI779066B (en) * | 2017-07-19 | 2022-10-01 | 日商東洋紡股份有限公司 | adhesive composition |
| KR20200043969A (en) * | 2017-08-24 | 2020-04-28 | 도요보 가부시키가이샤 | Conductive paste, three-dimensional printed circuit, touch sensor and their manufacturing method |
| CN110097998B (en) * | 2018-01-31 | 2021-06-15 | 上海宝银电子材料有限公司 | Conductive silver paste for transfer printing process touch screen and preparation method thereof |
| CN108749244B (en) * | 2018-06-07 | 2020-07-14 | 浙江欣麟新材料技术有限公司 | Optical high-flexibility conductive glass film and preparation method thereof |
| CN109903885B (en) * | 2018-12-29 | 2020-10-02 | 无锡帝科电子材料股份有限公司 | Conductive paste, application thereof, solar cell electrode and solar cell |
| CN110993149A (en) * | 2019-12-26 | 2020-04-10 | 无锡晶睿光电新材料有限公司 | Silver paste for metal grid capacitive flexible touch screen and preparation method and application thereof |
| CN111370159A (en) * | 2020-03-11 | 2020-07-03 | 中国人民解放军国防科技大学 | Conductive paste and preparation method and application thereof |
| CN114189983B (en) * | 2020-09-15 | 2024-03-26 | 北京梦之墨科技有限公司 | Flexible conductive paste and flexible circuit board |
| CN113593776B (en) * | 2021-07-30 | 2023-03-10 | 长春捷翼汽车零部件有限公司 | Wire harness production method and wire harness |
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- 2014-09-22 JP JP2014551449A patent/JP6767089B2/en active Active
- 2014-09-22 CN CN201480052717.9A patent/CN105612585B/en active Active
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| Publication number | Publication date |
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| JPWO2015046096A1 (en) | 2017-03-09 |
| TW201517060A (en) | 2015-05-01 |
| CN105612585A (en) | 2016-05-25 |
| TWI648748B (en) | 2019-01-21 |
| WO2015046096A1 (en) | 2015-04-02 |
| JP6767089B2 (en) | 2020-10-14 |
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Address after: No. 1, No. 13, meitian-1, Shibei District, Osaka, Osaka, Japan Patentee after: TOYOBO Co.,Ltd. Address before: Japan's Osaka Osaka North Doushima Haji chome 2 times 8 Patentee before: TOYOBO Co.,Ltd. |
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