CN103571275B - Conductive ink composition, the manufacture method of conductive pattern and electroconductive circuit - Google Patents
Conductive ink composition, the manufacture method of conductive pattern and electroconductive circuit Download PDFInfo
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- CN103571275B CN103571275B CN201310341926.2A CN201310341926A CN103571275B CN 103571275 B CN103571275 B CN 103571275B CN 201310341926 A CN201310341926 A CN 201310341926A CN 103571275 B CN103571275 B CN 103571275B
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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
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
-
- 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
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
Abstract
The present invention provides low viscosity and printing adaptability is excellent, can solidify under more low temperature shorter time, can obtain having high conductivity and the conductive ink composition of the pattern of fine, the manufacture method of conductive pattern and electroconductive circuit.Described conductive ink composition is characterised by, described conductive ink composition contains electroconductive stuffing, compositions of thermosetting resin, organic solvent as required composition, contains the organic compound with least one functional group selecting from the group being made up of phosphate group, phosphate group, bound phosphate groups further.
Description
Technical field
The present invention relates to for formed the conductive ink composition of conductive film, the manufacture method of conductive pattern and
Electroconductive circuit.
Background technology
As the conductive pattern such as conducting channel, electrode used in touch screen, Electronic Paper and various electronic unit
Forming method is it is known that print process or etching method.
In the case that conductive pattern is formed by etching method, photoetching shape is passed through on the substrate being deposited with various metal films
It is necessary to unwanted deposited metal film is passed through chemistry or electrochemical dissolution removing after becoming the resist film of patterning, finally will
Resist film removes, and this operation is complicated in the extreme and not can manufacture.
On the other hand, desired pattern can be produced in a large number with low cost by print process, passing through further will
Printing dried coating film or solidification can easily give electric conductivity.
As these mode of printings, according to the line width of the pattern being formed, thickness, speed of production it is proposed that flexographic printing,
Silk screen printing, intaglio printing, intaglio offset printing, ink-jet etc..
As printed patterns, the viewpoint such as improve from the miniaturization of electronic equipment, design and consider it is desirable to form line width 50
The conductive pattern of the fine below μm.
In addition, the volume high in order to tackle the slimming to electronic equipment, lightweight, the requirement raising of softness, productivity ratio
Volume printing it is desirable to print on a plastic film and pass through burning till between low-temperature short-time can get high conductivity, base material adaptation,
The conductive ink of film hardness etc..Further it is desirable in plastic sheeting, in cheap and transparent high PET（Poly- terephthaldehyde
Sour glycol ester）Thin film, PET film defines carry out on the non-heat-resistant base material as transparent conductive film of ito film
The conductive ink of above-mentioned physical property during printing, can be obtained.
In such a case it is known that various conductive ink composition is containing silver powder, being heating and curing property（Thermosetting
Resin combination）The heat-curing type conductive paste feed composition of composition and solvent, above-mentioned being heating and curing property（Thermosetting resin group
Compound）Composition comprises closure polyisocyanate compounds and thermoplastic resin, and this thermoplastic resin is from by epoxy resin, line
At least one above thermoplastic resin selecting in the group that shape polyester resin and chloride vinylacetate copolymer are formed
（Patent documentation 1～6）.
However, the viscosity of these conductive ink compositions is all higher, printing adaptability is not excellent.In addition, in order to only change
Good printing adaptability, can add surfactant etc. in conductive ink composition, although majority of case is printing
Adaptability can be improved but can damage electric conductivity in turn.
Patent documentation 1：Japanese Unexamined Patent Publication 2002-161123
Patent documentation 2：Japanese Unexamined Patent Publication 2006-302825
Patent documentation 3：Japanese Unexamined Patent Publication 2009-26558
Patent documentation 4：Japanese Unexamined Patent Publication 2009-24066
Patent documentation 5：Japanese Unexamined Patent Publication 2012-38614
Patent documentation 6：Japanese Unexamined Patent Publication 2012-38615
Content of the invention
Problems to be solved by the invention
The invention solves the problems that problem for providing a kind of low viscosity and printing adaptability is excellent, can obtain with high connductivity
The conductive ink composition of the pattern of property.
Method for solve problem
The present inventor etc. in order to solve above-mentioned problem, further investigation it is found that：By in existing conductive ink
The compound with phosphate group is comprised, then the height that also will not damage the conductive pattern obtaining after heat cure is led in compositionss
Electrically, obtain the conductive ink composition that can form low viscosity and the excellent conductive pattern of printing adaptability, thus complete
Become the present invention.
I.e. the present invention provides a kind of conductive ink composition it is characterised in that being containing electroconductive stuffing, thermosetting tree
Oil/fat composition, organic solvent, as the conductive ink composition of essential component, contain further and have from by phosphate group, phosphorus
The organic compound of at least one functional group selecting in the group that acid salt group, bound phosphate groups are formed.
In addition, the present invention provides a kind of manufacture method of conductive pattern, by above-mentioned conductive ink composition coating
On non-heat-resistant base material, heated.
Further, the present invention provides a kind of electroconductive circuit, and it is included on non-heat-resistant base material and is formed with above-mentioned conduction
The conductive pattern of the cured film of property ink composite.
The effect of invention
Have from by phosphate group, phosphate group, phosphate-based because the conductive ink composition of the present invention contains
The organic compound of at least one functional group selecting in the formed group of group, therefore can achieve low viscosity and printing adaptability is excellent
Different so especially significant effect.Thus, even if it is also possible to manufacture in the case of using the non-heat-resistant base material such as PET film
The conductive pattern of high conductivity.
Specific embodiment
（Electroconductive stuffing）
As electroconductive stuffing used in the present invention, it is possible to use known material.For example can enumerate nickel, copper, gold,
Silver, aluminum, zinc, stannum, lead, chromium, platinum, palladium, tungsten, molybdenum etc., and the chemical combination of these alloys of more than two kinds, mixture or these metals
Thing and there is material of satisfactory electrical conductivity etc..Especially because stable electric conductivity can easily be realized by argentum powder, in addition conduction of heat is special
Property also good, therefore preferably.
（Argentum powder）
Be used argentum powder as the electroconductive stuffing of the present invention in the case of, as mean diameter, preferably use intermediate value grain
Footpath（D50）Spherical argentum powder for 0.1～10 μm, more preferably 0.1～3 μm.Within the range, with containing from by phosphate group,
The organic compound of at least one functional group selecting in the group that phosphate group, bound phosphate groups are formed is used in combination, and can make
The improvement of the mobility of conductive ink composition is bigger, and mobility is better, in flexographic printing, silk screen printing, intaglio plate
In the specific printing process such as printing or intaglio offset printing, even if in the case of continuously being printed on these printer,
Also be readily obtained be difficult to break down, stably good conductive pattern.
As this argentum powder, for example, can enumerate AG2-1C（DOWA electronics（Strain）System, mean diameter D50：0.8μm）、
SPQ03S（Mitsui Metal Co., Ltd. mine（Strain）System, mean diameter D50：0.5μm）、EHD（Mitsui Metal Co., Ltd. mine（Strain）System, mean diameter
D50：0.5μm）、SYLVESTER C-34（（Strain）Moral power chemical research is made, mean diameter D50：0.35μm）、AG2-1（DOWA
Electronics（Strain）System, mean diameter D50：1.3μm）、SYLVESTER AgS-050（（Strain）Moral power chemical research is made, average grain
Footpath D50：1.4μm）Deng.
Electroconductive stuffing can also be in advance containing from by phosphate group, phosphate group, bound phosphate groups with described later
The electroconductive stuffing that the organic compound surface of at least one functional group selecting in the group being formed is coated to and is formed.
In the conductive ink composition of the present invention, the ratio of the compositions of thermosetting resin of electroconductive stuffing and postscript
It is not particularly limited, but from the viewpoint of the electric conductivity of the conductive pattern obtaining, preferably according in terms of mass conversion every 100
Part electroconductive stuffing compositions of thermosetting resin is that 3～15 parts of mode is modulated.
（Compositions of thermosetting resin）
In the present invention using compositions of thermosetting resin.So-called compositions of thermosetting resin, it is simply by can not solidify
Host and firming agent combine the compositionss constituting.With regard to host and firming agent, even if according to by both mixing at normal temperatures
Also will not react, each select by way of heating just proceeds by solidification.As host, it is used mostly and itself has into
The thermoplastic resin of film, because be readily obtained the conductive pattern of fine.As this compositions of thermosetting resin, for example
Can enumerate：As the epoxide of host and combining of the epoxy curing agents such as anhydride, amine, phenol resin, as host
The Chlorovinyl-acetate vinyl resin containing hydroxyl, the polyester resin containing hydroxyl, the acrylic resin containing hydroxyl etc.
The thermoplastic resin of the film property containing hydroxyl is combined with isocyanate curing agent as blocked polyisocyanate.In modulation
During compositions of thermosetting resin, above-mentioned illustrated host, firming agent can be used alone it is also possible to and with more than two kinds.
As the commercially available product of the thermoplastic resin of the film property containing hydroxyl, such as the vinyl chloride-second containing hydroxyl
Vinyl acetate resin, can enumerate day letter chemical industry SOLBIN serial, as the polyester resin containing hydroxyl, Japan can be enumerated
BYRON series processed of weaving etc..
Particularly preferably the combining, because can make of blocked polyisocyanate and the film property thermoplastic resin with hydroxyl
The dispersibility of electroconductive stuffing is excellent, contains this combination more in the composition, and its result is can to improve electric conductivity further,
And the excellent adhesion to base material during solidification.This adaptation, is the nonrefractory of softness in the object forming conductive pattern
Property base material in the case of, in terms of improving the bendability of the electrical and electronic parts being provided with electroconductive circuit, can be highly integrated
Change aspect is extremely advantageous.
（Blocked polyisocyanate）
Blocked polyisocyanate using in the present invention, making sealer thermal dissociation and produce free isocyanate groups by
Polyisocyanate compounds and sealer are constituted.
As the species of polyisocyanate compounds, it is not particularly limited, can be aromatic series, aliphatic, alicyclic two different
Cyanate, 2 or 3 aggressiveness being obtained by the modification of diisocyanate, the compound containing terminal isocyanate group etc..Can be independent
Using can also be used in combination.As aromatic diisocyanate, for example, can enumerate 2,4 toluene diisocyanate, 2,6- toluene two different
Cyanate, diphenyl methane -4,4 '-diisocyanate, diphenyl methane -2,4 '-diisocyanate, dianisidine two Carbimide.
Ester etc..As aliphatic diisocyanate, for example, can enumerate Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,5- pentamethylene two isocyanide
Acid esters, 1,6- hexamethylene diisocyanate（Following HMDI）, 2,2,4- trimethyl -1,6- hexamethylene diisocyanate etc..
As alicyclic diisocyanate, for example, can enumerate lysinediisocyanate, isophorone diisocyanate（Below
IPDI）, 1,3- double（Isocyanatomethyl）- hexamethylene, HMDI etc., can arrange further
Lift 2 or 3 aggressiveness being obtained by the modification of these diisocyanate.Biuretized, isocyanide urea can be enumerated as modified method
Esterification etc..Or can enumerate above-mentioned two or polyisocyanate compounds and such as ethylene glycol, propylene glycol, trihydroxy methyl
What propane, ethanolamine, PEPA, polyether polyol, polyamide isoreactivity reactive hydrogen compound obtained contains terminal isocyanate
Compound of perester radical etc..
As sealer, for example, can enumerate the known usual sealer such as phenol, methyl ethyl ketoxime, sodium sulfite.To
Glass, metal, silicon dioxide or pottery etc. are arranged on by the conductive pattern that the conductive ink composition of the present invention is formed
In the case of on heat-resistant material, as these sealers, it is possible to use any material, but it is being disposed at PET film, PP
In the case of on the non-heat-resistant base materials such as thin film, transparent ITO electrode thin film, preferably use sealer and dissociate at lower temperatures and make
The blocked polyisocyanate that NCO dissociates.Particularly be used on base material PET film as plastic sheeting in the case of,
As long as containing temperature when employing NCO generation in conductive ink composition as 70～125 DEG C
The blocked polyisocyanate compound of sealer, then do not produce warpage etc. on a pet film, can be formed on electric conductivity figure
Case.
As such sealer that can dissociate at lower temperatures, activity methene compound or pyrazoles chemical combination can be enumerated
Thing.As activity methene compound, isopropylidene malonate can be enumerated（meldrum′s acid）, dialkyl malonate,
Acetacetic acid alkyl ester, 2- acetoacetic acid ethylmethyl acrylate, acetylacetone,2,4-pentanedione, ethyl cyanoacetate etc., as pyrazoles chemical combination
Thing, can enumerate pyrazoles, 3，5-dimethylpyrazole, 3- methylpyrazole, 4- benzyl -3，5-dimethylpyrazole, 4- nitro -3,5- diformazan
Base pyrazoles, 4- bromo- 3,5- dimethyl pyrazole, 3- methyl -5- Phenylpyrazole etc..Wherein preferred diethyl malonate, 3,5- diformazan
Base pyrazoles etc..
Sealer thermal dissociation is made to produce the blocked polyisocyanate compound of free isocyanate groups with regard to this, permissible
For the polyisocyanate compounds with free isocyanate groups, by monitoring infrared absorption spectrum, while with envelope
Close agent and reacted and disappear until the inherent absorption spectrum based on NCO, thus being readily available.
As the commercially available product of preferred blocked polyisocyanate, can enumerate sealer is activity methene compound
DURANATE MF-K60B（Asahi Chemical Industry's chemical company system）、DESMODUR BL-3475（Live to change Bayer polyurethane company system）,
Another aspect sealer is the TRIXENE BI-7982 of pyrazole compound（Baxenden company system）, active methylene group and pyrazoles
The mixed type TRIXENE BI-7992 of compound（Baxenden company system）.
Constitute host and the firming agent of compositions of thermosetting resin, as long as consumed according to their each functional group after solidification
Situation, selects respective usage amount, briefly, such as every 100 parts of hosts in terms of the mass conversion of nonvolatile component, Gu
Agent can be 30～800 parts.
By the film property thermoplastic resin containing hydroxyl and isocyanate curing agent as blocked polyisocyanate
In the compositions of thermosetting resin as required composition for the combination, from the aspect of printing adaptability is excellent, in terms of mass conversion, different
Every 100 parts of the nonvolatile component of cyanate firming agent, the nonvolatile component of the film property thermoplastic resin containing hydroxyl is more preferably
For 5～50 parts.
（Epoxide）
As the compositions of thermosetting resin in the present invention, using blocked polyisocyanate and the film property containing hydroxyl
In the case of the combination of thermoplastic resin, by wherein and use epoxide, can lowering viscousity while, can improve
Crosslink density, improve the adaptation of base material to the conductive pattern after solidification, solvent resistance further.As the epoxy using
Compound, is not particularly limited, but preferably uses aliphatic epoxide.In particular, it is preferred that using Polyethylene Glycol, gathering
The epoxide such as the glycidyl ether compound such as propylene glycol, hexanediol, trimethylolpropane, glycerol, tetramethylolmethane, Sorbitol,
Cycloaliphatic epoxy.Wherein, the more preferably glycidyl ether compound such as Polyethylene Glycol, polypropylene glycol, trimethylolpropane.
Because aliphatic epoxide is liquid or semisolid at room temperature, therefore electric conductivity can not damaged
In the case of make viscosity higher or solid composition compositions of thermosetting resin host composition decrement, therefore can make electric conductivity
The mobility of ink composite becomes good, in specific printings such as flexographic printing, silk screen printing, intaglio printing or intaglio offset printings
In method, even if in the case of continuously being printed on these printer, also readily available be difficult to occur obstacle and steady
Surely good conductive pattern.The epoxide of partially aromatic is liquid or semisolid, but the reasons why secure context
Consider not preferably use.
When modulate the present invention conductive ink composition when, and with epoxide as compositions of thermosetting resin
Constituent in the case of, the electric conductivity that finally gives from raising, obdurability, the performance of the conductive pattern such as solvent resistance
From the aspect of, in terms of mass conversion, the nonvolatile component of the total compositions of thermosetting resin containing in above-mentioned ink composite
Every 100 parts, preferably use 5～50 parts.
（The catalysts of blocked polyisocyanate）
In blocked polyisocyanate used in the present invention, catalysts if necessary can be used together.Anti- as this
Answer catalyst, be not particularly limited, but the catalysts of blocked polyisocyanate are preferably organic ammonium salt or organic amidine salt.
Specifically, it is possible to use as the quaternary alkylammonium halides of organic ammonium salt, tetra-alkyl ammonium hydroxide, tetraalkyl ammonium salt organic acid
Deng as the 1 of organic amidine salt, 8- diazabicyclo [5.4.0] endecatylene -7（Following DBU）, 1,5- diazabicyclo
[4.3.0] nonene -5（Following DBN）Phenates, caprylate, oleate, tosilate, formates.Wherein, preferably use
DBU- caprylate, DBN- caprylate.As commercially available product, organic ammonium salt can enumerate TOYOCAT-TR20（Eastern Cao's company system）, organic
Amidine salt can enumerate U-CAT SA1, U-CAT SA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, U-CAT
SA1102（San-APRO company system）.
The catalysts of blocked polyisocyanate, the electric conductivity finally giving from raising, the electric conductivity figure such as solvent resistance
From the aspect of the performance of case, in terms of mass conversion, every 100 parts of blocked polyisocyanate are preferably 3～30 parts.
（Organic solvent）
Various raw material used in the present invention itself is solid when 25 DEG C because it is most of, therefore generally has to
After dissolving etc. in liquid medium, base material is coated with or prints the thread pattern of conductive ink composition.Therefore, work as selection
Constitute when the host of compositions of thermosetting resin and firming agent the dissolubility it is considered preferred to liquid medium.
From the viewpoint, combined using dissolvable thermosetting resin in the conductive ink composition of the present invention
Thing, and with its do not have reactivity 25 DEG C be liquid organic compound.Such organic compound is organic molten
Agent, its species does not limit, and can enumerate ester system, ketone system, chlorine system, alcohol system, ether system, hydrocarbon system, ether-ether system etc..Specifically, for example
Methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, n-butyl alcohol, isobutanol, isophorone, gamma-butyrolacton, DBE can be enumerated（English
Japan of Weida system）, METHYLPYRROLIDONE, ethylcarbitol acetass, butyl cellosolve acetass, propanediol monoalkyl
Ether acetic acid ester etc..These can be used alone one kind it is also possible to and with more than two kinds.Wherein, regardless of printing process described later
Species, in order to be readily obtained conductive pattern, as this organic solvent, preferably uses boiling point 100 from the aspect of rate of drying
～250 DEG C of solvent.
As described later, in the case of using woodburytype or intaglio offset print process, preferably make this organic molten
The organosilicon adhesive plaster swelling rate of agent is 5～20%, particularly preferred diethylene glycol monobutyl ether acetass, TC
The ether-ether such as acetass system organic solvent.
Containing ratio in conductive ink composition for the organic solvent be preferably 5～30 mass %, more preferably 7～
15 mass %.If in this scope, make paste viscosity become more appropriate, particularly print in intaglio printing or intaglio offset
In, needle pore defect will not be produced in the cross point of the angle part of setting-out, matrix, the conductive pattern of more fine can be formed.
The conductive ink composition of the present invention in addition to known usual material composition as above, maximum feature
For containing further, there is at least one selecting from the group being made up of phosphate group, phosphate group, bound phosphate groups
The organic compound of functional group.Phosphate group refers to-H2PO4The group representing（P atom is 5 valencys）, phosphate group refers to
In-H2PO4In hydrogen atom at least one by alkali metal ion, alkaline-earth metal ionic replacement and form the group of salt form.
In addition, bound phosphate groups refer in-H2PO4In hydrogen atom at least one by alkyl, phenyl replace group.
Below by the organic compound containing phosphate group, the organic compound containing phosphate group, contain phosphate ester
The organic compound of group is concentrated and is abbreviated as the organic compound containing phosphate group.
As this organic compound containing phosphate group, for example, can enumerate polyalkylene glycol mono phosphate ester, poly- Asia
Alkylene glycol monoalkyl ether phosplate, perfluoroalkyl polyoxyalkylene phosphate ester, perfluorinated alkyl sulfonamide polyoxyalkylene phosphorus
Low molecular compound, vinyl phosphonate, acid phosphorus methylaminosulfonylethyl list as acid esters（Methyl）Acrylate, acid phosphoryl third
Base list（Methyl）Acrylate, acid phosphoryl polyoxyalkylene glycol are single（Methyl）The homopolymer of acrylate or above-mentioned list
Body contain phosphate group polymer such with the copolymer of other comonomers is as macromolecular compound.
In addition, above-mentioned middle as specific example, illustrate only the organic compound containing phosphate group, but contain phosphoric acid
The organic compound of salt groups can by by alkali metal hydroxide, alkaline-earth metal hydroxide with containing phosphate group
Organic compound reaction and be readily available, the organic compound containing bound phosphate groups can be by organic containing phosphate group
Compound makes the organic compound containing phosphate compound group and alcohol be contracted with the dehydrating condensation of alcohol, by base effect
Close, be similarly readily available.
As the organic compound containing phosphate group, in the contrast of commensurability nonvolatile component usage amount, from can
From the aspect of having more low viscosity and more low volume resistivity concurrently, compared with the organic compound containing bound phosphate groups, preferably comprise
One of the organic compound of phosphate group, the organic compound containing phosphate group.
As above-mentioned low molecular compound, can be from such as Ciba Specialty Chemicals EFKA series, on the other hand as high
Molecular compound, can select respectively from such as BYK company system DISPERBYK series and use.
As above-mentioned macromolecular compound, preferred number average molecular weight 1, more than 000, wherein number-average molecular weight 1,000～
10,000 polymer containing phosphate group, because in same usage amount compared with above-mentioned low molecular compound, not
In the case of infringement electric conductivity, the improved effect of the mobility of conductive ink composition is high.
The usage amount of the organic compound containing phosphate group used in the present invention, electroconductive stuffing, thermosetting resin
The mass conversion of compositionss and organic solvent adds up to every 100 parts, is preferably 0.1～3 part.
In the conductive ink composition of the present invention, in addition to mentioned component, can suitably join in right amount as needed
Close the various additives such as dispersant, defoamer, remover, levelling agent, plasticizer.
The conductive ink composition of the present invention can by any method, for example in plastic sheeting, ceramic membrane, silicon wafer
Form corresponding conductive pattern by being coated with or print on any one base material of piece, glass or metallic plate.However, in order that originally
The true value of the conductive ink composition of invention howsoever can play, when obtaining conductive pattern, using not
Can be exposed to the sun in the PET film of high temperature, PP film be thin or transparent conducting film as ito thin film.
The conductive ink composition of the present invention can be on any base material, using such as flexographic printing, silk screen printing, recessed
The printing process of version printing or intaglio offset printing is printed, and makes printed patterns be solidified to form cured film by heating,
Thus forming conductive pattern.
As the forming method of the conductive pattern being made up of the conductive ink composition of the present invention, can enumerate this
Bright conductive ink composition is coated on non-heat-resistant base material, the method being heated.The conductive ink group of the present invention
Compound is by containing the above-mentioned organic compound with phosphate group, can more easily make shear rate 10s at 25 DEG C-1
When viscosity be 1～50Pa s.As a result, being filled in conductive ink composition in intaglio plate, by this ink group of filling
After compound is transferred to adhesive plaster roller, by this ink composite is applied to non-heat-resistant base material from adhesive plaster roller transfer, thus will
Desired pattern printing, in non-heat-resistant substrate surface, carries out so-called intaglio offset printing, then passes through and heated and shape
Become conductive pattern.
As intaglio printing plate at this moment, it is possible to use common intaglio plate, by the photoresist on glass plate pass through expose
Light, development, washing and formed intaglio plate, glass plate, metallic plate, metallic roll are formed by chemical etching and laser-induced thermal etching
Intaglio plate.
In addition, being the thin plate with organic silicon rubber layer, pet layer, Rotating fields as spongy layer as organosilicon adhesive plaster,
Generally can be wound in be referred to as the having on rigid cylinder of blanket cylinder in the state of use.
In the forming method of the conductive pattern being made up of the conductive ink composition of the present invention, using above-mentioned recessed
In the case of version offset printing method, with regard to organosilicon adhesive plaster it is desirable to the transferability from intaglio plate and the transferability to base material.In order to
Obtain the sufficient transferability to base material it is necessary to the liquid in conductive ink composition be absorbed with certain proportion in blanket surface
Composition.If absorbing insufficient, when base material is transferred, conductive ink composition layer easily produces splitting, in turn,
If absorbing and exceeding certain proportion, conductive ink composition is dried in blanket surface, there is the easy transfer producing to base material
Bad the problems such as.
It is 1～50Pa s by making the viscosity when 25 DEG C for the conductive ink composition, using intaglio offset print process
And in the case of continuously carrying out the printing of conductive pattern, pin is easily produced on the angle part of setting-out, the cross point of matrix
Hole defect, can form good elecroconductive thin line pattern, and is difficult to produce the inking to intaglio plate, from intaglio plate to adhesive plaster
Transitivity be problem.
The conductive ink composition of the present invention, the mode being 10～150 μ m according to such as line width, on base material
It is coated with and form printed patterns, by being heated solidification, such that it is able to form conductive pattern.
Then, the printed patterns arranging on base material, for example, pass through to heat 20～5 minutes at 100～130 DEG C, thus shape
Become cured film, form conductive pattern and manifest electric conductivity.
The conductive pattern being formed by the conductive ink composition of the present invention, can be thick line width as β
Setting-out, but the feature in the case of employing the conductive ink composition of the present invention, before by ratio as described above more
When thin line width setting-out is arranged on base material, particularly marked degree play.
As noted previously, as the conductive pattern being made up of the conductive ink composition of the present invention can be than in the past more
Formed in low temperature and short time, therefore, the feature of the conductive ink composition of the present invention, with ceramic membrane, glass or metal
The high base material of thermostability as plate is compared, lower and form electric conductivity on the non-heat-resistant base material of easy thermal deformation in thermostability
During pattern, particularly marked degree play.Therefore, the consolidating of conductive ink composition of the present invention is formed with non-heat-resistant base material
The conductive pattern changing film can be preferably used as the electroconductive circuit of formation on non-heat-resistant base material.
So, with regard to the conductive ink composition using the present invention, by using various printing sides on various base materials
Method carries out printing heating and is formed and be provided with the base material of conductive pattern, as electroconductive circuit, as desired by carrying out cloth
Line etc., can form various electric components, electronic unit.Specifically, the conductive ink composition of the present invention is to transparent ITO
The adaptation of transparent conductive film as electrode is also excellent.
As final products, for example, can enumerate the extraction electrode of touch screen, the extraction electrode of display, Electronic Paper, the sun
Can battery, other distribution product etc..
Embodiment
Specifically describe the present invention below by embodiment.Here " % " is just " quality % " if not otherwise specified.
Use each raw material according to the mass fraction described in table 1, these raw materials are sufficiently mixed, modulation is as embodiment
Each conductive ink composition of the present invention and the former each conductive ink composition as comparative example.
With regard to these each conductive ink compositions, by following mensure project, evaluate conductive ink composition originally
The characteristic of body and the characteristic of conductive pattern therefrom.This evaluation result is also concentrated and is shown in table 1 below, in table 2.
（Viscosity）
Using rotary rheometer, measure at 25 DEG C, shear rate is 10s-1When the present invention conductive ink group
The viscosity of compound.
（Printing adaptability）
Using the conductive ink composition of the present invention, carry out intaglio offset printing by following methods, make conductive electricity
Road.
Using scraping blade (doctor blade) by conductive ink composition inking on the intaglio plate of glass system after, winding
Have on the cylinder of adhesive plaster extruding, contact it would be desirable to pattern transfer on adhesive plaster.Afterwards, the film on this adhesive plaster extruded, turn
Print to the transparent conductive film as base material, make the conducting channel of 30 μm～100 μm of line width.In above-mentioned conducting channel
In, 30 μm of lines of microexamination line width, according to following benchmark evaluation line reproducibility.
◎：The rectilinearity of line is especially excellent, no breaks local
○：The rectilinearity of line is excellent, no breaks local
×：The rectilinearity of line is poor, has broken string local
（Specific insulation）
According to the mode that dried thickness is 4 μm, conductive ink composition is coated on electrically conducting transparent using spreader
On film（Ito film face）, it is dried 10 minutes at 125 DEG C.Using this ink film, using LORESTA GP MCP-T610（Rhizoma Sparganii
Chemical company's system）It is measured by four-terminal method.Specific insulation is the standard of electric conductivity height.
[table 1]
[table 2]
Argentum powder：
AG-2-1C（DOWA electronics（Strain）System, mean diameter D50:0.8μm）
BYRON 200：Molecular weight 17,000, hydroxyl valency 6, vitrification point（Tg）67 DEG C, thermoplastic polyester（Japan
Textile company system）
SOLBIN AL：Number-average molecular weight 22,000, vitrification point（Tg）76 DEG C, vinyl chloride/vinyl acetate/ethylene
The combined polymerization mass ratio of alcohol is 93/2/5 vinyl chloride vinyl acetate copolymer（Xin chemical industrial company system）
DENACOL EX-321：Trimethylolpropane polyglycidyl ether（Nagasechemtex company system）
TRIXENE BI7982：Sealer is the blocked isocyanate of 3,5- dimethyl pyrazole（Baxenden company system）
DISPER BYK-111：Number-average molecular weight is the polymer containing phosphate group of 1,000～10,000 scope
（Macromolecular compound）（BYK company system）
EFKA-8512：Phosphate ester containing polyoxyalkylene（Low molecular compound）（Ciba Specialty Chemicals' system）
U-CAT SA 102：DBU- caprylate（San-APRO company system）
U-CAT SA 603：DBU- formates（San-APRO company system）
CUREZOL 2E4MZ：2-ethyl-4-methylimidazole（Four countries are melted into company system）
EDGAc：TC acetass
From the evaluation result of table 1, the electric conductivity oil of the embodiment 4 containing the organic compound with bound phosphate groups
Ink composition, compared with the not conductive ink composition containing its comparative example 1, viscosity and printing adaptability are all excellent.By
The contrast of embodiment 3 and 4 understands, when employing macromolecular compound as the organic compound containing phosphate group, with use
The situation of the low molecular compound containing bound phosphate groups is compared, and viscosity and electric conductivity is substantially excellent.
Understand：With regard to the conductive ink composition of embodiment 3～4, the film property thermoplastic resin containing hydroxyl with different
The relation of each nonvolatile component ratio of cyanate firming agent is that the firming agent of the latter is more, more with the former thermoplastic resin
The conductive ink composition of embodiment 1～2 compare, printing adaptability is more excellent.
Further, since the sealer that the conductive ink composition of embodiment is all blocked isocyanate is low temperature dissociative
Activity methene compound and/or pyrazole compound, therefore, even if nonrefractory as transparent conductive film, PET film
It is also possible to form down the conductive pattern being made up of cured film between the low-temperature short-times such as no warpage on property base material, the conduction that obtains
Property pattern is also fully satisfactory in electric conductivity, base material adaptation.
Industry utilizability
The conductive ink composition of the present invention can act as various electric components, the conductive pattern of electronic unit is formed
Conductive silver thickener.
Claims (8)
1. a kind of conductive ink composition is it is characterised in that described conductive ink composition contains electroconductive stuffing, thermosetting
Property resin combination, organic solvent as required composition, contain further and have from by phosphate group, phosphate group, phosphoric acid
In the group that ester group is formed select at least one functional group organic compound, described compositions of thermosetting resin be containing
There is the film property thermoplastic resin of hydroxyl and the compositions of thermosetting resin of blocked polyisocyanate, described closing polyisocyanate
The sealer of ester is activity methene compound or pyrazole compound.
2. conductive ink composition according to claim 1, described organic compound is containing from by phosphate group, phosphorus
In the group that acid salt group, bound phosphate groups are formed select at least one functional group, and number-average molecular weight 1, more than 000 gather
Compound.
3. conductive ink composition according to claim 1, described electroconductive stuffing is 0.1～3 μm of mean diameter
Spherical argentum powder.
4. conductive ink composition according to claim 1, further and use epoxide.
5. the conductive ink composition according to any one of Claims 1 to 4, at 25 DEG C, shear rate 10s-1
When viscosity be 1～50Pa s.
6. a kind of manufacture method of conductive pattern, the conductive ink composition any one of Claims 1 to 4 is applied
Cloth, on non-heat-resistant base material, is heated.
7. the manufacture method of conductive pattern according to claim 6, by leading any one of Claims 1 to 4
Conductive ink compositionss are filled in intaglio plate, and the described conductive ink composition of filling is transferred to after adhesive plaster roller, by inciting somebody to action
Described conductive ink composition is applied to non-conductive supporter from adhesive plaster roller transfer, thus by desired pattern printing non-
Heat-resistant material surface, is then heated.
8. a kind of electroconductive circuit, it is included on non-heat-resistant base material and is formed with leading any one of Claims 1 to 4
The conductive pattern of the cured film of conductive ink compositionss.
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| JP2012-174909 | 2012-08-07 | ||
| JP2012174909A JP6031882B2 (en) | 2012-08-07 | 2012-08-07 | Conductive ink composition, method for producing conductive pattern, and conductive circuit |
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| JP2015193722A (en) * | 2014-03-31 | 2015-11-05 | Dic株式会社 | Ink composition and method for manufacturing ceramic substrate |
| CN106715609A (en) * | 2014-09-30 | 2017-05-24 | 株式会社大赛璐 | Silver particle coating composition |
| US20170306172A1 (en) * | 2014-10-02 | 2017-10-26 | Daicel Corporation | Silver particle coating composition |
| JP6429192B2 (en) * | 2015-01-29 | 2018-11-28 | 株式会社シマノ | Ink for inkjet printing |
| JP6673322B2 (en) * | 2017-12-20 | 2020-03-25 | 住友ベークライト株式会社 | Conductive paste and stretchable wiring board |
| WO2019239610A1 (en) * | 2018-06-12 | 2019-12-19 | Dic株式会社 | Highly electrically conductive silver ink composition and wiring obtained using same |
| CN109385145A (en) * | 2018-10-30 | 2019-02-26 | 宁波石墨烯创新中心有限公司 | A kind of organic system electrically conductive ink, preparation method and flexible device |
| KR20240027774A (en) * | 2021-07-02 | 2024-03-04 | 스미또모 베이크라이트 가부시키가이샤 | Conductive resin compositions, high thermal conductivity materials and semiconductor devices |
| CN113782252B (en) * | 2021-11-15 | 2022-03-01 | 西安宏星电子浆料科技股份有限公司 | UV heating dual-curing conductive slurry and preparation method thereof |
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| CN1354208A (en) * | 2000-11-16 | 2002-06-19 | 国家淀粉及化学投资控股公司 | Conductive ink composition |
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| JPS6088027A (en) * | 1983-10-20 | 1985-05-17 | Toyobo Co Ltd | Electroconductive resin composition |
| JP3558593B2 (en) | 2000-11-24 | 2004-08-25 | 京都エレックス株式会社 | Heat-curable conductive paste composition |
| JP4547623B2 (en) | 2005-04-25 | 2010-09-22 | 東洋紡績株式会社 | Conductive paste |
| JP5068468B2 (en) * | 2006-03-24 | 2012-11-07 | Ｄｉｃ株式会社 | Conductive ink composition and printed matter |
| JP5082281B2 (en) * | 2006-04-10 | 2012-11-28 | Ｄｉｃ株式会社 | Cationic curable conductive ink |
| JP4943254B2 (en) | 2007-07-18 | 2012-05-30 | 太陽ホールディングス株式会社 | Conductive paste composition, translucent conductive film using the composition, and method for producing the same |
| JP5255792B2 (en) | 2007-07-18 | 2013-08-07 | 太陽ホールディングス株式会社 | Conductive paste composition, translucent conductive film using the composition, and method for producing the same |
| KR101356810B1 (en) * | 2010-05-10 | 2014-01-28 | 주식회사 엘지화학 | Conductive metal ink composition and preparation method for conductive pattern |
| JP5569733B2 (en) | 2010-08-09 | 2014-08-13 | Ｄｉｃ株式会社 | Conductive silver paste, conductive pattern forming method, and printed conductive pattern |
| JP5569732B2 (en) | 2010-08-09 | 2014-08-13 | Ｄｉｃ株式会社 | Conductive silver paste, conductive pattern forming method, and printed conductive pattern |
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