CN101976591B - Transparent conductive film - Google Patents
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- CN101976591B CN101976591B CN2010102672541A CN201010267254A CN101976591B CN 101976591 B CN101976591 B CN 101976591B CN 2010102672541 A CN2010102672541 A CN 2010102672541A CN 201010267254 A CN201010267254 A CN 201010267254A CN 101976591 B CN101976591 B CN 101976591B
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Abstract
The invention discloses a transparent conductive film, which comprises a substrate and a conductive coating, wherein the conductive coating contains a conductive macromolecular polymer and metal particles; and the weight ratio of the conductive macromolecular polymer to the metal particles is 1:0.001-0.02. Due to the combined use of the conductive macromolecular polymer and the metal particles, the transparent conductive film solves the problem that the two indexes of transparency and conductivity of the film are mutually restrictive, can meet requirements on the transparency and the conductivity at the same time, and can be widely applied to the manufacture of plated through holes of printed circuit boards, organic solar cells (OSC), organic light emitting diodes (OLED), organic thin film transistors, the films of touch screens and the like.
Description
Technical field
The present invention relates to a kind of transparent conducting film.
Background technology
Universal day by day along with computer and network technology, screen displaying device application is expanded rapidly, and the consumption of conductive film for touch screen is enlarged rapidly.Should satisfy low resistance and the high performance requirement that passes through rate of visible light as conductive film for touch screen.
In order to satisfy low-resistance performance requirement, generally, the touch-screen conducting film uses oxide semiconductor materials such as ITO more; Produce through vacuum evaporation chemical deposition mode; But said method all is to realize through the vapor deposition mode, and production equipment is expensive, and production efficiency is on the low side.
In order to satisfy the performance requirement of visible light high permeability; Disclose in the prior art at conductive layer and used the conductive polymer polymer; To improve the conductivity and the light transmittance of conducting film; Application number is that 99122391.8 Chinese patent discloses a kind of electric conductive polymer fluid composition based on the polythiophene base, and said composition contains the polythiophene base electric conductive polymer aqueous solution, alcoholic solvent, amide solvent, contains the alkoxy silane of sulfonic monomeric dopant and optional selection.Though this technology discloses the polythiophene base conducting polymer fluid composition with high conductivity and transparency; But this high molecular polymer demonstrates the drastic change of electrical property along with its conductive polymer membrane of change of time; Especially under hot and humid condition, can't satisfy low-resistance performance requirement.
Summary of the invention
The technical problem that the present invention will solve is to improve a kind of nesa coating, makes it have high transmission rate and high conductivity, can satisfy the demand of touch-screen and has the high characteristics of production efficiency.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of nesa coating, it comprises base material and conductive coating, contains conducting high polymers thing and metallic in the said conductive coating, the weight ratio of conducting high polymers thing and metallic is 1: 0.001～0.02.
In the above-mentioned nesa coating, the component of said conductive coating and parts by weight thereof are:
0.4～1.5 part of film-forming resin,
60～90 parts of conducting high polymers things,
0.1～2 part of metallic,
2～10 parts of high bp polar solvent,
0.1～1 part in surfactant.
In the above-mentioned nesa coating, said conducting high polymers thing is based on the conducting high polymers thing aqueous solution of polythiophene base.
In the above-mentioned nesa coating, said metallic is gold particle, silver particles, copper particle, palladium particle or ruthenium particle.
In the above-mentioned nesa coating, the average grain diameter of said metallic is 2nm～100nm.
In the above-mentioned nesa coating, said film-forming resin is selected from polyvinyl alcohol resin, polyurethane resin, melamine resin and/or mylar.
In the above-mentioned nesa coating, said high bp polar solvent is selected from a kind of in dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO) or the N-methyl pyrrolidone.
Compared with prior art; Adopt the combination of conducting high polymers thing and metallic to use among the present invention; Through the weight ratio between adjustment conducting high polymers thing and the metallic; Solve the problem of transparency and conductivity two big index mutual restriction in the prior art, obtained to satisfy simultaneously the conducting film that transparency and conductivity require.
Embodiment
We know that transparency and conductivity are to estimate two most important indexs of conducting film performance.If use single conductive polymer polymer; The situation that possibly occur is: when improving one of them performance, will inevitably reduce another performance; This is because transparency is all relevant with the thickness of conducting film conductive coating with conductivity; Conductive coating is thin more, and transparency is high more, but conductivity is low more; On the contrary, conductive coating is thick more, and transparency is low more, but conductivity is high more, so single conductive polymer polymer is difficult to satisfy simultaneously the problem of transparency and conductivity requirement in the prior art.For addressing this problem; Adopt conducting high polymers thing and metallic jointly as conductive materials in the conductive coating among the present invention; Adopt the combination of high-conductivity polymer polymer and metallic to use; Can satisfy transparency properties, promptly confirm recently to obtain to be fit to the conductivity of demand through the weight of adjustment conducting high polymers thing and metallic under the condition of conductive coating thickness; So just solved the problem of transparency and conductivity two big index mutual restriction in the conducting film, satisfied the conducting film that transparency and conductivity requires simultaneously new method is provided for making.Conducting high polymers thing and the weight ratio between the metallic in the conductive coating of nesa coating provided by the invention are 1: 0.001～0.02.Weight ratio through between adjustment conducting high polymers thing and metallic is satisfying under the condition of transparency properties, receives the conductivity that is fit to demand simultaneously.Here, said high conductivity scope is at 300～1500S/cm.
Conducting high polymers thing among the present invention is based on the conducting high polymers thing aqueous solution PEDT of polythiophene base; Commodity of Beyer Co., Ltd " Baytron P " for example are like the CLEVIOS PH500 of Beyer Co., Ltd, CLEVIOS PH750; CLEVIOS P HC V4, CLEVIOS PH510 etc.Owing to be doped with poly styrene sulfonate (PSS), the very easy dispersion and show good thermal stability and air stability in water of this PEDT polymer.And find that control solid (PEDT and PSS) content is 1.0-1.5 weight %, make the dispersive property optimization.PEDT and water, alcohol or solvent with high dielectric constant be mixing well, and can easily be applied by the coating material that uses this solvent dilution.This coating has bigger advantage than the coating of other electric conductive polymer such as polyaniline and polypyrrole aspect transparency in addition.
In the conductive coating of the present invention, in weight portion, the conducting high polymers thing is 60～90 weight portions, preferred 80～90 weight portions.If should measure less than 60 weight portions, then when this product of preparation, will meet difficulty, even as being prone to produce crawling, the apparent color spot etc. that occurs; And if should measure on the other hand greater than 90 weight portions, because the increase of painted conducting polymer amount then can not obtain the desirable high grade of transparency, as be higher than 95% transmitance.
Be fit to metallic of the present invention and can select metallics such as gold, silver, copper, palladium for use; Be preferably gold, silver, palladium metal particle; The particle diameter of these particles is different because of the degree of the needed scattering of purposes of conducting film, and its shape cannot treat different things as the same, but generally below 200nm; Better below 100nm, best in 2nm-100nm scope class.
The addition of metallic is at 0.1～2 weight portion in the conductive coating.If add metallic less than 0.1 weight portion, then the raising for the electric conductivity of film does not just have effect, if addition is greater than 2 weight portions then can have influence on transmitance.The consumption of metallic is generally below 2 weight portions, and is better at 0.1～1 weight portion, best in 0.2～0.8 weight portion scope.
Be fit to the LK nano silver particles that metallic of the present invention can be selected from Lekai company; The VK-G01 nano silver particles of Hangzhou ten thousand scape new material Co., Ltds; The TJH board nanometer copper particle of Tai Ji nanometer Products Co., Ltd; The gold particle of Shanghai positive nanosecond science and technology company, the iNnao-Pd03N003 of Dalian Clean Inano Technology Co., Ltd. palladium particle etc.
Among the present invention; Metallic can be handled before use in advance, so that obtain best performance, can metallic be joined in the alcoholic solution of 10-30 times of weight; Alcohol does not have any special restriction, can enumerate out methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc.The dispersant that adds metallic 1-3 weight % then, dispersant can be anionic or one or more dispersants such as DISPERBYK-102, DISPERBYK-109, DISPERBYK-2096.Anionic dispersing agents can be enumerated out three (1-Methylethyl) sodium naphthalene sulfonate, neopelex etc.
It is the modes such as dispersion, high-speed stirred, ultrasonic dispersing of medium that the mode that metallic is handled has high speed shear to disperse, adopt zirconia.
Film-forming resin can improve the weatherability and the conductivity of conducting film, and the film-forming resin in the conductive coating is 0.4～1.5 weight portion, preferred 0.9～1.2 weight portion.If should measure less than 0.4 weight portion, then the weatherability of conducting film can be very poor, if should measure greater than 1.5 weight portions, the conductivity of film obviously reduces.Adopt the film-forming resin of 0.4～1.5 weight portion in the conductive coating, can under the prerequisite that guarantees the conducting film weatherability, significantly improve its conductivity.
Be fit to film-forming resin of the present invention; Can be fluoropolymer, silicones, acrylic resin, polyvinyl alcohol resin, carboxymethyl cellulose, hydroxypropyl cellulose, polyurethane resin, melamine formaldehyde resin or mylar; Preferably polyethylene alcohol resin, polyurethane resin, melamine formaldehyde resin or mylar, these film-forming resins can use separately also and can be used in combination.
Be fit to fluoropolymer of the present invention, can enumerate out polytetrafluoroethylene, polyvinylidene fluoride (PVDF), vinylidene fluoride-three and fluoridize ethylene copolymer etc.
Be fit to polyvinyl alcohol resin of the present invention and can be selected from the PVA17-88 of Beijing DongFang petroleum chemical engineering Co., Ltd. Organic Chemical Plant's production and the PVA-2090 that PVA17-99, Shandong Province's Accessories during Binzhou victory reach Industrial Co., Ltd.'s production, the SD-5 that Shanghai four happiness chemical industry Co., Ltds produce etc.; Polyurethane resin can be selected from the PU628-1 that spins the auxiliary reagent factory in Taixing City and produce, the ADM-Z706 of the U.S. macromolecular material of Guangzhou Order Co., Ltd production and the DU-1030 that ADM-F206A, Guangdong Tyen Chemicals Co., Ltd. produce etc.; Melmac can be selected from Linan City rich ability resin Co., Ltd provide LF-800, LF-9010 and the LF-9080 of production, the DHM-301 that Weihai is big and Fine Chemical Co., Ltd produces etc.; Mylar can be selected from great MD-1200, MD-1400, MD-1480 and the MD-1250 etc. that raise the production of industry development Co., Ltd in Shanghai.
Be fit to high bp polar solvent of the present invention, preferably dimethyl formamide (DMF), ethylene glycol (EG), dimethyl sulfoxide (DMSO) (DMSO) or N-methyl pyrrolidone (NMP), these high bp polar solvent can be used separately also and can be used in combination.
High bp polar solvent in the conductive coating is 2～10 weight portions, preferred 6～8 weight portions.If should measure less than 2 weight portions, then can not realize high conductivity, if should measure greater than 10 weight portions, though realize high conductivity so, because its boiling point is higher, addings will force coating dry under very high temperature in a large number, the conductivity of destruction conducting polymer.
Be fit to surfactant of the present invention, do not have what special qualification, one or more mix use can to enumerate out non-ion fluorin surfactant, anion surfactant, non-ionic surface active agent etc.
Be fit to non-ion fluorin surfactant of the present invention and can be selected from F [CF (CF
3) CF
2O]
1CF (CF
3) SO
2NH (CH
2)
4OH, C
4F
9SO
2NH (CH
2)
5OH, F [CF (CF
3) CF
2O]
5CF (CF
3) SO
2NH (CH
2)
3OH, C
8F
17CONH (CH
2)
2OH etc.
Be fit to anion surfactant of the present invention, can enumerate: C
12H
25NaO
4S, C
18H
29NaO
3S etc.
Be fit to non-ionic surface active agent of the present invention, can enumerate: AEO (AEO) AEO3, APES (TX-10, OP-10, O ∏-10).
Surfactant 0.1～1 weight portion among the present invention, preferred 0.3～0.7 weight portion.If should measure less than 0.1 weight portion, then levelability and the wetability of conductive coating in applying film forming procedure is not enough, if should measure greater than 1 weight portion, then can produce a certain amount of bubble, has influenced the apparent of conducting film.
The coating fluid of the conductive coating among the present invention can adopt following method and obtain:
Under strong agitation, add high bp polar solvent, film-forming resin, surfactant and scattered in advance nano metal particles with 1～5 minute interval in the conductive high molecular polymer successively by suitable order, then its dispersion 10～30 minutes is made coating fluid.
Nesa coating provided by the invention can prepare through following method:
With above-mentioned preparation coating fluid be coated on the base material, obtained having the conducting film of high conductivity and high transparent in dry 3-10 minute through warm braw (100～150 ℃).
Said base material can be PETG (PET) film, PEN (PEN) film, polyimides (PI) film and polypropylene (PP) film etc.; The coating method that adopts can use known dip-coating, roller coat, scraper coating and plate gravure coating method, and preferably with plate gravure coating method, the thickness of coating is 0.05～5 μ m, and the square resistance of film is 5～645 Ω/.
Through specific embodiment the present invention is done further detailed description below.The embodiment of this paper only is intended to explain the present invention, should be with its scope that is construed as limiting the invention.
Embodiment 1-5 and comparative example 1-3
Table 1 has provided employed composition and consumption.The vigorous agitation PEDT conducting polymer aqueous solution then with about 2 minutes interval, adds high bp polar solvent, film-forming resin, surfactant and metallic successively.Mixture was disperseed about 20 minutes,, obtain coating fluid thus so that it becomes evenly.
After coating fluid filtered with nylon cloth, adopt the mode of intaglio plate coating to be coated on the transparent base,, thereby prepare nesa coating through dry about 5 minutes of warm braw (120 ℃).The thickness of the dry film of crossing is 0.1-1 μ m.The method that is described below is measured so performance of the nesa coating of preparation, and the result is listed in the table 2.
Table 1:
Table 2: each embodiment performance data table
| Performance | Square resistance (Ω/) | Transmitance | Uniformity | High-temp resisting high-humidity resisting |
| Embodiment 1 | ?323 | 93.1％ | Well | Well |
| Embodiment 2 | ?279 | 90.7％ | Well | Well |
| Embodiment 3 | ?338 | 91.2％ | Well | Well |
| Embodiment 4 | ?315 | 92.1％ | Well | Well |
| Embodiment 5 | ?240 | 90.1％ | Well | Well |
| The comparative example 1 | ?436 | 91.3％ | Well | Well |
| The comparative example 2 | ?479 | 89.5％ | Well | Well |
| The comparative example 3 | ?454 | 90.5％ | Well | Well |
Performance evaluation:
1. square resistance method of testing
Measure the square resistance of film through RTS-8 type four point probe resistance meter, and come the uniformity of evaluated for film through the rate of change of the square resistance of multiple spot relatively.
< rate of change of square resistance >
1. less than 8%: good
2. 8%-15%: general
3. greater than 15%: poor
2. the method for testing of light transmittance
Under 550nm, estimate light transmittance.Be regarded as the transmitance that 100% mode is represented coated substrate according to light transmittance, on WGT-S type transmitance analyzer (Shanghai precision instrument science Co., Ltd), measure according to the GB2410-80 standard with transparent substrates.
3. high-temp resisting high-humidity resisting performance
At steady temperature (60 ℃) and humidity (90%RH) held 240h, obtain the high-temp resisting high-humidity resisting performance through the rate of change of estimating square resistance.
< rate of change of square resistance >
1. less than 15%: good
2. 15%-30%: general
3. greater than 30%: poor.
Claims (6)
1. nesa coating, it comprises base material and conductive coating, it is characterized in that, contains conducting high polymers thing and metallic in the said conductive coating, the weight ratio of conducting high polymers thing and metallic is 1: 0.001～0.02;
The component of said conductive coating and parts by weight thereof are:
0.4～1.5 part of film-forming resin,
60～90 parts of conducting high polymers things,
0.2～2 part of metallic,
2～10 parts of high bp polar solvent,
0.1～1 part in surfactant.
2. according to the said nesa coating of claim 1, it is characterized in that said conducting high polymers thing is based on the conducting high polymers thing aqueous solution of polythiophene base.
3. according to the said nesa coating of claim 2, it is characterized in that said metallic is gold particle, silver particles, copper particle, palladium particle or ruthenium particle.
4. according to the said nesa coating of claim 3, it is characterized in that the average grain diameter of said metallic is 2nm～100nm.
5. according to the said nesa coating of claim 4, it is characterized in that said film-forming resin is selected from polyvinyl alcohol resin, polyurethane resin, melamine resin or mylar.
6. according to the said nesa coating of claim 5, it is characterized in that said high bp polar solvent is selected from a kind of in dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO) and the N-methyl pyrrolidone.
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| CN2010102672541A CN101976591B (en) | 2010-08-31 | 2010-08-31 | Transparent conductive film |
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| CN101976591B true CN101976591B (en) | 2012-07-25 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103827976A (en) * | 2011-06-17 | 2014-05-28 | 普瑞凯瑟安质提克斯公司 | Deposition processes for photovoltaics |
| JP2015502048A (en) * | 2011-11-28 | 2015-01-19 | オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー | Polymer solar cell and manufacturing method thereof |
| WO2014121456A1 (en) * | 2013-02-06 | 2014-08-14 | 深圳市海富莱电子有限公司 | Conductive material for capacitive touch screen, capacitive touch screen and preparation method thereof |
| CN107039100A (en) * | 2015-07-29 | 2017-08-11 | 上海赤龙科技有限公司 | A kind of conductive polythiophene/silver quantum dot composite conducting slurry and preparation method thereof |
| CN106674571B (en) * | 2016-12-14 | 2020-07-24 | 乐凯胶片股份有限公司 | Transparent conductive film |
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| CN1367219A (en) * | 2002-03-08 | 2002-09-04 | 清华大学 | Anisotropic conductive adhesive and its UV light solidification method |
| CN101037509A (en) * | 2006-03-15 | 2007-09-19 | 华东理工大学 | Novel organic-inorganic hybrid transparent conductive film and preparation method thereof |
| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
| CN101569245A (en) * | 2006-07-17 | 2009-10-28 | 纳幕尔杜邦公司 | Metal compositions, thermal imaging donors and patterned multilayer compositions derived therefrom |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4934993B2 (en) * | 2005-05-25 | 2012-05-23 | 住友電気工業株式会社 | Conductive paste and wiring board using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367219A (en) * | 2002-03-08 | 2002-09-04 | 清华大学 | Anisotropic conductive adhesive and its UV light solidification method |
| CN101037509A (en) * | 2006-03-15 | 2007-09-19 | 华东理工大学 | Novel organic-inorganic hybrid transparent conductive film and preparation method thereof |
| CN101569245A (en) * | 2006-07-17 | 2009-10-28 | 纳幕尔杜邦公司 | Metal compositions, thermal imaging donors and patterned multilayer compositions derived therefrom |
| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
Non-Patent Citations (1)
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Owner name: CHINA LUCKY GROUP CORPORATION Free format text: FORMER NAME: CHINESE LEKAI FILM GROUP CO |
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Address after: South Street, Hebei city of Baoding Province in new lucky number 6 Patentee after: China Lucky Group Corporation Patentee after: Lucky Film Co., Ltd. Address before: 071054 Kennan street, Hebei, Baoding, No. 6 Patentee before: Chinese Lekai Film Group Co Patentee before: Lucky Film Co., Ltd. |