CN107964111A - Flexible conductive film based on conductive nano silver wire - Google Patents

Flexible conductive film based on conductive nano silver wire Download PDF

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Publication number
CN107964111A
CN107964111A CN201711264453.5A CN201711264453A CN107964111A CN 107964111 A CN107964111 A CN 107964111A CN 201711264453 A CN201711264453 A CN 201711264453A CN 107964111 A CN107964111 A CN 107964111A
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nano silver
silver wire
parts
conductive film
flexible conductive
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CN201711264453.5A
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Chinese (zh)
Inventor
夏厚君
杨晓明
江叔福
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Zhejiang Ouren New Material Co Ltd
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Zhejiang Ouren New Material Co Ltd
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Priority to CN201711264453.5A priority Critical patent/CN107964111A/en
Publication of CN107964111A publication Critical patent/CN107964111A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • 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
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The present invention discloses a kind of flexible conductive film based on conductive nano silver wire, comprises the following steps：By nano silver wire aqueous dispersions, water-based acrylic resin, 2 ~ 5 parts of diallylamine, 30 ~ 40 parts of double solvents；It is added to vacuum defoamation in de-airing mixer, is uniformly mixed, obtains mixed liquor, the concentration of the nano silver wire aqueous dispersions is 2~10mg/mL, and the double solvents is mixed by alcohols solvent, ketones solvent；Wet film is dried into 3 ~ 10min in 150 DEG C of vacuum drying chambers, treats to volatilize completely in wet film, it is the flexible conductive film to take out.Present invention reduces conductive resistance rate, also further avoid nano silver wire accumulation, ensure that the uniformity of conduction, also improve light transmittance.

Description

Flexible conductive film based on conductive nano silver wire
Technical field
The present invention relates to a kind of nano silver wire technical field, more particularly to a kind of compliant conductive based on conductive nano silver wire Film.
Background technology
Flexible product such as wearable device is increasingly praised highly be subject to people.And the exploitation of flexible product be unable to do without flexible substrates. But the immature exploitation for causing flexible product of current flexible substrates is absorbed in bottleneck.PSS, the stone of flexible conducting substrate can be achieved In black alkene, carbon nanotubes, nano metal line, nano silver wire is as the most possible material for realizing commercialization flexible conductive film at present Material, its research receive much concern.For nano silver wire as metal nano material, it does not dissolve in various solvents.Thus, can be used it The processing methods such as lower-cost spraying, roller coating, blade coating, it is necessary to add various auxiliary agents and prepare nano silver wire stable dispersion, coating The nano silver wire coating liquid of excellent performance.The performance for the silver-colored conductive film that the decision of coating liquid performance processes, and the choosing of auxiliary agent Select, determine the performance of coating liquid.Therefore, to obtain optimal nano silver wire film, people attempt to be prepared with various different auxiliary agents The coating liquid of different performance.The index such as the product electric conductivity of the nano silver wire coating liquid formation of existing formula and light transmittance still has Wait to improve, how to overcome above-mentioned technical problem and improve, become the direction of those of ordinary skill in the art's effort.
The content of the invention
It is an object of the present invention to provide a kind of flexible conductive film based on conductive nano silver wire, this is based on conductive nano silver wire Nano silver wire slurry can both reduce nano silver wire content in flexible conductive film, effectively disperse nano-silver thread, reduce conductive electricity Resistance rate, also improves the adhesive force of nano silver wire water and basement membrane after subsequent coated.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of compliant conductive based on conductive nano silver wire Film, the compliant conductive film surface are coated with nano silver wire coating, this nano silver wire coating layer thickness is 20 ~ 100 microns, described Nano silver wire coating is dried by nano silver wire slurry and obtained, this nano silver wire slurry is made of the component of following parts by weight：Yin Na 100 parts of rice noodles aqueous dispersions, 6 ~ 10 parts of water-based acrylic resin, 2 ~ 5 parts of diallylamine, 1 ~ 2 part of pyrroloquinoline quinone, carboxymethyl 0.1 ~ 0.3 part of sodium cellulosate, 0.2 ~ 0.4 part of fatty alcohol polyoxyethylene ether, 0.3 ~ 0.5 part of isopropoxide ethanol, double solvents 30 ~ 40 parts；
Comprise the following steps：
Step 1: by 100 parts of nano silver wire aqueous dispersions, 6 ~ 10 parts of water-based acrylic resin, 2 ~ 5 parts of diallylamine, compound 30 ~ 40 parts of solvent；It is added to vacuum defoamation in de-airing mixer, is uniformly mixed, obtain mixed liquor, the nano silver wire moisture dissipates The concentration of liquid is 2~10mg/mL, and the double solvents is mixed by alcohols solvent, ketones solvent；
Step 2: 1 ~ 2 part of pyrroloquinoline quinone, 0.1 ~ 0.3 part of sodium carboxymethylcellulose are added in mixed liquor under agitation, it is rear to continue Stir about 10 minutes, makes to be sufficiently mixed uniformly, this water-soluble resin liquid is water-soluble polyester resin liquid；
Step 3: adding 0.2 ~ 0.4 part of fatty alcohol polyoxyethylene ether according to quantity, 0.3 ~ 0.5 part of isopropoxide ethanol is added to vacuum In mixer, continue to stir evenly, that is, obtain the nano silver wire slurry for being based on nano silver wire；
Step 4: using PET as transparent flexible base material, the nano silver wire slurry is evenly applied in a manner of bar roller coating PET, wherein bar spacing are 15 μm, and roller coating speed is 80cm/min, and substrate surface forms one layer of uniform wet film；
Step 5: the wet film is dried 3 ~ 10min in 150 DEG C of vacuum drying chambers, treat to volatilize completely in wet film, take out i.e. described Flexible conductive film.
Further improved technology scheme is as follows in above-mentioned technical proposal：
1st, in such scheme, a diameter of 20 ~ 150nm of nano silver wire, nano-silver thread length are in the nano silver wire aqueous dispersions 50~500μm。
2nd, in such scheme, the alcohols solvent is one kind in methanol, ethanol and isopropanol.
3rd, in such scheme, the ketones solvent is acetone, one kind in butanone, cyclohexanone, isophorone.
4th, in such scheme, the double solvents is by alcohols solvent, ketones solvent according to 10：（2~4）Parts by weight mixing Form.
Since above-mentioned technical proposal is used, the present invention has following advantages and effect compared with prior art：
The flexible conductive film based on conductive nano silver wire of the invention, its nano silver wire slurry 100 parts of nano silver wire aqueous dispersions, 6 ~ 10 parts of water-based acrylic resin, 0.1 ~ 0.3 part of sodium carboxymethylcellulose, 0.2 ~ 0.4 part of fatty alcohol polyoxyethylene ether, isopropyl oxygen 2 ~ 5 parts of diallylamine, 1 ~ 2 part of pyrroloquinoline quinone are further added in 0.3 ~ 0.5 part of system of base ethanol, can both reduce silver nanoparticle Line content, effectively disperses nano-silver thread, reduces conductive resistance rate, also improve nano silver wire water and basement membrane after subsequent coated Adhesive force；Secondly, its be formulated further using 0.3 ~ 0.5 part of isopropoxide ethanol and by alcohols solvent, ketones solvent according to 10：（2~4）Parts by weight mix double solvents, effectively adjust nano silver wire slurry viscosity and rate of drying, further Nano silver wire accumulation is avoided, the uniformity of conduction is ensure that, also improves light transmittance.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1 ~ 4：A kind of flexible conductive film based on conductive nano silver wire, the compliant conductive film surface are coated with silver nanoparticle Line coating, this nano silver wire coating layer thickness are 20 ~ 100 microns, and the nano silver wire coating is obtained by the drying of nano silver wire slurry , this nano silver wire slurry is made of the component of following parts by weight, as shown in table 1：
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Nano silver wire aqueous dispersions 100 parts 100 parts 100 parts 100 parts
Water-based acrylic resin 18 20 16 15
Diallylamine 15 14 20 12
Pyrroloquinoline quinone 10 8 5 6
Sodium carboxymethylcellulose 50 45 60 55
Fatty alcohol polyoxyethylene ether 25 30 20 28
Isopropoxide ethanol 20 25 20 16
Double solvents 1.5 1.5 1.4 1.58
；
In embodiment 1 double solvents by methanol, cyclohexanone according to 10：2 parts by weight mix, in embodiment 2 double solvents by Isopropanol, butanone are according to 10：2.5 parts by weight mix, in embodiment 3 double solvents by ethanol, cyclohexanone according to 10：3 weights Amount part mix, in embodiment 4 double solvents by methanol, isophorone according to 10：3.8 parts by weight mix.
The flexible conductive film is obtained by following steps：
Step 1: by 100 parts of nano silver wire aqueous dispersions, 6 ~ 10 parts of water-based acrylic resin, 2 ~ 5 parts of diallylamine, compound 30 ~ 40 parts of solvent；It is added to vacuum defoamation in de-airing mixer, is uniformly mixed, obtain mixed liquor, the nano silver wire moisture dissipates The concentration of liquid is 2~10mg/mL；The double solvents is mixed by alcohols solvent, ketones solvent；
Step 2: 1 ~ 2 part of pyrroloquinoline quinone, 0.1 ~ 0.3 part of sodium carboxymethylcellulose are added in mixed liquor under agitation, it is rear to continue Stir about 10 minutes, makes to be sufficiently mixed uniformly, this water-soluble resin liquid is water-soluble polyester resin liquid；
Step 3: adding 0.2 ~ 0.4 part of fatty alcohol polyoxyethylene ether according to quantity, 0.3 ~ 0.5 part of isopropoxide ethanol is added to vacuum In mixer, continue to stir evenly, that is, obtain the nano silver wire slurry for being based on nano silver wire；
Step 4: using PET as transparent flexible base material, the nano silver wire slurry is evenly applied in a manner of bar roller coating PET, wherein bar spacing are 15 μm, and roller coating speed is 80cm/min, and substrate surface forms one layer of uniform wet film；
Step 5: the wet film is dried 3 ~ 10min in 150 DEG C of vacuum drying chambers, treat to volatilize completely in wet film, take out i.e. described Flexible conductive film.
A diameter of 20 ~ the 150nm of nano silver wire in above-mentioned nano silver wire aqueous dispersions, nano-silver thread length are 50 ~ 500 μm.
The test result of flexible conductive film of the present embodiment 1 ~ 4 based on conductive nano silver wire, as shown in table 2：
Table 2
It was found from form 2, during using flexible conductive film of the present invention based on conductive nano silver wire, its nano silver wire slurry can both drop Low nano silver wire content, effectively disperses nano-silver thread, reduces conductive resistance rate, also improve nano silver wire after subsequent coated The adhesive force of water and basement membrane；Secondly, it effectively adjusts the viscosity of nano silver wire slurry and rate of drying, further avoid Yin Na Rice noodles are accumulated, and be ensure that the uniformity of conduction, are also improved light transmittance.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.

Claims (5)

  1. A kind of 1. flexible conductive film based on conductive nano silver wire, it is characterised in that：The compliant conductive film surface is coated with silver Nano wire coating, this nano silver wire coating layer thickness are 20 ~ 100 microns, and the nano silver wire coating is dried by nano silver wire slurry Obtain, this nano silver wire slurry is made of the component of following parts by weight：100 parts of nano silver wire aqueous dispersions, water soluble acrylic acid tree 6 ~ 10 parts of fat, 2 ~ 5 parts of diallylamine, 1 ~ 2 part of pyrroloquinoline quinone, 0.1 ~ 0.3 part of sodium carboxymethylcellulose, fatty alcohol polyoxy second 0.2 ~ 0.4 part of alkene ether, 0.3 ~ 0.5 part of isopropoxide ethanol, 30 ~ 40 parts of double solvents；
    The flexible conductive film is obtained by following steps：
    Step 1: by 100 parts of nano silver wire aqueous dispersions, 6 ~ 10 parts of water-based acrylic resin, 2 ~ 5 parts of diallylamine, compound 30 ~ 40 parts of solvent；It is added to vacuum defoamation in de-airing mixer, is uniformly mixed, obtain mixed liquor, the nano silver wire moisture dissipates The concentration of liquid is 2~10mg/mL；The double solvents is mixed by alcohols solvent, ketones solvent；
    Step 2: 1 ~ 2 part of pyrroloquinoline quinone, 0.1 ~ 0.3 part of sodium carboxymethylcellulose are added in mixed liquor under agitation, it is rear to continue Stir about 10 minutes, makes to be sufficiently mixed uniformly, this water-soluble resin liquid is water-soluble polyester resin liquid；
    Step 3: adding 0.2 ~ 0.4 part of fatty alcohol polyoxyethylene ether according to quantity, 0.3 ~ 0.5 part of isopropoxide ethanol is added to vacuum In mixer, continue to stir evenly, that is, obtain the nano silver wire slurry for being based on nano silver wire；
    Step 4: using PET as transparent flexible base material, the nano silver wire slurry is evenly applied in a manner of bar roller coating PET, wherein bar spacing are 15 μm, and roller coating speed is 80cm/min, and substrate surface forms one layer of uniform wet film；
    Step 5: the wet film is dried 3 ~ 10min in 150 DEG C of vacuum drying chambers, treat to volatilize completely in wet film, take out i.e. described Flexible conductive film.
  2. 2. the flexible conductive film according to claim 1 preparation process of nano silver wire slurry, it is characterised in that：It is described A diameter of 20 ~ the 150nm of nano silver wire in nano silver wire aqueous dispersions, nano-silver thread length are 50 ~ 500 μm.
  3. 3. the flexible conductive film according to claim 1 preparation process of nano silver wire slurry, it is characterised in that：It is described Alcohols solvent is one kind in methanol, ethanol and isopropanol.
  4. 4. the flexible conductive film according to claim 1 preparation process of nano silver wire slurry, it is characterised in that：It is described Ketones solvent is acetone, one kind in butanone, cyclohexanone, isophorone.
  5. 5. the flexible conductive film according to claim 1 preparation process of nano silver wire slurry, it is characterised in that：It is described Double solvents is by alcohols solvent, ketones solvent according to 10：（2~4）Parts by weight mix.
CN201711264453.5A 2017-12-05 2017-12-05 Flexible conductive film based on conductive nano silver wire Pending CN107964111A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108749244A (en) * 2018-06-07 2018-11-06 苏州袭麟光电科技产业有限公司 A kind of optics high flexibility electro-conductive glass film and preparation method thereof
WO2019109710A1 (en) * 2017-12-05 2019-06-13 浙江欧仁新材料有限公司 Preparation process for silver nanowire slurry for flexible conductive thin film
CN110791136A (en) * 2019-09-25 2020-02-14 深圳市华科创智技术有限公司 Silver nanowire coating solution and transparent conductive film

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CN104640697A (en) * 2012-07-02 2015-05-20 卡尔斯特里姆保健公司 Transparent conductive film
CN105111825A (en) * 2015-10-09 2015-12-02 重庆文理学院 Alcohol-based silver nano-wire conducting ink and preparation method of conducting film of alcohol-based silver nano-wire conducting ink
CN105273471A (en) * 2015-12-07 2016-01-27 苏州艾达仕电子科技有限公司 Water-soluble nano-silver conductive coating
CN105295488A (en) * 2015-12-07 2016-02-03 苏州艾达仕电子科技有限公司 High-transparency waterborne conductive coating based on silver nanowire serving as medium

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Publication number Priority date Publication date Assignee Title
CN104640697A (en) * 2012-07-02 2015-05-20 卡尔斯特里姆保健公司 Transparent conductive film
CN105111825A (en) * 2015-10-09 2015-12-02 重庆文理学院 Alcohol-based silver nano-wire conducting ink and preparation method of conducting film of alcohol-based silver nano-wire conducting ink
CN105273471A (en) * 2015-12-07 2016-01-27 苏州艾达仕电子科技有限公司 Water-soluble nano-silver conductive coating
CN105295488A (en) * 2015-12-07 2016-02-03 苏州艾达仕电子科技有限公司 High-transparency waterborne conductive coating based on silver nanowire serving as medium

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019109710A1 (en) * 2017-12-05 2019-06-13 浙江欧仁新材料有限公司 Preparation process for silver nanowire slurry for flexible conductive thin film
CN108749244A (en) * 2018-06-07 2018-11-06 苏州袭麟光电科技产业有限公司 A kind of optics high flexibility electro-conductive glass film and preparation method thereof
CN108749244B (en) * 2018-06-07 2020-07-14 浙江欣麟新材料技术有限公司 Optical high-flexibility conductive glass film and preparation method thereof
CN110791136A (en) * 2019-09-25 2020-02-14 深圳市华科创智技术有限公司 Silver nanowire coating solution and transparent conductive film

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