CN109074919A - The forming method of transparent conductive patterns - Google Patents
The forming method of transparent conductive patterns Download PDFInfo
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- CN109074919A CN109074919A CN201780026692.9A CN201780026692A CN109074919A CN 109074919 A CN109074919 A CN 109074919A CN 201780026692 A CN201780026692 A CN 201780026692A CN 109074919 A CN109074919 A CN 109074919A
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- conductive patterns
- transparent conductive
- forming method
- transparent
- scraper plate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
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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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1216—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by screen printing or stencil printing
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing Of Electric Cables (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Conductive Materials (AREA)
Abstract
Project is to provide a kind of forming method of transparent conductive patterns, in using the silk-screen printing comprising metal nanometer line and/or metal nano-tube as the transparent conductivity ink of conductive compositions, by mitigating the damage to metal nanometer line and/or metal nano-tube, transparent conductive patterns can be formed using easy manufacturing process, inhibit manufacturing cost and carrying capacity of environment.Solution is the circle scraper plate (3) for having curve form using the top end part contacted with screen mask (2), transparent conductivity black (5) is subjected to silk-screen printing, transparent conductivity ink (5) includes at least one of metal nanometer line and metal nano-tube and decentralized medium.
Description
Technical field
The present invention relates to the forming methods of transparent conductive patterns.
Background technique
Transparent conductive film liquid crystal display (LCD), plasma display panel (PDP), organic electroluminescence device (OLED),
The transparent electrode of solar battery (PV) and touch screen (TP), antistatic (ESD) film and electromagnetic wave shielding (EMI) film etc. are various
Field uses, it is desirable that (1) low sheet resistance, (2) high transparency, (3) high reliability.
For example, sheet resistance is in the range of 10~300 Ω/ for the transparent electrode of LCD, and light transmittance is can
It is suitable that light-exposed range, which is 85% or more,.It is 20~100 Ω/ that preferred range, which is sheet resistance, and light transmittance is
90% or more.For the transparent electrode of OLED, sheet resistance is in the range of 10~100 Ω/, and light transmittance is in visible light
It is suitable that range, which is 80% or more,.It is 10~50 Ω/ that preferred range, which is sheet resistance, and light transmittance be 85% with
On.For the transparent electrode of PV, sheet resistance is in the range of 5~100 Ω/, and light transmittance is in visible-range
65% or more is suitable.Preferred range is that sheet resistance is 5~20 Ω/, and light transmittance is 70% or more.For TP
Electrode, sheet resistance is in the range of 100~1000 Ω/, and it is to close that light transmittance, which is 85% or more in visible-range,
Suitable.More preferably sheet resistance is in the range of 150~500 Ω/, and light transmittance visible-range be 90% with
On.For ESD film, sheet resistance is in the range of 500~10000 Ω/, and light transmittance visible-range be 90% with
On be suitable.More preferably sheet resistance is in the range of 1000~5000 Ω/, and light transmittance is in visible-range
It is 95% or more.
As transparent conductive film used in these transparent electrodes, ITO (tin indium oxide) was used always in the past.But ITO
Indium used is rare metal, therefore is supplied in recent years with the stabilisation of price as project.In addition, the film of ITO uses always
Need sputtering method, the vapour deposition method etc. of high vacuum, it is therefore desirable to which vacuum manufacturing device, not only manufacturing time is long, and cost is also got higher.And
And ITO is easy to be cracked and damaged due to physical stress such as bendings, therefore, it is difficult to imparting substrate application flexible.Cause
This, the exploration for eliminating the ITO alternative materials of these problems just constantly promotes, as do not need using vacuum manufacturing device can
Coating film forming material once reported the conductive material (see, for example patent document 1 and non-patent literature 1) containing metal nanometer line
Deng the conductive component containing nanostructure conductive material.
Conductive material containing metal nanometer line shows low sheet resistance and high transparency, and has flexibility, because
This is suitable as " ITO alternative materials ".
Here, transparent conductive film needs to form pattern corresponding with purposes in order to use as transparent electrode, it is taken as
The method that conductive material containing metal nanometer line forms pattern, generally formed with the pattern of ITO in the same manner as using
The photoetching process of anticorrosive additive material.In either above patent document 1 and non-patent literature 1 method, require comprising metal
The process with photosensitive layer for being used to form pattern is re-formed on the layer of nano wire.In addition, it is necessary to have photosensitive
The removal step of the developing procedure of layer and the layer comprising metal nanometer line exposed, so can not only waste the Yin Na for removing region
Rice noodles, it is also necessary to the liquid waste processing of developer solution.Moreover, with photosensitive layer development and exposing include metal nanometer line
Layer removing after, the removal step that sometimes also needs that there is photosensitive layer.
Therefore, it is intended that using the print process of ink jet printing, silk-screen printing, intaglio printing, flexible printing etc, by silver nanoparticle
Line directly forms pattern.But adhesive resin is needed when being printed, and in order to ensure the transparency needs to reduce silver nanowires
Usage amount, therefore there is the adhesive resin that uses and be coated the surface of silver nanowires and asked to not embody as electric conductivity
Topic.In addition, there are being unable to ensure pattern when printing, or even if terminating to print just in the case where not using adhesive resin
It can barely ensure pattern after brush, pattern can also lose shape such problems in dry solvent.
Patent document 2 discloses a kind of transparent conductivity ink that can be printed without using adhesive resin, special
Sign is that at least one and decentralized medium comprising metal nanometer line and metal nano-tube, the decentralized medium contain shape
Retention agent, the shape retention agent include the organic compound that molecular weight ranges are 150~500 and 25 DEG C of viscosity be 1.0 ×
103~2.0 × 106mPa·s。
According to the condition of silk-screen printing in this method, during printing is gone down repeatedly can to metal nanometer line and/or
Metal nano-tube causes to damage, and there are the projects of the damage influence electric conductivity.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application Publication 2009-505358 bulletin
Patent document 2: No. 2013/161996 handbook of International Publication No.
Non-patent literature
Non-patent literature 1:Shih-HsiangLai, Chun-YaoOu, Chia-HaoTsai, Bor-ChuanChuang,
Ming-YingMa,and Shuo-WeiLiang；SID Symposium Digest of Technical Papers,
Vol.39,Issue 1,pp.1200-1202(2008)
Summary of the invention
The object of the present invention is to provide a kind of forming methods of transparent conductive patterns, are using comprising metal nanometer line
And/or in silk-screen printing of the metal nano-tube as the transparent conductivity ink of conductive compositions, by mitigate to metal nanometer line and/
Or the damage of metal nano-tube, transparent conductive patterns can be formed using easy manufacturing process, inhibit manufacturing cost and environment
Load.
To achieve the goals above, the present invention includes the following embodiments and the accompanying drawings.
[1] a kind of forming method of transparent conductive patterns, which is characterized in that had using the top end part contacted with screen mask
Have the scraper plate of curve form, by transparent conductivity ink carry out silk-screen printing, the transparent conductivity ink include metal nanometer line with
At least one of metal nano-tube and decentralized medium.
[2] forming method of the transparent conductive patterns according to [1], the top of the scraper plate contacted with screen mask
The radius of curvature of the curved surface in portion is 0.1~20mm.
[3] forming method of the transparent conductive patterns according to [2], the top of the scraper plate contacted with screen mask
The radius of curvature of the curved surface in portion is 2~10mm.
[4] according to the forming method of described in any item transparent conductive patterns of [1]~[3], the material of the scraper plate is
Any one of synthetic rubber, natural rubber, metal, plastics.
[5] forming method of the transparent conductive patterns according to [4], the synthetic rubber is by polyurethane rubber or silicon rubber
Glue is constituted.
[6] according to the forming method of described in any item transparent conductive patterns of [1]~[5], scraper velocity is set as 5~
Progress silk-screen printing in 200mm/ seconds.
[7] according to the forming method of described in any item transparent conductive patterns of [1]~[6], the transparent conductivity ink
In, include 0.01~10 matter relative to transparent conductivity ink gross mass as the total amount of metal nanometer line and metal nano-tube
Measure %.
[8] according to the forming method of described in any item transparent conductive patterns of [1]~[7], the decentralized medium includes
Shape retention agent, the shape retention agent are made of the organic compound that molecular weight ranges are 150~500.
[9] forming method of the transparent conductive patterns according to [8], the organic compound of the shape retention agent are single
Any one of saccharide compound, polyol compound, compound with alkyl and hydroxyl, the alkyl have quaternary carbon atom
And/or bridge ring skeleton.
[10] forming method of the transparent conductive patterns according to [9], the organic compound of the shape retention agent are
Two glycerol, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate, xylulose, ribulose, bornyl cyclohexanol, borneol, different dragon
Any one of brain cyclohexanol and isoborneol.
[11] according to the forming method of described in any item transparent conductive patterns of [8]~[10], the decentralized medium is also
Viscosity comprising adjusting the viscosity of shape retention agent adjusts solvent.
[12] forming method of the transparent conductive patterns according to [11], viscosity adjustment solvent be water, alcohol, ketone,
At least one of ether, the hydrocarbon solvent of aliphatic category and hydrocarbon solvent of aromatic.
[13] alcohol of the forming method of the transparent conductive patterns according to [12], the viscosity adjustment solvent is pine tar
Alcohol.
[14] according to the forming method of described in any item transparent conductive patterns of [8]~[13], the shape retention agent
Content relative to decentralized medium gross mass be 10~90 mass %.
In accordance with the invention it is possible to mitigating the damage to metal nanometer line and/or metal nano-tube by transparent conductivity ink
Silk-screen printing is repeated, the transparent conductivity ink uses metal nanometer line and/or metal nano-tube as conductive compositions, energy
It is enough to form the film for taking into account electric conductivity and translucency, therefore, can yield rate manufacture stablize and with low sheet resistance well
The transparent conductive patterns of value.
Detailed description of the invention
Fig. 1 is the concept map for having used the silk-screen printing of round scraper plate.
Fig. 2 is the figure for illustrating the definition of pulsed light.
Fig. 3 is other the figure for indicating round scraper plate.
Fig. 4 is the side view of flat scraper plate used in comparative example 1.
Specific embodiment
Hereinafter, illustrating mode for carrying out the present invention (hereinafter referred to as embodiment).
The forming method for the transparent conductive patterns that embodiment is related to, which is characterized in that use what is contacted with screen mask
Top end part has the scraper plate of curve form, transparent conductivity ink is carried out silk-screen printing, the transparent conductivity ink includes metal
At least one of nano wire and metal nano-tube and decentralized medium.
The top end part contacted with screen mask has the scraper plate (hereinafter sometimes referred to " circle scraper plate ") of curve form, in silk screen
The scraper plate cross sectional shape for the part that mask is contacted with scraper plate has curved surface as shown in text.Curved surface can be the circular arc of constant curvature
Shape or the different ellipticity of curvature, but not limited thereto.By conceptual representation when such circle scraper plate being used to carry out silk-screen printing
In Fig. 1.
In Fig. 1, substrate 1 and screen mask 2 have the gap (clearance) of certain intervals and configure, and scraper plate 3 is pressed
Being pressed in screen mask 2 makes substrate 1 be bonded with screen mask 2 and move along print direction 4, makes to be located in screen mask 2
Transparent conductivity ink 5 squeezes out to 1 side of substrate and carries out silk-screen printing.
The radius of curvature R of the top end part (screen mask 2 with justify the part that contacts of scraper plate 3) of circle scraper plate 3 is preferably 0.1~
20mm, more preferably 1~15mm, further preferably 2~10mm.It can be by scraping if radius of curvature R is 0.1mm or more
Plate applies enough printing pressures to transparent conductivity ink 5.In addition, in screen mask if radius of curvature R is 20mm or less
On the influence that grinds of ink is small, can reduce bending, the cutting equivalent damage of metal nanometer line and metal nano-tube.
In the example of Fig. 1, the cross sectional shape of the tip portion of circle scraper plate 3 is expressed as arc-shaped, but as long as at least covering with silk screen
The part that mould 2 contacts has curve form, and there is no limit for the shape for the part not contacted with screen mask 2.That is, can also
So that the tip edge of the general flat scraper plate of previous screen mask 2 forms fillet, connect the fillet part with screen mask 2
Touching carries out silk-screen printing.
Fig. 3 (a), (b), other examples that round scraper plate 3 is shown in (c).The example of Fig. 3 (a) is the tip edge for making flat scraper plate
Both sides formed fillet example, the example of Fig. 3 (b) be make flat scraper plate tip edge on one side formed fillet example, Fig. 3
(c) example is the example for making the top of flat scraper plate form ellipse.Furthermore the end shape shape of scraper plate in the example of Fig. 3 (c)
At ellipse, but not limited to this, the whole circumstances that are non-constant including radius of curvature but being processed to curved surface.
The material of circle scraper plate 3 is not particularly limited, and the material same with scraper plate used in previous silk-screen printing can be used.
Can illustrate such as synthetic rubber of polyurethane rubber, silicon rubber, natural rubber, stainless steel etc. metal, polyester etc. plastics etc.
Blank.
The hardness of the circle scraper plate 3 of rubber stocks is not particularly limited, and the hardometer that such as JIS K6031 standard can be used obtains
The scraper plate that Hs (Shore) hardness arrived is 55~90.
As circle scraper plate 3 as described above, such as APOLAN International company rounding scraper plate, slope can use
Eastern chemistry Zhu Shihui company rounding scraper plate, flat scraper plate with rounded corners, angle sweep (band fillet) etc..
It the use of the scraper velocity (to the movement speed of print direction 4) in the printing of circle scraper plate 3 is preferably 5~200mm/
Second, more preferably 10~150mm/ seconds, further preferably 20~100mm/ seconds.It is given birth to if scraper velocity is 5mm/ seconds or more
Yield is good, misplacing of stencil caused by black transfer amount surplus when being able to suppress printing if scraper velocity is 200mm/ seconds or less
Deteriorate.
It the use of the scraper plate printing pressure in the printing of circle scraper plate 3 is preferably 0.10~0.45MPa, more preferably 0.15~
0.30MPa.The film thickness uniformity that can ensure printed ink if scraper plate printing pressure is 0.10MPa or more, if scraped
Plate printing pressure is that the film thickness for the ink that 0.45MPa or less is then printed will not become too thin, and suitably forms transparent conductive patterns.
It is not particularly limited other than restriction using the blade angle removing device in the printing of circle scraper plate 3.Circle scraper plate 3
Top end part is curve form, therefore even if blade angle is finely adjusted, to the metal nanometer line and gold in transparent conductivity ink
Belong to nanotube also not big influence, can be printed under 60~80 ° of the blade angle used in the general silk-screen printing, such as
Fruit does not have the restriction of device that can then print under smaller blade angle.
Using screen mask 2 with common intensity and tension, the gap in the printing of circle scraper plate 3 is used
Preferably the 1/600~1/150 of the inside dimension of screen frame, more preferably 1/450~1/200.If it is the inside of screen frame
Misplacing of stencil when 1/600 or more of size is then able to suppress printing deteriorates, and is then able to suppress when printing repeatedly if it is 1/150 or less
Damage to screen mask 2.Furthermore in the case where use intensity high screen mask, even if being the inside dimension of screen frame
1/100 or less also can inhibit damage to screen mask 2.
Screen mask 2 is set to be stained with ink in silk-screen printing, after making the ink expansion in screen mask 2 with scraper (scraper),
With scraper plates such as scraper plates 3 in printing on substrates.If the amount for the transparent conductivity ink 5 being stained in screen mask 2 is more, that prints is scraped
The damage of metal nanometer line and/or metal nano-tube in transparent conductivity ink 5 can be accumulated in plate operation.Therefore repeatedly big
In the case where amount printing, by limiting the amount for the transparent conductivity ink 5 being stained in screen mask 2, it is repeated to screen mask 2
The upper operation for suitably supplementing the transparent conductivity ink 5 consumed with printing, thus, it is possible to by the metal in transparent conductivity ink 5
The average length of nano wire and/or metal nano-tube maintains desired length.
The transparent conductivity ink of the silk-screen printing used in the forming method of the transparent conductive patterns of present embodiment
5, it include at least one of metal nanometer line and metal nano-tube and decentralized medium, as long as silk-screen printing can be used by having
The proper viscosity of holding pattern shape can be applicable in.If decentralized medium includes shape retention agent below, gold can be made
Belong to nano wire and/or metal nano-tube disperses well, it is advantageous to.By using transparent conductivity ink and use circle scraper plate
3 carry out silk-screen printing, can form the pattern obtained by printing well and be capable of forming and take into account by distillating decentralized medium
The film of electric conductivity and translucency.
Above-mentioned shape retention agent is the organic compound that molecular weight ranges are 150~500, the dispersion comprising shape retention agent
Medium is preferably 1.0 × 10 in 25 DEG C of viscosity3~2.0 × 106mPa·s.Here, organic compound is above-mentioned viscosity at 25 DEG C
Shape retention agent can be made only to be made of above-mentioned organic compound in the case where the liquid of range.On the other hand, viscous at 25 DEG C
Degree is higher than the case where above-mentioned range of viscosities or (can dissolve organic with solvent appropriate in the case where being solid for 25 DEG C
The solvent of compound can enumerate aftermentioned viscosity adjustment solvent etc.) it is pre-mixed (dilution, dissolution) formation decentralized medium.
It cannot keep the pattern form printed out if the viscosity of decentralized medium is lower than above range, if be higher than above-mentioned
The baneful influence of stringiness when range is then printed etc..Viscosity as decentralized medium at 25 DEG C is more preferably 5.0 × 104
~1.0 × 106The range of mPas.Furthermore viscosity is the value determined using cone-plate type rotational viscometer (cone-plate type).
In addition, if the shape retention agent used the i.e. molecular weight of organic compound greatly if be sintered when shape retention agent can not
Efficiency removes well, and resistance does not decline.It therefore, is 500 hereinafter, preferably 400 hereinafter, more preferably 300 as molecular weight
Below.
Be preferably added to the compound of hydroxyl as such organic compound, for example, monosaccharide, polyalcohol, have alkyl with
The compound of hydroxyl, the alkyl have quaternary carbon atom and/or bridge ring skeleton, can enumerate such as two glycerol, 2,2,4- trimethyls-
1,3- pentanediol mono isobutyrate, xylulose, ribulose, bornyl cyclohexanol, borneol, isobornyl cyclohexanol, isoborneol etc..
Particularly preferably with the compound of isobornyl and hydroxyl among the above-mentioned compound enumerated.Because in addition to isoborneol
Other than the complicated stereochemical structure that base has, due also to the hydrogen bond of hydroxyl and assign adherence appropriate to ink.In addition, because having
The compound of isobornyl and hydroxyl has high viscosity although volatilization temperature is less high, therefore the height that can be realized ink is viscous
Degreeization.As the compound with isobornyl and hydroxyl, times in isobornyl cyclohexanol or isobornyl phenol can be enumerated
One or both.The above-mentioned compound enumerated has adherence appropriate, therefore assigns adherence appropriate to ink.Separately
Outside, show boiling point appropriate as black solvent, thus can in printing, after drying, pass through heating appropriate, light sintering etc.
Reduce residue.The content of shape retention agent in ink is preferably 10~90 mass % relative to decentralized medium gross mass, more preferably
For 30~80 mass %.If the content of shape retention agent is 10~90 mass % relative to decentralized medium gross mass, ink becomes
For the viscosity for being suitable for printing, the printing for a problem that being able to carry out floating when not printing, stringiness.
In addition, as shape retention agent, itself is desirably in the sticky of the range of viscosities of above-mentioned preferred decentralized medium
Liquid is also possible to mix the adjustment solvent modulation of other viscosity in a manner of meeting above-mentioned range of viscosities with the viscous of above range
The decentralized medium of degree forms metal nanometer line and/or metal nano-tube in a dispersion medium as conductive compositions dispersion transparent
Electric conductivity ink.
As the example of viscosity adjustment solvent, the hydrocarbon solvent and aromatic series of water, alcohol, ketone, ester, ether, aliphatic category can be enumerated
The hydrocarbon solvent of class.From the viewpoint of making each ingredient fine dispersion in ink composition, preferably water, ethyl alcohol, isopropanol, 1- methoxy
Base -2- propyl alcohol (PGME), ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol ether, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropyl
Glycol monopropyl ether, diethylene glycol monobutyl ether, tripropylene glycol, Triethylene glycol ethyl ether, terpinol (terpineol), dihydro pine tar
Alcohol, dihydro pine tar monoacetate, methyl ethyl ketone, cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate, diethylene glycol monomethyl ether
It is acetic acid esters, butyl carbitol acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, butyl oxide, pungent
Alkane, toluene, particularly preferred terpinol.These solvents can be used alone, and can also mix two or more use.
So-called metal nanometer line and metal nano-tube, are the metals that diameter thickness is nano-grade size, and metal nanometer line is
Threadiness, metal nano-tube are porous (porous) or the non-porous conductive material with tubular form.In the present specification,
" threadiness " and " tubulose " is all linear, but the former center is not hollow, and the center of the latter is hollow.Character can
Be it is soft, be also possible to rigid.Both any one can be used in metal nanometer line or metal nano-tube, can also mix
It uses.
As the type of metal, can enumerate in gold, silver, platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium
It is at least one kind of and by alloy made of these metallic combinations etc..In order to obtain the painting with low sheet resistance and high full light transmittance
Film preferably comprises at least one kind of of any one of gold, silver and copper.The electric conductivity of these metals is high, therefore is obtaining certain table
When surface resistance, density metal shared by face can be reduced, so can be realized high full light transmittance.
Among these metals, more preferably comprising golden or silver at least one kind of.As optimal mode, the nanometer of silver can be enumerated
Line.
Metal nanometer line and/or the diameter thickness of metal nano-tube, the length of long axis in transparent conductivity ink and in length and breadth
Than preferably having certain distribution.The distribution is selected, so that the film obtained by the transparent conductivity ink of present embodiment
Become the film that full light transmittance is high and sheet resistance is low.Specifically, the diameter thickness of metal nanometer line and metal nano-tube
Average value preferably 1~500nm, more preferable 5~200nm, further preferred 5~100nm, particularly preferred 10~100nm.In addition,
Preferably 1~100 μm of the average value of the long axis length of metal nanometer line and/or metal nano-tube, more preferable 1~50 μm, further
It is preferred that 2~50 μm, particularly preferred 5~30 μm.The average value and length of metal nanometer line and/or the preferred diameter thickness of metal nano-tube
The average value of shaft length is met the above range, and the average value of aspect ratio is greater than 5, more preferably 10 or more, further preferably
It is 100 or more, particularly preferably 200 or more.Here, being averaged for the diameter of metal nanometer line and/or metal nano-tube is thick
It is approximately carefully b, and in the case where being approximately a for the average length of long axis, aspect ratio is the value acquired by a/b.A and b can make
With scanning electron microscope, it is measured using the method that embodiment is recorded.The section of metal nanometer line and/or metal nano-tube
It is preferably shaped to circle or ellipse without corner, even if having corner that can also be applicable in.Furthermore compared to acute angle, corner
Preferably obtuse angle.In the case where section has multiple corners, the angle in each corner be may be the same or different.
As the manufacturing method of metal nanometer line and/or metal nano-tube, well known manufacturing method can be used.For example,
Silver nanowires can be by using polyalcohol (Poly-ol) method, by silver nitrate reduction in the presence of polyvinylpyrrolidone
To synthesize (referring to Chem.Mater., 2002,14,4736).Nanowires of gold similarly can be by polyvinylpyrrolidone
In the presence of the also synthesis originally by gold chloride hydrate (referring to J.Am.Chem.Soc., 2007,129,1733).About silver nanoparticle
The extensive technology synthesized and refine of line and nanowires of gold, it is public in International Publication bulletin WO2008/073143 handbook and the world
Opening No. 2008/046058 handbook has detailed description.Gold nanotubes with porous structure can be by forming silver nanowires
Casting mold, and chlorauric acid solution was also synthesized originally.Here, silver nanowires used in casting mold is anti-by the redox with gold chloride
Answer and dissolve out in the solution, as a result formed there is porous structure gold nanotubes (referring to J.Am.Chem.Soc., 2004,126,
3892-3901)。
The content of metal nanometer line and/or metal nano-tube in transparent conductivity ink of the present embodiment, from it
Good patternability, high conductivity and the good optics spy of good dispersion and the film obtained by transparent conductivity ink
Property from the perspective of, preferably with respect to transparent conductivity ink gross mass, metal nanometer line and/or metal nano-tube are 0.01~10
The amount of quality %, more preferably 0.05~5 mass %, the further preferably amount of 0.1~2 mass %.If metal nanometer line
And/or metal nano-tube is 0.01 mass % or more, then without printing transparency conducting layer in order to ensure desired electric conductivity
It brushes very thick, gets higher so being able to suppress printing difficulty and floating etc. occurs when inhibiting dry.In addition, if it is 10 matter
Amount % or less in order to ensure desired transparency then without printing very thin, to be easy printing.Furthermore not to light
The range that characteristic, electrical characteristics etc. make a very bad impression is learned, may include other conductive compositions (metallics in transparent conductivity ink
Deng) and inorganic particulate (silica etc.).The partial size of these particles is preferably small, and average grain diameter is preferably 1~30nm, more preferably
5~25nm is hereinafter, further preferably 10~20nm.In addition, gold of the use level of these particles preferably with respect to 100 mass parts
Belonging to nano wire and/or metal nano-tube is 30 below the mass.
In the range for not damaging its property, transparent conductivity ink of the present embodiment may include mentioned component (shape
Shape retention agent, viscosity adjust solvent, metal nanometer line, metal nano-tube) other than any ingredient, such as it is adhesive resin, anti-
Rotten agent, fitting promotor, surfactant etc..
As adhesive resin, the polyacrylamide of polymethyl methacrylate, polyacrylate, polyacrylonitrile etc. can be enumerated
Based compound；Polyvinyl alcohol；Polyethylene terephthalate, the polyester of polyethylene naphthalate etc.；Polycarbonate；Phenol
The high conjugacy polymer of Novolac etc.；The acid imide of polyimides, polyamidoimide, polyetherimide etc.；More vulcanizations
Object；Polysulfones；Polyphenyl；Polyphenylene oxide；Polyurethane；Epoxy resin；The fragrance of polystyrene, polyvinyl-toluene, polyethylene dimethylbenzene etc.
Adoption alkene；The aliphatic poly alkene of polypropylene, polymethylpentene etc.；The ester ring type alkene of polynorbornene etc., poly N-ethylene
The poly N-ethylene based compound of base pyrrolidones, poly-N-vinylcaprolactam, poly N-ethylene yl acetamide etc.；Acrylic nitrile-butadiene
Diene-styrene copolymer (ABS)；The cellulose family of hydroxypropyl methyl cellulose (HPMC), NC Nitroncellulose etc.；Silicone tree
Rouge；Poly- acetic acid esters；Synthetic rubber；Polyvinyl chloride, the chlorine-containing polymer of haloflex, chlorinated polypropylene etc.；Kynoar,
The fluoropolymer etc. of polytetrafluoroethylene (PTFE), poly- hexafluoroethylene, fluorinated olefins-hydrocarbon olefin copolymer etc..
In addition, benzotriazole etc. can be enumerated as preservative, 2- hydroxymethyl cellulose etc. can be enumerated as fitting promotor,
Trade name F-472SF (DIC (strain) system) etc. can be enumerated as surfactant.
Mentioned component suitably can selectively be stirred by using known method, mix, adding by transparent conductivity ink
Heat, cooling, dissolution, dispersion etc. manufacture.
About the preferred viscosities of transparent conductivity ink of the present embodiment, at 25 DEG C viscosity be preferably 100~2 ×
105MPas, more preferably 103~5 × 104mPa·s.Furthermore viscosity is using cone-plate type rotational viscometer (cone-plate
Type) value that determines.
Using the transparent conductivity ink modulated in this way, pattern printing is carried out using silk-screen printing.
It, can be hard (rigidity) or flexible (pliability) as the substrate for carrying out pattern printing.And it can be by
Coloring.As substrate, it is (poly- to benzene that such as glass, polyimides, polycarbonate, polyether sulfone, acrylic resin, polyester can be enumerated
Naphthalate, polyethylene naphthalate etc.), polyolefin (include cyclic olefin polymer), polyvinyl chloride etc. material
Material.They preferably have high full light transmittance and low haze value.It is preferably resin film in terms of with bendability.Film thickness is excellent
Be selected as 1mm hereinafter, more preferably 500 μm hereinafter, further preferably 250 μm hereinafter, particularly preferably 125 μm or less.In addition,
From preferably 10 μm or more of operability aspect, more preferably 18 μm or more, further preferably 25 μm or more, particularly preferably
It is 38 μm or more.It is from excellent translucency, flexibility and mechanical property etc., it is preferable to use poly- among above-mentioned substrate
Ethylene glycol terephthalate, cyclic olefin polymer.As cyclic olefin polymer, the hydrogenated ring-opened easy of norbornene can be used
Position aggretion type cyclic olefin polymer (ZEONOR (registered trademark, Japanese ZEON corporation), ZEONEX (registered trademark, Japanese ZEON
Corporation), ARTON (registered trademark, JSR corporation) etc.) and/or norbornene/Addition on ethylene copoly type cyclic olefin polymer
(APEL (registered trademark, Mitsui Chemicals, Inc.'s system), TOPAS (registered trademark, treasured reason Plastics Company (POLYPLASTICSCO.,
LTD.) make)).Substrate can be the substrate for being also formed with the circuit of TFT element etc., can also form the functionality of colour filter etc.
Material.In addition, substrate can also be laminated it is multiple.
Transparent conductivity ink consider the film thickness of transparent conductivity pattern required depending on the application to the coating weight of substrate and
It determines.Film thickness is selected based on purposes.Desired film thickness is by adjusting the coating weight of transparent conductivity ink and the item of coating method
Part obtains.The thicker film thickness the better from the viewpoint of low sheet resistance, shows that undesirable viewpoint goes out from inhibition by differential generation
Hair gets over Bao Yuehao, so if comprehensively considering these factors, the preferred film thickness of 5~500nm, and the film thickness of more preferable 5~200nm,
The film thickness of further preferred 5~100nm.
Transparent conductivity ink by printing (coating), as needed makes it dry coating material heat treatment.Heating temperature
Degree is different according to the liquid parts for constituting decentralized medium, but if drying temperature is excessively high, the pattern formed sometimes can not be protected
It holds.Therefore, drying temperature is up to 120 DEG C hereinafter, more preferably 100 DEG C or less.Especially initial drying temperature is critically important,
So drying particularly preferably since 40~80 DEG C or so and periodically being risen as needed in the range no more than 120 DEG C
Temperature.The shape retention agent of thick liquid generally boiling point is high, and the viscosity adjustment solvent of low boiling point coexists compared with shape retention agent
Low-boiling viscosity adjustment solvent is preferentially distillated in the case where in decentralized medium.Therefore, the viscosity of decentralized medium is due to dry
Direction that is dry and becoming rising, printed patterns when can inhibit dry lose shape.
The sheet resistance of obtained transparent conductivity pattern and full light transmittance can be by its film thickness i.e. coatings of composition
Metal nanometer line or metal nano-tube in amount and the adjustment of the condition of coating method, transparent conductivity of the present embodiment ink
Concentration adjustment, to form desired value.
General film thickness is thicker, and sheet resistance and full light transmittance just become lower.In addition, the metal in transparent conductivity ink is received
The concentration of rice noodles or metal nano-tube is higher, and sheet resistance and full light transmittance just become lower.
The film obtained as described above, the preferably value of sheet resistance are 5~1000 Ω/, and full light transmittance is
60% or more, the value of more preferable sheet resistance is 10~200 Ω/, and full light transmittance is 80% or more.
Even if transparent conductivity ink of the present embodiment is only dried, sheet resistance can also become to a certain extent
It is low, but in order to more effectively reduce, preferred irradiating pulsed light.
So-called in the present specification " pulsed light ", (irradiation time) short light during being light irradiation, in repeated multiple times progress
Light irradiate in the case where as shown in Figure 2, it is meant that during (connections) and the second light irradiate during the irradiation of the first light (connection) it
Between there is the light at not (irradiation interval (disconnections)) during irradiation light to irradiate.The luminous intensity of pulsed light is indicated in Fig. 2 with constant, but
(connection) interior luminous intensity can also change during 1 light irradiates.Above-mentioned pulsed light by xenon flash lamp etc. the flash lamp that has
Light source irradiation.Using such light source, to the metal nanometer line or metal nano-tube irradiating pulsed light being deposited on aforesaid substrate.
In the case where the irradiation of n times repeatedly, by the n times repeatedly of 1 circulation (connection+disconnection) in Fig. 2.Furthermore in the feelings irradiated repeatedly
It is preferably cooling from substrate side in order to make substrate be cooled near room temperature when carrying out next pulsed light irradiation under condition.
In addition, it is the electromagnetic wave of 1pm~1m, it is preferable to use wavelength model that wave-length coverage, which can be used, as above-mentioned pulsed light
Enclose the electromagnetic wave (far ultraviolet~far infrared) for 10nm~1000 μm, further preferably using wave-length coverage be 100nm~
The electromagnetic wave of 2000nm.As the example of such electromagnetic wave, gamma-rays, X-ray, ultraviolet light, visible light, infrared can be enumerated
Line, microwave, in electric wave of long wavelength side of microwave etc..Furthermore it is too short in wavelength in the case where considering the conversion to thermal energy
In the case where, it is big to the damage of shape retention agent, the resin base material for carrying out pattern printing etc. to not preferred.In addition, in wavelength
Fever can not be effectively absorbed in the case where too long, so not preferably.Therefore, special among aforementioned wavelength as wave-length coverage
Range not preferably from ultraviolet to infrared, the more preferably wavelength of the range of 100~2000nm.
1 irradiation time (connection) of pulsed light is depending on luminous intensity, but the range of preferably 20 microsecond~50 millisecond.Such as
The fruit then sintering without metal nanometer line or metal nano-tube shorter than 20 microseconds, the performance enhancing effects of conductive film are lower.Separately
Outside, if longer than 50 milliseconds due to light deterioration, heat deterioration and make a very bad impression to substrate, and metal nanometer line or metal
Nanotube is easy to disperse.More preferably 40 microsecond~10 millisecond.Due to above-mentioned reason, in present embodiment using pulsed light without
It is continuous light.The irradiation of pulsed light is effective with single-shot to implement, but can also implement repeatedly as described above.Repeatedly
Irradiating interval (disconnection) in the case where implementation if considering productivity is preferably 20 microsecond~5 second, and more preferably 2 milliseconds~2 seconds
Range.If shorter than 20 microseconds, it can let cool after once irradiating and shortly irradiate again, so substrate quilt close to continuous light
Heating temperature gets higher to deteriorate.In addition, the process time is elongated so not preferably if longer than 5 seconds.
In the case where manufacturing transparent conductive patterns of the present embodiment, this embodiment party is used on substrate appropriate
The pattern for the transparent conductivity ink print arbitrary shape (the whole face shape for being also contained in the formation of substrate entire surface) that formula is related to, carries out
After heat treatment makes it dry, the pulsed exposure lamp etc. of xenon formula is used the pattern, and radiation pulses amplitude (connection) is 20 micro-
Second~50 milliseconds, the pulsed light for being more preferably 40 microsecond~10 millisecond, by the mutual intersection point of metal nanometer line or metal nano-tube
Engagement.Here, so-called engagement, is to make the material of nano wire or nanotube in metal nanometer line or the mutual intersection point of metal nano-tube
Expect that (metal) absorbs pulsed light, more effectively causes inner heat in cross section, thus the part welding.By the engagement,
Connection area between the nano wire or nanotube of cross section increases, and sheet resistance can be made to decline.In this way, passing through irradiation arteries and veins
It washes off and engages the intersection point of metal nanometer line or metal nano-tube, forming metal nanometer line or metal nano-tube becomes cancellous
Conductive layer.Therefore, it can be improved the electric conductivity of transparent conductive patterns, sheet resistance value becomes 10~800 Ω/.Furthermore shape
At metal nanometer line or the mesh of metal nano-tube, under high density state not spaced apart not preferably.Because if not empty
The standard width of a room in an old-style house declines every the transmissivity of then light.Furthermore light irradiation can be implemented under air atmosphere, but as needed can also be in nitrogen etc.
Inert atmosphere under and/or decompression is lower implements.
In addition, preferably attaching protective film after pulsed light irradiation on the top of transparent conductive patterns, protecting conductive film.
It is also effective for replacing irradiation aforementioned pulse light and being suppressed (pressurization) to the film after drying.It is said here
Compacting, which refers to, applies pressure to substrate, can be various modes as its mode, but particularly preferably clamp base in two pieces of plates
Method that material is pressed and the side using roller for applying stressed mode, especially the latter to substrate using columned roller
Formula can apply in heterogeneity pressure it is advantageous to.
By pressure roller apply pressure in the case where, line pressure be preferably 0.1kgf/cm (98Pam) or more and
1000kgf/cm (980kPam) is hereinafter, more preferably 1kgf/cm (980Pam) or more and 100kgf/cm (98kPam)
Below.The transmission speed (linear velocity) of substrate can also suitably select in usage range, but be generally preferred to 10mm/ minutes with
Above and 10000mm/ minutes hereinafter, more preferably 10mm/ minutes or more and 100m/ minutes or less.Because if it is too fast then no
To enough pressing times, and it is difficult to precision and uniformly applies pressure well.In addition, repeatedly being increased by the radical for increasing pressure roller
Add compression number, increase pressing time, to ensure that the connection of metal nanometer line is also useful method.In addition, in order to stronger
Ground fitting can be heated in compacting.
Be clipped in by common pressure setting pressurizeed in 2 pieces of plates in the case where, no image of Buddha pressure roller is equal like that
It pressurizes, therefore wishes as pressure for 0.1MPa~200MPa, more preferably 1MPa~100MPa evenly.
In addition, can be heated in pressurization to more firmly be bonded.By pressurizeing under not only volume resistivity
Drop, the mechanical property of bending strength etc. also can be improved.Furthermore for pressure, original pressure is higher under volume resistivity
The raising of drop and/or mechanical strength is more effective, but in the case where pressure is too high, the cost of pressurizing device becomes very high, obtains
To effect do not get higher instead but, therefore the value that the upper limit value is desirable to.
Both the light irradiation and compacting can only implement any one, also can be used together.
Embodiment
Hereinafter, illustrating the embodiment of the present invention.Furthermore embodiment below is example of the invention for ease of understanding
Son, the present invention is not limited to these Examples.
Embodiment 1
<production of silver nanowires>
By polyvinylpyrrolidone K-90 ((strain) Japan catalyst Co. system) (0.49g), AgNO3(0.52g) and
FeCl3(0.4mg) is dissolved in ethylene glycol (125ml), and heating reaction in 1 hour is carried out at 150 DEG C.Using centrifuge separation to
To precipitate separated, precipitate has been dried to obtain to the silver nanowires (average diameter 36nm, 20 μm of average length) of target.
Above-mentioned ethylene glycol, AgNO3And FeCl3Being can corporation with Wako Pure Chemical Industries strain formula.
<production of transparent conductivity ink>
The two of 6 times of capacity is added in the reaction solution of silver nanowires obtained from reacting to the heating carried out 1 hour at 150 DEG C
After butyl ether and stirring, standing precipitates nano wire.After nano wire precipitating, using decantation by supernatant separation, solvent is thus carried out
Displacement obtains the suspension for the silver nanowires dispersed in the butyl oxide (viscosity adjustment solvent) comprising about 20 mass % silver nanowiress
Liquid.
Terpinol (Japanese terpene chemistry strain of the 6g as viscosity adjustment solvent is added into the suspension of the 0.5g silver nanowires
Formula commercial firm (Nippon Terpene Chemicals, Inc.) system), after well dispersing it, 14g is added and is kept as shape
The テ Le ソ Le Block MTPH (Terusolve MTPH, Japanese terpene Chemical Co., Ltd. system, isobornyl cyclohexanol) of agent is used
The ARV-310 of (strain) new base corporation disperses it well, has obtained transparent conductivity ink.
Obtained ink carries out thermogravimetry, and the residue after 500 DEG C of heating is calculated as the silver nanowires in ink, tied
Silver nanowires concentration in fruit ink is 0.5 mass %.The analytical equipment of thermogravimetric amount is Block ル カ ー エ イ ッ Network ス Co., Ltd.
The differential-type superhigh temperature thermobalance TG-DTA galaxy (S) of (Bruker AXS company) system.
Obtained ink determines the viscosity at 25 DEG C using the model DV-II+Pro of BROOKFIELD corporation.Using turn
The viscosity that sub- number 52 determines is 1.5 × 104mPa·s.Furthermore silver nanowires content contained in ink is 0.5 matter
It amount %, is a small amount of, therefore the black viscosity and the viscosity of decentralized medium itself are substantially same.
<printing of transparent conductivity ink>
Circle scraper plate (APOLAN is installed in screen process press MT-320TVZ (MICROTECH (strain) system)
International company rounding scraper plate, polyurethane system, hardness 70, thickness 9.5mm, radius of curvature 4.8mm), using by above-mentioned
The transparent conductivity ink print 2.5cm modulated2Comprehensive film (gap: 1.0mm, blade angle: 70 °, scraper velocity:
100mm/ seconds, scraper plate moving distance when printing: 15cm, scraper plate printing pressure: 0.2MPa, scraper (scraper) pressure:
0.15MPa, back pressure: 0.1MPa).In addition, having used eastern beautiful (strain) company polyester film: Lumirror (registered trademark) as substrate
T60 (125 μm of thickness).It after printing, uses hot air circular drying machine 1 hour dry with 100 DEG C, has obtained transparent conductivity ink
Printed article.
<light of the printed article of transparent conductivity ink is burnt into>
The printed article of transparent conductivity ink uses the light burning apparatus Pulse Forge of NovaCentrix corporation
3300, the pulsed light of 40 microseconds is irradiated with 600V single-shot.
Comparative example 1
<printing of transparent conductivity ink>
Substitute circle scraper plate (APOLAN International company rounding scraper plate, hardness 70, radius of curvature 4.8mm), peace
Flat scraper plate (the micro- scraper plate of Microtec corporation, polyurethane system, hardness 70, thickness 9mm) is filled, in addition to this similarly to Example 1
Ground printing.Furthermore the side of the flat scraper plate used is illustrated in Fig. 4.
<light of the printed article of transparent conductivity ink is burnt into>
Using NovaCentrix corporation light burning apparatus Pulse Forge 3300, the pulse of 600V, 40 microseconds are substituted
Light irradiation carries out the pulsed light single-shot irradiation of 600V, 50 microseconds with the device.
<measurement of silver nanowires>
The average diameter of prepared silver nanowires and average length (average diameter 36nm, 20 μ of average length as described above
It m), is that the above-mentioned reaction solution for heating the silver nanowires after reacting carried out 1 hour with 150 DEG C is carried out solvent with butyl oxide to set
It changes, a part of the suspension of the silver nanowires by solvent displacement is further diluted with butyl oxide, is drenched on glass, it is dry
The diameter of 100 silver nanowiress is measured using SEM (Hitachi Co., Ltd S-5000) afterwards and length and is found out respectively
Average value.
The length of the silver nanowires of (print pass 0 time) before printing is by prepared electrically conducting transparent as described above
Property a small amount of sampling of ink, with methanol dilution and drench on glass, use SEM (Hitachi Co., Ltd S-5000) after dry
The length for measuring 100 silver nanowiress finds out its average value.
In addition, implementing 200 printings repeatedly using embodiment 1 and the method for comparative example 1, just will terminate 5,50,100,
150, the ink in the screen mask after 200 printings and the ink before printing are sampled on a small quantity, with methanol dilution and are drenched in glass
On, the length of 100 silver nanowiress is measured after dry using SEM (Hitachi Co., Ltd S-5000), it is flat to find out it
Length of the mean value as the silver nanowires after 5,50,100,150,200 printings.
Table 1 shows the length of the silver nanowires after (print pass 0 time) and 5,50,100,150,200 times before printing are printed.
<measurement of sheet resistance>
It, can corporation LORESTA-GP using Mitsubishi Chemical's strain formula for the sedimentary of the silver nanowires after irradiating pulsed light
4 sonde method surface resistivity of MCP-T610, volume resistivity measurement device determine sheet resistance.The result determined is shown
In table 1.Measuring number is 2, shows its average value.
<measurement of full light transmittance>
Using Japanese electric color industry (strain) nephelometer NDH2000 processed, full light transmittance is determined.The result determined is shown in
Table 1.Measuring number is 2, shows its average value.
With repeatedly print alternative line length, it is known that print pass be 50 times or more when embodiment 1 maintain relative to than
Compared with the state that example 1 is about 3 double-lengths, and sheet resistance stablizes passage.In addition, using in the embodiment 1 of circle scraper plate, other printings
When condition is identical, the power of the vertical direction applied compared with the case where using flat scraper plate to ink becomes larger, and printing film thickness correspondingly becomes
Thickness, as a result sheet resistance and full light transmittance are lower.
Table 1
Description of symbols
1 substrate, 2 screen masks, 3 circle scraper plates, 4 print directions, 5 transparent conductivities ink.
Claims (14)
1. a kind of forming method of transparent conductive patterns, which is characterized in that there is song using the top end part contacted with screen mask
Transparent conductivity ink is carried out silk-screen printing by the scraper plate of face shape, and the transparent conductivity ink includes metal nanometer line and metal
At least one of nanotube and decentralized medium.
2. the forming method of transparent conductive patterns according to claim 1, the top of the scraper plate contacted with screen mask
The radius of curvature of the curved surface of end is 0.1~20mm.
3. the forming method of transparent conductive patterns according to claim 2, the top of the scraper plate contacted with screen mask
The radius of curvature of the curved surface of end is 2~10mm.
4. the forming method of described in any item transparent conductive patterns according to claim 1~3, the material of the scraper plate is to close
At any one of rubber, natural rubber, metal, plastics.
5. the forming method of transparent conductive patterns according to claim 4, the synthetic rubber is by polyurethane rubber or silicon
Rubber is constituted.
6. the forming method of transparent conductive patterns according to any one of claims 1 to 5, scraper velocity is set as 5~
Progress silk-screen printing in 200mm/ seconds.
7. the forming method of described in any item transparent conductive patterns according to claim 1~6, the transparent conductivity ink
In, include 0.01~10 matter relative to transparent conductivity ink gross mass as the total amount of metal nanometer line and metal nano-tube
Measure %.
8. the forming method of transparent conductive patterns according to any one of claims 1 to 7, the decentralized medium includes shape
Shape retention agent, the shape retention agent are made of the organic compound that molecular weight ranges are 150~500.
9. the organic compound of the forming method of transparent conductive patterns according to claim 8, the shape retention agent is
Any one of monosaccharide compound, polyol compound, compound with alkyl and hydroxyl, the alkyl have quaternary carbon former
Son and/or bridge ring skeleton.
10. the organic compound of the forming method of transparent conductive patterns according to claim 9, the shape retention agent is
Two glycerol, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate, xylulose, ribulose, bornyl cyclohexanol, borneol, different dragon
Any one of brain cyclohexanol and isoborneol.
11. according to the forming method of described in any item transparent conductive patterns of claim 8~10, the decentralized medium is also wrapped
The viscosity of the viscosity of the shape retention agent containing adjustment adjusts solvent.
12. the forming method of transparent conductive patterns according to claim 11, the viscosity adjustment solvent be water, alcohol, ketone,
At least one of ether, the hydrocarbon solvent of aliphatic category and hydrocarbon solvent of aromatic.
13. the alcohol of the forming method of transparent conductive patterns according to claim 12, the viscosity adjustment solvent is pine tar
Alcohol.
14. according to the forming method of described in any item transparent conductive patterns of claim 8~13, the shape retention agent
Content is 10~90 mass % relative to decentralized medium gross mass.
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| PCT/JP2017/019330 WO2017208924A1 (en) | 2016-05-31 | 2017-05-24 | Method for forming transparent conductive pattern |
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| KR (1) | KR102228232B1 (en) |
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| CN110247193A (en) * | 2019-05-13 | 2019-09-17 | 华中科技大学 | A kind of flexible gradual change resistive film, preparation method and application |
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| WO2021131099A1 (en) * | 2019-12-27 | 2021-07-01 | 昭和電工株式会社 | Method for manufacturing transparent conductive film |
| CN111629528B (en) * | 2020-05-21 | 2021-04-02 | 北京航空航天大学 | Curved surface micro-pen electrostatic direct writing forming device based on two-degree-of-freedom balance ring |
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| WO2015068654A1 (en) * | 2013-11-05 | 2015-05-14 | 昭和電工株式会社 | Conductive pattern formation method, production method for on-cell-type touch panel using same, transfer film used in same, and on-cell-type touch panel |
| JP6251012B2 (en) * | 2013-11-18 | 2017-12-20 | 株式会社ケー・アイ・エス | Pattern forming device |
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| JP2000043237A (en) * | 1998-07-29 | 2000-02-15 | Toppan Printing Co Ltd | Squeegee, squeegeeing mechanism and method for screen printing using it |
| CN104303238A (en) * | 2012-04-26 | 2015-01-21 | 国立大学法人大阪大学 | Transparent conductive ink, and method for producing transparent conductive pattern |
| CN104553408A (en) * | 2014-02-05 | 2015-04-29 | 北京智膜科技有限公司 | Manufacture method of transparent induction film material |
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| CN110247193A (en) * | 2019-05-13 | 2019-09-17 | 华中科技大学 | A kind of flexible gradual change resistive film, preparation method and application |
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| JPWO2017208924A1 (en) | 2019-03-28 |
| TWI787185B (en) | 2022-12-21 |
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