CN102737750A - Conductive paste - Google Patents
Conductive paste Download PDFInfo
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- CN102737750A CN102737750A CN2012100920090A CN201210092009A CN102737750A CN 102737750 A CN102737750 A CN 102737750A CN 2012100920090 A CN2012100920090 A CN 2012100920090A CN 201210092009 A CN201210092009 A CN 201210092009A CN 102737750 A CN102737750 A CN 102737750A
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- Prior art keywords
- conductive paste
- polyurethane resin
- conducting channel
- resin
- thin film
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a conductive paste, which has excellent fitness with an ITO thin film and enables a conductive circuit formed by a low-temperature technology to have excellent conductivity and also good printing adaptability. The conductive paste provided in the invention is characterized by comprising polyurethane resin, conductive powder and an organic solvent. The organic solvent also comprises 30-90 weight percent of high-boiling-point solvents which have a boiling point ranging from 240 degrees to 330 degrees under a 760mmHg condition.
Description
Technical field
The present invention relates to the manufacturing approach of conductive paste and the conducting channel of using it.
Background technology
In recent years, in the electronic installation that has used touch panels such as dull and stereotyped terminal, using the ito thin film that for example on films such as PET, forms ITO (Indium Tin Oxide) electrode.
This ito thin film is through forming the ITO layer on film, carry out the removal (etching Etch out) based on etching method and form with the mode that stays the electrode part.And, using the conductive paste formation conducting channel that conductive powders such as Ag is scattered in organic binder bond on the film that exposes and on the ITO layer.
Various that in the equipment of the low heat resistant that adopts this film etc., use, conductive pastes that can low temperature calcination (for example, with reference to patent documentation 1 etc.) have been proposed.But, in the conducting channel on ito thin film, there are problems such as also insufficient to the adaptation of film and ITO layer, that generation is peeled off, the part that particularly etches is more remarkable.
On the other hand, during high meticulous conducting channel in forming electronic installation, generally use photoetching process, it has utilized the photoelectric sensitivity conductive property paste of in organic binder bond etc. employing photoresist etc.But photoetching process is through removing the subtractive processes that material forms conducting channel, and the service efficiency of the conductive paste of use is low, complex procedures, the large-scale equipment of needs in wet processing etc.
To this, as the addition technology that adds material in desired place, print processes such as photogravure, intaglio offset receive much concern.For example can through conductive paste is supplied to intaglio plate, in order it be transferred to for example blanket, the base material of organosilicon system, thereby form conducting channel according to intaglio offset.
In this print process, being situated between is transferred to conductive paste on the base material by version, and the conductive paste that therefore requires to use has good transfer printing property.Intaglio offset particularly; Conductive paste is transferred on the base material from intaglio plate by blanket owing to be situated between; Therefore need be in each operation transfer printing conductive paste positively; In continuous printing, require to be 100% to the transferring rate of base material, to suppress to be transferred to the excellent paste of printabilities such as shape defect of the printed article of base material from blanket.
In addition, when the conducting channel that forms through print process in the low equipment of thermal endurance, not only require paste to have good printability, also require in the conducting channel that forms through low temperature calcination, to obtain good electrical characteristics.Yet, have the problem be difficult to obtain satisfy simultaneously the paste of these conditions.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-355933 communique
Summary of the invention
The problem that invention will solve
The present invention develops in order to solve such problem, and its first purpose is, provides adaptation with ito thin film excellent and can in the conducting channel that forms through low temperature process, obtain the conductive paste of good electrical conductivity; Second purpose is, is provided on the basis of above-mentioned characteristic, in intaglio offset, has the conductive paste of excellent printability.
The scheme that is used to deal with problems
The conductive paste of a mode of this execution mode is characterised in that it contains polyurethane resin and conductive powder and organic solvent.Through such formation, excellent with the adaptation of ito thin film, and can in the conducting channel that forms through low temperature process, obtain good electrical conductivity.
In addition, in the conductive paste of this execution mode, polyurethane resin preferably comprises and contains the carboxyl polyurethane resin.
Through such formation, the cohesive force of polyurethane resin improves, and can further improve the adaptation with ito thin film.
In addition, the conductive paste of this execution mode is characterised in that, its further contain in 1 molecule, comprise 2 above glycidyls at least epoxy resin as crosslinking agent.
Through such formation, when conducting channel forms the three-dimensional grid chain, the solvent resistance of resulting conducting channel, adaptation improve.
In addition, the formation method of the conducting channel of this execution mode is characterised in that, on ito thin film, is formed with filming of above-mentioned conductive paste pattern, and this is filmed 80～200 ℃ of dry down or curing.
Through such formation, excellent with the adaptation of ito thin film, in the conducting channel that forms, can obtain good electrical conductivity.
In addition, the conductive paste of a mode of this execution mode is characterised in that said organic solvent comprises the high boiling solvent of 30～90 quality %, and the boiling point of said high boiling solvent under 760mmHg is 240～330 ℃.Through such formation, on the basis of above-mentioned characteristic, can also obtain excellent printability such as craspedodrome property, live width reproducibility at the printed article of intaglio offset.
In addition; The formation method of the conducting channel of this execution mode is characterised in that; On version, fill above-mentioned conductive paste; With said conductive paste once transfer printing on the blanket cylinder surface of filling, with said conductive paste secondary transfer printing on substrate surface of primary transfer, the said conductive paste that makes secondary transfer printing is 80～200 ℃ of dry down or curing.
In the conducting channel that forms through such formation, owing to have satisfactory electrical conductivity, and have good craspedodrome property, live width reproducibility, therefore can obtain to have the electronic installation of high reliability, conductive characteristic.
In addition, the electronic installation of this execution mode is characterised in that, the conducting channel that comprises polyurethane resin and conductive powder that it possesses ito thin film and on said ito thin film, forms.
Through such formation, excellent with the adaptation of ito thin film in conducting channel, have satisfactory electrical conductivity, therefore can obtain to have the electronic installation of high reliability, conductive characteristic.
The effect of invention
According to the present invention, can provide excellent with the adaptation of ito thin film, in the conducting channel that forms through low temperature process, can obtain the conductive paste of good electrical conductivity.In addition, on the basis of above-mentioned characteristic, has the conductive paste of the excellent printability of the craspedodrome property, live width reproducibility etc. of printed article in the time of can also intaglio offset being provided.
Description of drawings
Fig. 1 is the figure of operation of intaglio offset of second mode of this execution mode of expression.
Fig. 2 is the optical microscope photograph of the printed article of embodiment 7.
Fig. 3 is the optical microscope photograph of the printed article of comparative example 3.
Description of reference numerals
11 intaglio plates
The 11a recess
12 conductive pastes
13 organosilicon blankets
14 objective tables
15 base materials
16 film
Embodiment
Inventors of the present invention etc. find through further investigation in view of above-mentioned problem; Through containing polyurethane resin and conductive powder and organic solvent, can obtain adaptation and the good electrical conductivity in the conducting channel that forms through low temperature process with the excellence of ito thin film as conductive paste; Through in above-mentioned organic solvent, further comprising boiling point 30～90 quality %, under 760mmHg is 240～330 ℃ high boiling solvent; Can be on the basis of above-mentioned characteristic; When intaglio offset, obtain to the transfer printing property of transfer printing bodies such as substrate, the excellent printabilities such as craspedodrome property, live width reproducibility of printed article after the transfer printing, thereby accomplish the present invention.
Below, the conductive paste of this execution mode is described.
The conductive paste of this execution mode contains polyurethane resin and conductive powder and organic solvent.
Polyurethane resin in the conductive paste of this execution mode uses as resin glue, and said resin glue gives paste good printability, and is perhaps remaining in its solidfied material (conducting channel), gives rerum naturas such as adaptation, resistance to deflection, hardness.As this polyurethane resin, do not contain carboxyl polyurethane resin, phenolic hydroxy group polyurethane resin with regard to limiting especially, for example can enumerating out, contain amino polyurethane resin etc. as long as can give printability to conductive paste.
Wherein, especially preferably comprise and contain the carboxyl polyurethane resin.For example; Can use the amino-formate bond that forms in the reaction that has by polyisocyanates (a) and bisphenol type epoxy alkane addition product glycol (b) and polycarbonate polyol (c) and dimethylolalkanoic acids (d), and have the carboxyl that imports by dimethylolalkanoic acids (d) contain the carboxyl polyurethane resin.When reaction, also can add monohydroxy compound (e) as reaction terminating agent (end-capping reagent).
This polyurethane resin for example can obtain through being mixed together to react with polyisocyanates (a), bisphenol type epoxy alkane addition product glycol (b), polycarbonate polyol (c), dimethylolalkanoic acids (d) with as the monohydroxy compound (e) of reaction terminating agent (end-capping reagent) effect; Perhaps can be through after making the reaction of polyisocyanates (a), bisphenol type epoxy alkane addition product glycol (b), polycarbonate polyol (c) and dimethylolalkanoic acids (d), then make monohydroxy compound (e) reaction and obtain.This reaction is carried out under the catalyst-free condition through under room temperature to 100 ℃, mixing, in order to improve reaction speed, preferably 70～100 ℃ of heating down.
As polyisocyanates (a); Particularly; For example can enumerate out 2; 4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), IPDI, hexamethylene diisocyanate, methyl diphenylene diisocyanate, (adjacent, or to) XDI, (adjacent, or to) hydrogenated xylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1; 4-dimethylene diisocyanate, 1, vulcabond such as 5-naphthalene diisocyanate.These polyisocyanates can use a kind or make up more than 2 kinds and to use.
In them, preferred toluene di-isocyanate(TDI), trimethyl hexamethylene diisocyanate.When using these vulcabond, can obtain the solidfied material of the excellent performance of anti-the sweating heat.
As bisphenol type epoxy alkane addition product glycol (b), can enumerate the ethylene oxide adduct, propylene oxide adduct, epoxy butane addition product of bisphenol-A etc., in them, the propylene oxide adduct of preferred bisphenol-A.
Then, as polycarbonate polyol (c), optimization polycarbonate glycol.As PCDL, can enumerate out contain with the repetitive that is derived from the straight chain aliphatic diols more than a kind or 2 kinds as the PCDL that constitutes the unit, contain with the repetitive that is derived from the ester ring type glycol more than a kind or 2 kinds as the PCDL that constitutes the unit, or contain with the repetitive that is derived from their two kinds of glycol as the PCDL that constitutes the unit.These PCDLs can be through straight chain aliphat or ester ring type glycol and for example carbonic ester ester exchange reaction, wait with the reaction of phosgene and to make.
As containing with the repetitive that is derived from straight chain aliphatic diols, particularly, for example can enumerate out by 1 as the PCDL that constitutes the unit; The PCDL that the 6-hexylene glycol derives, by 1,5-pentanediol and 1, the PCDL that the 6-hexylene glycol derives, by 1; 4-butanediol and 1; The PCDL that the 6-hexylene glycol derives, by the 3-methyl isophthalic acid, 5-pentanediol and 1, the PCDL that the 6-hexylene glycol derives.
As containing with the repetitive that is derived from the ester ring type glycol, particularly, for example can enumerate out by 1 the PCDL that the 4-cyclohexanedimethanol derives as the PCDL that constitutes the unit.
As containing with the repetitive that is derived from straight chain aliphatic diols and these two kinds of glycol of ester ring type glycol as the PCDL that constitutes the unit; Particularly; For example can enumerate out by 1 6-hexylene glycol and 1, the PCDL that the 4-cyclohexanedimethanol derives.
Contain the tendency that low warpage properties, pliability excellence are arranged as the PCDL that constitutes the unit with the repetitive that is derived from straight chain aliphatic diols.In addition, the repetitive that contains to be derived from the ester ring type glycol has crystallinity to uprise as the PCDL that constitutes the unit, the tendency of anti-zinc-plated property, the excellent performance of anti-the sweating heat.By above viewpoint, can make up and use these PCDLs more than 2 kinds, perhaps use and contain with the repetitive that is derived from straight chain aliphatic diols and these two kinds of glycol of ester ring type glycol PCDL as the formation unit.In order balancedly to show low warpage properties, pliability and anti-sweating heat performance, anti-zinc-plated property, the copolymerization ratio of preferably using straight chain aliphatic diols and ester ring type glycol is 3: 7～7: 3 PCDL by quality ratio.
The PCDL preferred number average molecular weight is 200～5000; Contain with the repetitive that is derived from straight chain aliphatic diols and ester ring type glycol as constituting the unit at PCDL; The copolymerization ratio of straight chain aliphatic diols and ester ring type glycol is that preferred number average molecular weight is 400～2000 under 3: 7～7: 3 the situation by quality ratio.
Dimethylolalkanoic acids (d) is the dihydroxy aliphatic carboxylic acid with carboxyl, particularly, for example can enumerate out dihydromethyl propionic acid, dimethylolpropionic acid etc.Through using dimethylolalkanoic acids, can easily carboxyl be imported in the polyurethane resin.
As monohydroxy compound (e), be the material that becomes the end-capping reagent of polyurethane, get final product so long as have the compound of 1 hydroxyl in the molecule, can enumerate out aliphatic alcohol, monohydroxy list (methyl) acrylate compounds etc.
As aliphatic alcohol, particularly, for example can enumerate out methyl alcohol, ethanol, propyl alcohol, isobutanol etc., as monohydroxy list (methyl) acrylate compounds, particularly, for example can enumerate out acrylic acid 2-hydroxyl ethyl ester etc.
The weight average molecular weight that contains the carboxyl polyurethane resin is preferably 500～100000.When containing the weight average molecular weight less than 500 of carboxyl polyurethane resin, destroy percentage elongation, pliability and the intensity of cured film sometimes, on the other hand, surpass at 100000 o'clock, the meeting hardening might make pliability reduce.More preferably 4000～50000, further be preferably 6000～30000.Wherein, in this manual weight average molecular weight is the value through the polystyrene conversion of gel permeation chromatography.
The acid number that contains the carboxyl polyurethane resin is preferably in the scope of 5～150mgKOH/g.During acid number deficiency 5mgKOH/g, the cohesive force of paste reduces, and causes easily during printing that transfer is bad.On the other hand, when acid number surpassed 150mgKOH/g, the viscosity of paste was too high, and needing etc. of a large amount of crosslinking agent of compounding arranged, and was difficult to give printability.10～100mgKOH/g more preferably.In addition, the acid number of resin is the value of measuring according to JIS K5407.
In addition, be purpose to replenish printing, also can contain the organic binder bond beyond the polyurethane resin.Particularly, for example can enumerate out the various modified polyester resins, vinyl chloride-vinyl acetate copolymer, epoxy resin, phenolic resins, acrylic resin, polyvinyl butyral resin, polyamidoimide, polyimides, polyamide, celluloid, cellulose-acetic acid-butyric acid (CAB), cellulose-acetic acid-propionic acid modified celluloses such as (CAP) class etc. of mylar, urethane modified polyester resin, epoxy modified polyester resin, acrylic acid modified polyester resin etc.
Wherein, preferably be contained in the carboxy resin that contains that comprises 2 above carboxyls in 1 molecule at least especially.As this carboxy resin that contains, particularly, can enumerate following resin of giving an example, but be not limited to these resins.
(1) unsaturated carboxylic acid such as (methyl) acrylic acid obtains with in addition the compound copolymerization more than a kind with unsaturated double-bond contains carboxy resin.
(2) in unsaturated carboxylic acid such as (methyl) acrylic acid and in addition the copolymer of compound more than a kind with unsaturated double-bond, monofunctional epoxy compound such as addition butyl glycidyl ether, phenyl glycidyl ether and obtain contain carboxy resin.
(3) (methyl) glycidyl acrylate, (methyl) acrylic acid 3; The copolymer of the compound with epoxy radicals and unsaturated double-bond of 4-epoxycyclohexyl methyl esters etc. and compound in addition with unsaturated double-bond, with saturated carboxylic acid reaction such as propionic acid, the secondary hydroxyl of generation react with multi-anhydride and obtain contain carboxy resin.
(4) anhydrous maleic acid etc. have the copolymer of the acid anhydrides of unsaturated double-bond and in addition compound with unsaturated double-bond, have the compound reaction of hydroxyl with butanols etc. and obtain contain carboxy resin.
(5) make multi-functional epoxy compound and saturated mono carboxylic acid reaction, the reaction of the hydroxyl of generation and saturated or unsaturated multi-anhydride and obtain contain carboxy resin.
(6) reaction of the hydroxyl polymer-containing of polyvinyl alcohol derivative etc. and saturated or unsaturated multi-anhydride and the hydroxyl that obtains and contain carboxy resin.
(7) have in multi-functional epoxy compound and saturated mono carboxylic acid and a part at least 1 alcohol hydroxyl group and with the product of the compound of 1 reactive base beyond the alcohol hydroxyl group of epoxy reaction, obtain with saturated or unsaturated multi-anhydride reaction contain carboxy resin.
The multifunctional oxetane compound and the saturated mono carboxylic acid reaction that have at least 2 oxetanes rings in (8) 1 molecules, for the primary hydroxyl in the modification oxetane resin that obtains make the reaction of saturated or unsaturated multi-anhydride and obtain contain carboxy resin.
(9) behind polyfunctional epoxy resin and the saturated mono carboxylic acid reaction, make multi-anhydride reaction and obtain contain carboxy resin further with molecule in have the compound reaction of 1 oxirane ring and obtain contain carboxy resin.
Wherein, be preferably the carboxy resin that contains of use (1), (2) and (3) especially.They can at random adjust molecular weight, glass transition temperature etc., can adjust the printability of paste, and suitably control is to the adaptation of base material.
In addition, this acid number that contains carboxy resin is preferably 40～200mgKOH/g.When containing the acid number deficiency 40mgKOH/g of carboxy resin, the cohesive force of paste reduces, and it is bad that transfer takes place when printing easily.On the other hand, when surpassing 200mgKOH/g, the viscosity of paste is too high, and needing etc. of a large amount of crosslinking agent of compounding arranged, and is difficult to give printability.45～150mgKOH/g more preferably.
It is desirable that the compounding amount of the organic binder bond beyond the polyurethane resin is added in the scope of not damaging the adaptation of ito thin film.The compounding ratio of the organic binder bond beyond the polyurethane resin is preferably in organic binder bond below the 50 quality %.When the compounding amount surpasses 50 quality %,, not preferred with the adaptation reduction of ito thin film, base material.In addition, when intaglio offset, the live width that printed article can take place is mixed and disorderly, and the characteristic of infringement paste is not preferred.More preferably below the 30 quality %.
Conductive powder in the conductive paste of this execution mode is to give the paste of the conducting channel of formation with conductivity, particularly, for example can enumerate out Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru etc.
These conductive powders are not limited to use with the form of simple substance, also can be their arbitrary alloys, they are arbitrary as nuclear or tectal polylayer forest.And then also can use tin oxide (SnO
2), indium oxide (In
2O
3), ITO oxides such as (Indiumu Tin Oxide).
As its shape, can use different shapes such as spherical, sheet, dendroid, particularly consider printability, when dispersed, be preferably spherical conductive powder and use as main body.
This conductive powder with the non-volatile component of conductive paste (in the drying process not from paste volatilization and remain in the composition of film) be that benchmark is preferably 85～95 quality %.During less than 85 quality %, be difficult to obtain sufficient conductivity, when surpassing 95 quality %, be difficult to the shape that obtains sufficient printability, is difficult to keep conducting channel.90～94 quality % more preferably.
Under the situation of using spherical conductive powder, the particle diameter of conductive powder is preferably 0.1～5 μ m in the average grain diameter of electron microscope (SEM) with 10000 times of observations, 10 conductive powders at random.During average grain diameter less than 0.1 μ m, be difficult between the conductive powder come in contact, conductivity reduces.On the other hand, when average grain diameter surpasses 5 μ m, the craspedodrome property at the line edge when being difficult to obtain to print.0.4～2 μ m more preferably.
In addition, it is the conductive powder of 0.5～3.5 μ m that the average grain diameter of measuring through MacxKerodt thunder gram particle footpath appearance (microtrac) is preferably used size.
In addition, under the situation of the conductive powder of use sheet,, be preferably 0.1～10 μ m with the average grain diameter of electron microscope (SEM) with 10000 times of observations, 10 conductive powders at random.During average grain diameter less than 0.1 μ m, be difficult between the conductive powder come in contact, conductivity reduces.On the other hand, when average grain diameter surpasses 10 μ m, the craspedodrome property at the line edge when being difficult to obtain to print.0.4～5 μ m more preferably.
In addition, it is the conductive powder of 0.5～7 μ m that the average grain diameter of measuring through MacxKerodt thunder gram particle footpath appearance (microtrac) is preferably used size.
Be preferably silver powder as this conductive powder, at this moment, the specific area of silver powder is preferably 0.01～2m
2/ g.The not enough 0.01m of specific area
2During/g, when preserving, cause sedimentation easily, on the other hand, specific area surpasses 2m
2During/g, the oil suction quantitative change is big, paste mobile impaired.0.5～1.5m more preferably
2/ g.
Organic solvent in the conductive paste of this execution mode is used to give good printability.As this organic solvent; It is the organic solvent that just can not dissolve with polyurethane resin generation chemical reaction; Particularly for the drying that prevents paste in the printing process such as intaglio offset, keep transfer printing property; Need make organic solvent contained in the conductive paste comprise high boiling solvent, the boiling point of said high boiling solvent under 760mmHg is 240～330 ℃ scope.
When the boiling point of high boiling solvent under 760mmHg was lower than 240 ℃, the paste that is transferred to blanket in the Off operation-Set operation during printing can be dry easily, becomes in the Set operation not to the base material transfer printing.On the other hand, when being higher than 330 ℃, though can be suppressed at the drying in the above-mentioned printing process, in the drying process after the printing, solvent remains in the rising that causes resistance value in the printed article, the problems such as reduction of adaptation easily.More preferably 240 ℃～300 ℃.
In addition, the ratio of the high boiling solvent in the contained organic solvent of conductive paste is preferably 30～90 quality %.The ratio of high boiling solvent can cause printed article to print forr a short time than the version size during less than 30 quality %, is difficult to obtain good printed article.On the other hand, during greater than 90 quality %, in printed article, be easy to generate and ooze out, still be difficult to obtain good printed article.The ratio of 30～80 quality % more preferably.
As this high boiling solvent; Can enumerate out diamyl benzene (boiling point: 260～280 ℃), 3 penta benzene (boiling point: 300～320 ℃), Decanol (boiling point: 255～259 ℃), diethylene glycol (boiling point: 245 ℃), diethylene glycol monobutyl ether acetate (boiling point: 247 ℃), dibutyl ethylene glycol ether (boiling point: 255 ℃), diethylene glycol monoacetate (boiling point: 250 ℃), triethylene glycol (boiling point: 276 ℃), triethylene glycol monomethyl ether (boiling point: 249 ℃), Triethylene glycol ethyl ether (boiling point: 256 ℃), triethylene glycol butyl ether (boiling point: 271 ℃), TEG (boiling point: 327 ℃), TEG monobutyl ether (boiling point: 304 ℃), tripropylene glycol (boiling point: 267 ℃), tripropylene glycol monomethyl ether (boiling point: 243 ℃), 2; 2; 4-trimethyl-1,3-pentanediol mono isobutyrate (boiling point: 253 ℃) etc.In addition; As oil is hydro carbons; Also can enumerate out Nippon Petrochemicals Co.; Ltd. No. 4 (boiling point: 240～265 ℃), No. 5 (boiling points: 275～306 ℃) of AF Solvent, No. 6 (boiling point: 296～317 ℃), No. 7 (boiling point: 259～282 ℃) and No. 0 Solvent H (boiling point: 245～265 ℃) etc. that make, also can contain as required they more than 2 kinds.In the middle of them, be fit to use triethylene glycol derivative or tripropylene glycol derivative.
As the organic solvent beyond the above-mentioned high boiling solvent, for example can enumerate out toluene, xylenes, ethyl acetate, butyl acetate, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, 1-butanols, DAA, diethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, terpineol, MEK, carbitol, carbitol acetate, BC etc.They can use separately or mix and use more than 2 kinds.
During especially for intaglio offset, in order to obtain good printability, the viscosity of the conductive paste of this execution mode is preferably 50～1000dPas in the measured value (25 ℃) based on cone and plate viscometer.During viscosity deficiency 50dPas, the ratio of the organic solvent in the conductive paste is too much, and the reduction of transfer printing property is difficult to carry out good print.On the other hand, when viscosity surpasses 1000dPas, be difficult to be filled into intaglio plate, and with blade coating machine scrape getting property variation, be easy to generate dirty edition (paste is attached to non-setting-out part).100～650dPas more preferably.In addition, also can when printing, suitably dilute.
In addition, the dynamic fusible viscosity value of representing this conductive paste is preferably 5～35.During viscosity value less than 5, the metastatic when printing sometimes is poor, and press quality is worsened.On the other hand, viscosity value surpasses at 35 o'clock, is printed plucking (picking is printed the breakage of thing), the paperboard (jam is printed thing and blocks printing machine) of thing when occurring in printing easily.More preferably 10～30.In addition, viscosity value be to use rotation viscometer (general name: inkometer (inkometer)), the value of under 30 ℃, the condition of 400 rotating speeds, measuring.
In addition, in the conductive paste of this execution mode,, improve solvent resistance, the adaptation of formed conducting channel, preferably further contain crosslinking agent in order to form three-dimensional grid chain structure.
As crosslinking agent, only otherwise make the printability deterioration, can make its crosslinked getting final product with the polyurethane resin reaction.As this crosslinking agent; So long as do not limit through the resin that is heating and curing is just special; For example can enumerate out epoxy resin, phenolic resins, melmac, alkyd resins, mylar, acrylic resin, polyimide resin and their modified resin, they can use separately or make up more than 2 kinds and use.In addition, can enumerate except that the oxetane compound etc. that has at least 2 oxa-cyclobutyl in the molecule.
In this crosslinking agent, preferably be contained in the epoxy resin that has 2 above glycidyls in 1 molecule at least.As this epoxy resin; For example can enumerate out the known epoxy resin such as epoxy resin, alicyclic epoxy resin of phenolic varnish type, xenol type, bis-xylene phenol type, triphenol methylmethane type, N-glycidol ether type, the N-glycidol ether type of bisphenol A-type, hydrogenated bisphenol A type, Bisphenol F type, bisphenol S type, phenol phenolic varnish type, cresols phenolic varnish type, bisphenol-A; Be not limited to specific epoxy resin; In addition, they can use separately or make up more than 2 kinds and use.Wherein, through using the epoxy resin of epoxide equivalent (the gram number of resin that contains 1 gram equivalent epoxy radicals) in 100～300 scope, can efficient be crosslinked well with a spot of interpolation, therefore preferred.
As far as the compounding rate of these epoxy resin, per 100 mass parts polyurethane resins are that 1～100 mass parts is fit to, and are preferably 5～40 mass parts.
In addition; Except that these; Also can compounding be used to promote the curing catalysts of the amines, imdazole derivatives etc. of the reaction of polyurethane resin and crosslinking agent, additives such as compounding metal dispersion, thixotropy imparting agent, antifoaming agent, levelling agent, plasticizer, oxidation inhibitor, matal deactivator, coupling agent, filler in the scope of not damaging printability.
Use this conductive paste, form conducting channel as follows.
At first, on ito thin film, be formed with the filming of pattern of conductive paste.At this moment, as printing process, can be silk screen printing, hectographic printing, intaglio offset etc., not special the qualification.
Be formed on filming 60～120 ℃ of dryings after 1～60 minute on the ito thin film with this,, make curing of coating, form conducting channel through 100～250 ℃ of following low temperature calcinations 1～60 minute.
Through such formation conducting channel, both adaptation of part that etches with ITO in the ito thin film and ITO layer is excellent, can obtain good electrical conductivity.And touch panel through this conducting channel being used for electronic installations such as dull and stereotyped terminal etc. can obtain high reliability and conductive characteristic.
In addition, as stated, in conductive paste, comprise under the situation of high boiling solvent in the contained organic solvent, in intaglio offset, can obtain good printability, the boiling point of said high boiling solvent under 760mmHg is 240～330 ℃.Use contains the conductive paste of this high boiling solvent, on base material, forms circuit as follows.
Fig. 1 is the sketch map of expression intaglio offset.
As shown in Figure 1, be that the recess 11a that forms according to desired pattern form on the intaglio plate 11 goes up filled conductive property paste 12.Then, transfer printing (primary transfer) on as the organosilicon blanket 13 of intermediate transfer body.Further be transferred to carry and put on the base material on the objective table 14 15 being transferred to conductive paste on the organosilicon blanket 13, film 16 thereby form.
As base material used herein,, can use the flexible substrate of resin film etc. except that printed circuit board (PCB), the glass substrate.In addition, used intaglio plate is made a plate through photo plate-making, laser engraving etc. are implemented in the surface of the barrel that is made up of copper, 42 alloys, glass etc., lithographic plate.As required, also can implement chromium plating processing, DLC (diamond-like carbon film) processing, the durability of intaglio plate is improved.
Through above-mentioned printing will be formed on the base material film 16 80～200 ℃ down dry or solidified 1～60 minute, thereby form conducting channel.
Embodiment
Below, embodiment and comparative example are shown this execution mode are carried out bright specifically, but the present invention is not limited to these embodiment.In addition, following " % " all is quality criteria when not specifying, in addition, weight average molecular weight is to use gel carrier liquid chromatography (HLC-8120 GPC TOSOH CORPORATION manufacturing) to obtain with the value of polystyrene conversion.
Synthesizing of organic binder bond resin
Synthetic example 1
In the reaction vessel that has agitating device, thermometer, condenser; Add 288g (0.36mol) as polyol component by 1; 5-pentanediol and 1; The PCDL that the 6-hexylene glycol derives (Asahi Kasei Chemicals Corporation manufacturing, T5650J, number-average molecular weight 800), 45g (0.09mol) bisphenol type epoxy propane addition product glycol (ADEKA CORPORATION manufactured, BPX33, number-average molecular weight 500), 81.4g (0.55mol) as the dimethylolpropionic acid of dimethylolalkanoic acids and 11.8g (0.16mol) as the n-butanol of molecular weight regulator (reaction terminating agent), 250g carbitol acetate (Daicel Corporation manufacturing) as solvent, at 60 ℃ with whole raw materials dissolvings.
Polyol component is stirred on the limit, and the limit drips the trimethyl hexamethylene diisocyanate of 200.9g (1.08mol) as polyisocyanates through dropping funel.After dripping termination, continue reaction, confirm the absorption spectrum (2280cm of NCO in the infrared absorption spectrum while under 80 ℃, stir
-1) disappear, reaction finishes.Add carbitol acetate so that solid constituent becomes 60%, obtain polyurethane resin solution (varnish 1).
The weight average molecular weight of the many polyurethane resins that obtain is 18300, and the acid number of solid constituent is 50.3mgKOH/g.
Synthetic example 2
In the reaction vessel that has agitating device, thermometer, condenser; Add 360g (0.45mol) as polyol component by 1; 5-pentanediol and 1; The PCDL that the 6-hexylene glycol derives (Asahi Kasei Chemicals Corporation manufacturing, T5650J, number-average molecular weight 800), 81.4g (0.55mol) as the dimethylolpropionic acid of dimethylolalkanoic acids and 11.8g (0.16mol) as the n-butanol of molecular weight regulator (reaction terminating agent), 250g carbitol acetate (Daicel Corporation manufacturing) as solvent, at 60 ℃ with whole raw materials dissolvings.
Polyol component is stirred on the limit, and the limit drips the trimethyl hexamethylene diisocyanate of 200.9g (1.08mol) as polyisocyanates through dropping funel.After dripping termination, continue reaction, confirm the absorption spectrum (2280cm of NCO with infrared absorption spectrum while under 80 ℃, stir
-1) disappear, finish reaction.Add carbitol acetate so that solid constituent becomes 60wt%, obtain polyurethane resin solution (varnish 2).
The weight average molecular weight of the polyurethane resin that obtains is 21200, and the acid number of solid constituent is 48.0mgKOH/g.
Synthetic example 3
In the flask that has thermometer, blender, dropping funel and reflux condenser; Add methyl methacrylate and acrylic acid according to 0.80: 0.20 mol ratio; Adding is as the tripropylene glycol monomethyl ether of solvent, as the azodiisobutyronitrile of catalyst, under nitrogen atmosphere; Stirred 6 hours at 80 ℃, obtain the acrylic resin soln that nonvolatile component is 40 weight % (varnish 3).
The number-average molecular weight of the resin that obtains is 15000, and weight average molecular weight is about 40000, and the acid number of solid constituent is 97mgKOH/g.
Synthetic example 4
In the reaction vessel that has agitating device, thermometer, dropping funel, condenser; Add methyl methacrylate and acrylic acid according to 0.80: 0.20 mol ratio; Adding is as the triethylene glycol butyl ether (boiling point: 271 ℃) of solvent, as the azodiisobutyronitrile of catalyst; Under nitrogen atmosphere, stirred 6 hours at 80 ℃, obtain the acrylic resin soln that nonvolatile component is 40wt% (varnish 4).The number-average molecular weight of the resin that obtains is 15000, and weight average molecular weight is about 40000, and acid number is 97mgKOH/g.
Synthetic example 5
Triethylene glycol butyl ether is replaced being diethylene glycol ether acetate alone, in addition, according to obtaining the acrylic resin soln that nonvolatile component is 40wt% (varnish 5) with synthetic example 4 identical methods.The number-average molecular weight of the resin that obtains is 15000, and weight average molecular weight is about 42000, and acid number is 98mgKOH/g.
The ITO adaptation is estimated
The making of conductive paste
According to each composition of the formula rate shown in the table 1 (mass ratio) compounding, grind with triple-roller mill, obtain the conductive paste of embodiment 1～3, comparative example 1,2.In addition, the viscosity of paste is adjusted into 150dPas.
Table 1
*1: spherical silver powder (average grain diameter: 0.8 μ m, specific area: 1.0m
2/ g)
*(Mitsubishi chemical Co., Ltd makes 2:jER828, epoxide equivalent=190g/eq)
*(Mitsubishi chemical Co., Ltd makes 3:jER1001, epoxide equivalent=500g/eq)
*4:CUREZOL 2E4MZ (Shikoku Chem's manufacturing)
The mensuration of resistivity value
Test pattern with silk screen printing formation live width 1mm, length 40cm uses the heated air circulation type drying oven, under 120 ℃, carries out 30 minutes heat treated.Use test device (milliohm high tester 3540; HIOKI E.E.CORPORATION makes) measure the resistance value of the conducting channel that obtains, calculate resistivity value from the film thickness gauge of conducting channel.
Table 2
Adaptation is estimated
Test is with the making of base material
On the ito thin film (Supreme Being people changes into manufactured) that the part with the ITO layer etches, use 200 purpose silk screen versions, form the full pattern of the conductive paste of embodiment 1～3, comparative example 1,2.Then, through in 120 ℃ baking oven, carrying out 30 minutes heat treated, on ito thin film, make the test that is formed with conducting channel and use film.
Initial driving fit evaluation
The test that obtains with film on, form with interval 1mm 10 lattice * 10 lattice total 100 lattice draw lattice, carry out adhesive tape and peel off (cellophane tape peeling).And, the situation of peeling off of filming of the part that visual valuation ITO and ITO etch.Metewand is as follows.
Zero: film is used in the test of not peeling off fully.
△: film is used in the test that a part is peeled off.
*: film is used in the test of peeling off more than 50%.
Driving fit evaluation after the hot and humid processing
The substrate that obtains is put into the hot and humid groove of 85 ℃-85%RH, carry out the processing of 96hr after, the test that obtains with film on, form with interval 1mm 10 lattice * 10 lattice total 100 lattice draw lattice, carry out adhesive tape and peel off.And, the situation of peeling off of filming of the part that visual valuation ITO and ITO etch.Metewand is as follows.
Zero: film is used in the test of not peeling off fully.
△: film is used in the test that a part is peeled off.
*: film is used in the test of peeling off more than 50%.
Table 3
Like table 2, can know shown in 3, the polyurethane resin through using this execution mode is as organic binder bond, can in conducting channel, obtain good electrical conductivity, and improves the ITO layer of conducting channel and the adaptation of the part that etches with ITO.
Printability is estimated
The making of conductive paste
Each composition of formula rate shown in table 4 (mass ratio) compounding grinds with triple-roller mill, obtains the conductive paste of embodiment 4～7, comparative example 3～5.In addition, the viscosity of paste is adjusted into 150dPas.In addition, viscosity value is between 10～25 (30 ℃, 60 seconds values).
Table 4
[remarks]
With reference to table 1 remarks
The ratio of the high boiling solvent in the contained organic solvent of the conductive paste of embodiment 4～7 and comparative example 3～5 is as shown in table 5.
Table 5
Evaluation based on the printability of simple and easy photogravure
With the steel blade coating machine form wired/μ m, version are dark at interval=70/30: fill each conductive paste that obtains in the recess of the glass intaglio plate of the striped of 10 μ m (stripe) pattern.
Then, this glass intaglio plate is attached on the blanket cylinder that the organic silicon rubber by 30 ° of rubber hardnesses forms, makes the conductive paste that is filled in recess be transferred to (Off operation, primary transfer) on the blanket cylinder surface.Make the conductive paste transfer printing on the blanket cylinder surface after last 30 second, the conductive paste (Set operation, secondary transfer printing) on transfer printing blanket cylinder surface on the surface of the soda-lime glass of thickness 1.8mm.Carry out following evaluation to the printed article that obtains like this.
Printability 1: the evaluation of craspedodrome property
With the observation by light microscope transfer printing glass substrate of each conductive paste, estimate the craspedodrome property of printed article.Metewand is following.Evaluation result is illustrated in the table 6.
Zero: craspedodrome property is good.
△: be short of craspedodrome property a little.
*: obviously be short of craspedodrome property, broken string is arranged.
Printability 2: the evaluation of live width reproducibility
With the observation by light microscope transfer printing glass substrate of conductive paste, estimate the live width of printed article.Metewand is following.Evaluation result is illustrated in the table 6.
Zero: live width is identical with the glass intaglio plate, and perhaps relative version scale error is in ± 10%.
△: the error of version size live width is above ± 10% and in ± 30% relatively.
*: the error of version size live width surpasses ± 30% relatively.
Printability 3: the transfer printing property evaluation after placing 60 seconds on the blanket
After Off operation (primary transfer), carry out Set operation (secondary transfer printing) after 60 seconds, whether visual valuation is residual on the blanket cylinder surface has a conductive paste.Metewand is following.Evaluation result is illustrated in the table 6.
Zero: on blanket surface, do not have remaining conductive paste (100% transfer printing).
△: remaining on blanket surface top have a conductive paste.
*: remaining on whole of blanket have a conductive paste.
The mensuration of resistivity value
The test pattern of printing live width 1mm, length 40cm uses the heated air circulation type drying oven, under 120 ℃, carries out 30 minutes heat treated.Use test device (milliohm high tester 3540; HIOKI E.E.CORPORATION makes) measure the resistance value of the printed article that obtains, calculate resistivity value from the film thickness gauge of printed article.
Table 6
As shown in table 6, in the embodiment 4～7 of the conductive paste that uses this execution mode, can know that the live width reproducibility of the conducting channel of printing, craspedodrome property are all excellent, even and the long transfer printing property that also can keep paste of the time from the Off operation to the Set operation.
As an example of the printed article image of the conductive paste that uses this execution mode, at the optical microscope photograph of the printed article (conducting channel) of embodiment shown in Fig. 27.As shown in Figure 2, the live width reproducibility is with respect to version size 70 μ m, and the live width of printed article (conducting channel) is 64～67 μ m (errors :-8.6%～-4.3%), can know that its craspedodrome property is also good.
On the other hand, can find out that under the situation of the length of the time from the Off operation to the Set operation, also can not guarantee transfer printing property though do not contain the comparative example 3 of the polyurethane resin of this execution mode, the printed article that obtains lacks live width reproducibility, craspedodrome property.In addition, in the polyurethane resin of this execution mode, comparative example 4 that high boiling solvent does not all contain, can find out that can cause paste dry when being placed on the blanket for a long time, transfer printing property is impaired.In addition, in the comparative example 5 of the high boiling solvent that does not contain this execution mode, paste is dry on blanket, the evaluation that can not print.
In Fig. 3, the optical microscope photograph of the printed article (conducting channel) of the conductive paste that has used comparative example 3 is shown.As shown in Figure 3, the live width reproducibility is with respect to version size 70 μ m, and the live width of printed article (conducting channel) is that (error :-17.1%～-11.4%), about craspedodrome property, printed article craspedodrome property has fluctuating to 58～62 μ m, can know and be short of craspedodrome property a little.
Claims (11)
1. a conductive paste is characterized in that, it contains polyurethane resin and conductive powder and organic solvent.
2. conductive paste according to claim 1 is characterized in that, said polyurethane resin comprise weight average molecular weight be 500～100,000 contain the carboxyl polyurethane resin.
3. conductive paste according to claim 2 is characterized in that, its further contain in 1 molecule, comprise 2 above glycidyls at least epoxy resin as crosslinking agent.
4. the formation method of a conducting channel is characterized in that, the filming of pattern of each described conductive paste in the requirement 1～3 of having the right that on ito thin film, form to be shaped,
Make said filming 80～200 ℃ of dry down or curing.
5. conductive paste according to claim 1 is characterized in that said organic solvent comprises the high boiling solvent of 30～90 quality %, and the boiling point of said high boiling solvent under 760mmHg is 240～330 ℃.
6. conductive paste according to claim 5 is characterized in that, said polyurethane resin comprise weight average molecular weight be 500～100,000 contain the carboxyl polyurethane resin.
7. conductive paste according to claim 6 is characterized in that, its further contain in 1 molecule, comprise 2 above glycidyls at least epoxy resin as crosslinking agent.
8. the formation method of a conducting channel is characterized in that, the filming of pattern of each described conductive paste in the requirement 5～7 of having the right that on ito thin film, form to be shaped,
Make said filming 80～200 ℃ of dry down or curing.
9. the formation method of a conducting channel; It is characterized in that; On version, fill each described conductive paste in the claim 5～7; With said conductive paste once transfer printing on the blanket cylinder surface of filling, with said conductive paste secondary transfer printing on substrate surface of primary transfer, the said conductive paste that makes secondary transfer printing is 80～200 ℃ of dry down or curing.
10. a conducting channel is characterized in that, it uses the described conductive paste of claim 1 and forms.
11. an electronic installation is characterized in that, the conducting channel that comprises polyurethane resin and conductive powder that it possesses ito thin film and on this ito thin film, forms.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-078848 | 2011-03-31 | ||
| JP2011078848A JP5767498B2 (en) | 2011-03-31 | 2011-03-31 | Conductive paste |
| JP2011-280005 | 2011-12-21 | ||
| JP2011280005A JP6001265B2 (en) | 2011-12-21 | 2011-12-21 | Conductive paste |
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| CN102737750A true CN102737750A (en) | 2012-10-17 |
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| KR (1) | KR101339618B1 (en) |
| CN (1) | CN102737750A (en) |
| TW (2) | TWI570197B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104751941A (en) * | 2013-12-25 | 2015-07-01 | 株式会社则武 | Thermosetting conductive paste |
| CN105612585A (en) * | 2013-09-30 | 2016-05-25 | 东洋纺株式会社 | Electro-conductive paste, electro-conductive film, electro-conductive circuit, electro-conductive laminate, and touch panel |
| CN106279740A (en) * | 2016-08-19 | 2017-01-04 | 清华大学深圳研究生院 | A kind of resin compound, nesa coating and preparation method thereof |
| CN110099963A (en) * | 2016-12-27 | 2019-08-06 | 纳美仕有限公司 | Resin combination, solidfied material, conductive film, conductive pattern and clothes |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160126169A (en) * | 2015-04-22 | 2016-11-02 | 삼성에스디아이 주식회사 | Composition for forming solar cell and electrode prepared using the same |
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- 2012-03-23 TW TW101110132A patent/TWI570197B/en active
- 2012-03-23 TW TW103136441A patent/TW201505034A/en unknown
- 2012-03-29 KR KR1020120032098A patent/KR101339618B1/en active IP Right Grant
- 2012-03-30 CN CN2012100920090A patent/CN102737750A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105612585A (en) * | 2013-09-30 | 2016-05-25 | 东洋纺株式会社 | Electro-conductive paste, electro-conductive film, electro-conductive circuit, electro-conductive laminate, and touch panel |
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| CN104751941A (en) * | 2013-12-25 | 2015-07-01 | 株式会社则武 | Thermosetting conductive paste |
| CN104751941B (en) * | 2013-12-25 | 2018-04-13 | 株式会社则武 | Heat-curing type conductive paste |
| CN106279740A (en) * | 2016-08-19 | 2017-01-04 | 清华大学深圳研究生院 | A kind of resin compound, nesa coating and preparation method thereof |
| CN110099963A (en) * | 2016-12-27 | 2019-08-06 | 纳美仕有限公司 | Resin combination, solidfied material, conductive film, conductive pattern and clothes |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI570197B (en) | 2017-02-11 |
| TW201505034A (en) | 2015-02-01 |
| KR20120112157A (en) | 2012-10-11 |
| TW201247808A (en) | 2012-12-01 |
| KR101339618B1 (en) | 2013-12-10 |
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