CN104293009A - Electroconductive coating composition, manufacturing method of the composition and electroconductive coatings - Google Patents

Electroconductive coating composition, manufacturing method of the composition and electroconductive coatings Download PDF

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Publication number
CN104293009A
CN104293009A CN201410340282.XA CN201410340282A CN104293009A CN 104293009 A CN104293009 A CN 104293009A CN 201410340282 A CN201410340282 A CN 201410340282A CN 104293009 A CN104293009 A CN 104293009A
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ether
solvent
pedot
acrylic monomer
pss
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CN104293009B (en
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梁桐演
金贤
沈元燮
赵庆仁
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Great River Man Taike Of Co Ltd
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Great River Man Taike Of Co Ltd
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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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of 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
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • 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 relates to a conductive coating solution composition capable of shielding electromagnetic interference, a manufacturing method thereof, and a conductive coating layer capable of shielding electromagnetic interference, manufactured using the same. The composition includes 1.0 to 20.0 wt% of an acrylic organic binder, 10.0 to 65.0 wt% of a PEDOT/PSS conductive polymer water dispersion solution, 25.0 to 65.0 wt% of a solvent for dispersing or dissolving the PEDOT/PSS conductive polymer, and 0.1 to 7.0 wt% of an inorganic binder. The PEDOT/PSS conductive polymer water dispersion solution is a water dispersion agent in which PSS is doped on PEDOT and which has a molar ratio of 1:1 to 5 between the PEDOT and PSS. The acrylic organic binder consists of acrylic polymer which is polymerized between a first acrylic monomer having no hydroxyl functional group (-OH) and 10 to 200 parts by weight of a second acrylic monomer having a hydroxyl functional group for 100 parts by weight of the first acrylic monomer.

Description

Electroconductibility coating fluid composition, its manufacture method and electroconductibility coated film
Technical field
The present invention relates to a kind of electroconductibility coating fluid composition, its manufacture method and the electroconductibility coated film utilizing above-mentioned composition to manufacture, more specifically, relating to can low-temperature stiffening, can be coated with easily with wet type coating way, and applied rear hardened coated film has flexibility, excellent to the bonding force of glass or film, also there is while there is electromagnetic wave shielding performance the electroconductibility coating fluid composition of high transparent and high conductivity characteristic, its manufacture method and utilize the electroconductibility coated film with electromagnetic wave shielding function of above-mentioned composition manufacture.
Background technology
Recently, in the mobile equipment used or automatic equipment, major part is equipped with touch Panel TSP (touch screen panel; Hereinafter referred to as " TSP ").When so-called TSP refers to and do not use keyboard but apply external force by hand or pen etc. to the word occurred in picture or signal, by confirming that the picture of particular procedure is carried out in its position.TSP like this, must need the transparency electrode utilizing high conductivity material.Transparency electrode major part is, by using indium tin oxide (indium tin oxide; Hereinafter referred to as " ITO ") etc. inorganic, metal oxide carry out on film or glass depositional mode dry type coating process and use.
The type of representational TSP has, by such as GFF, GF2, the mode that GF1 is coated with transparency electrode to use the samely on film equipment and by as GG, G1, the mode etc. that G2 is coated with transparency electrode to use the samely on glass, in TSP inside, with by using optical clear adhesive tape (OCA:Optically Clear Adhesive) etc. to paste compared with the mode of transparent electrode thin film on glass, most use is by directly embodying the mode of electrode layer at inorganic, metal oxides such as deposition on glass ITO (Indium Tin Oxide), to simplify technique and to save productive expense.The problem of the dry type coating of the inorganic, metal oxides such as such deposition ITO is, not only raw material high price itself, and in deposition process, consume the too much cost of technology, and be limited mineral in representatively property by the indium (indium) of the main raw material of the ITO in the inorganic, metal oxide that uses, along with the expansion of monitor market is exhausted hastily, practical situation inevitably cause price to add to rise accordingly.
In order to overcome the shortcoming that these use the deposition of ITO inorganic oxide, be necessary supply hertzian wave (the electro magnetic interference freely, relatively at a low price to the cheap wet of the cost of technology, raw material can be carried out; EMI) shielding high connductivity coating material is studied.
Further, need to use at most in mobile equipment, the indicating meter etc., but as the same equipment of the glass of difficulty attachment material can be directly coated with and the high conductivity coated material with flexibility is studied.
Summary of the invention
Technical problem
The technical problem to be solved in the present invention is, there is provided one can low-temperature stiffening, can be coated with easily in wet mode, applied rear hardened coated film has flexibility, excellent to the bonding force of glass or film, and there is also there is the electroconductibility coating fluid composition of high transparent and high conductivity characteristic, its manufacture method and utilize the electroconductibility coated film with electromagnetic wave shielding function of above-mentioned composition manufacture while electromagnetic wave shielding performance.
Technical scheme
The invention provides a kind of electroconductibility coating fluid composition with electromagnetic wave shielding function, it is characterized in that, comprise the acrylic acid series organic binder bond of 1.0 ~ 20.0 % by weight, the PEDOT/PSS electroconductive polymer aqueous dispersions of 10.0 ~ 65.0 % by weight, 25.0 ~ 65.0 % by weight for solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved and 0.1 ~ 7.0 % by weight inorganic system tackiness agent, wherein, above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid (PSS) in Polyglycolic acid fibre (PEDOT), the mol ratio of above-mentioned Polyglycolic acid fibre (PEDOT) and above-mentioned polystyrolsulfon acid (PSS) is 1:1 ~ 5, aforesaid propylene acid is organic binder bond by not having the first acrylic monomer of hydroxyl (-OH) and carrying out being polymerized the acrylic acid polymer formed relative to second acrylic monomer with hydroxyl (-OH) that above-mentioned first acrylic monomer of 100 weight parts is 10 ~ 200 weight parts and form.
Above-mentioned first acrylic monomer can comprise and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide, above-mentioned second acrylic monomer can comprise and is selected from Propylene glycol monoacrylate, HEMA, more than one material in vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
Above-mentioned solvent can comprise more than one the first solvent be selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, ethyl acetate and butylacetate.
Relative to above-mentioned first solvent of 100 weight parts, above-mentioned solvent can comprise more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
Above-mentioned inorganic system tackiness agent can comprise and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
And, the invention provides a kind of manufacture method with the electroconductibility coating fluid composition of electromagnetic wave shielding function, it is characterized in that, comprise: (a) puts into solvent when carrying out stirring in a reservoir, temperature is risen to the step of 100 ~ 150 DEG C, (b) by have hydroxyl (-OH) the first acrylic monomer, be that have second acrylic monomer of hydroxyl (-OH) and the Diisopropyl azodicarboxylate for initiated polymerization of 0.1 ~ 10 weight part or benzoyl peroxide of 10 ~ 200 weight parts mixes relative to above-mentioned first acrylic monomer of 100 weight parts, and drip the step in said vesse, c (), when the temperature in said vesse is maintained 100 ~ 150 DEG C, makes above-mentioned first acrylic monomer and above-mentioned second acrylic monomer carry out the step of polyreaction and acrylic acid synthesizing system organic binder bond, and (d) is mixed for the solvent disperseing or dissolve PEDOT/PSS electroconductive polymer, aforesaid propylene acid is organic binder bond and inorganic system tackiness agent, and drip to the result thing of mixing the step that PEDOT/PSS electroconductive polymer aqueous dispersions carrying out stirs, wherein, in above-mentioned (d) step, the aforesaid propylene acid of mixing 1.0 ~ 20.0 % by weight is organic binder bond, the above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions of 10.0 ~ 65.0 % by weight, 25.0 ~ 65.0 % by weight for above-mentioned solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved and 0.1 ~ 7.0 % by weight above-mentioned inorganic system tackiness agent, wherein, above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid (PSS) in Polyglycolic acid fibre (PEDOT), the mol ratio of above-mentioned Polyglycolic acid fibre (PEDOT) and above-mentioned polystyrolsulfon acid (PSS) is 1:1 ~ 5.
Above-mentioned first acrylic monomer can comprise and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide, above-mentioned second acrylic monomer can comprise and is selected from Propylene glycol monoacrylate, HEMA, more than one material in vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
Above-mentioned solvent can comprise more than one the first solvent be selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, ethyl acetate and butylacetate.
Relative to above-mentioned first solvent of 100 weight parts, above-mentioned solvent can comprise more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
Above-mentioned inorganic system tackiness agent can comprise and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
And, the invention provides a kind of electroconductibility coated film with electromagnetic wave shielding function, it is characterized in that, the electroconductibility coated film with electromagnetic wave shielding function is by above-mentioned electroconductibility coating fluid composition being coated the coated film that glass or film harden, having the surface resistivity of 50 ~ 250 Ω/ scopes.
Technique effect
The electroconductibility coating fluid composition with electromagnetic wave shielding function of the present invention uses PEDOT/PSS electroconductive polymer aqueous dispersions and the excellent and tack of alcohol dissolubility (especially, tack to glass) excellent acrylic acid series organic binder bond, therefore tool has the following advantages: surface resistance can be reduced to 50 ~ 250 Ω/, not only there is the electromagnetic wave shielding performance of 10 ~ 20dB, the transparency of more than 90% can also be guaranteed, and can be coated with easily in wet mode, thus can be applicable to being used in indicating meter transparency electrode.
The bonding force of the electroconductibility coating fluid composition with electromagnetic wave shielding function of the present invention to glass or film is excellent, and also has the characteristic of high transparent and high conductivity while having electromagnetic wave shielding performance.
The electroconductibility coating fluid composition with electromagnetic wave shielding function of the present invention, due to can low-temperature stiffening, can be coated with in wet mode, and therefore productivity is excellent, less can consume the cost of technology.
The electroconductibility coating fluid composition with electromagnetic wave shielding function of the present invention goes for the up/down portion electrode, cell phone inorganic el element (EL) electrode that are applied in TSP (Touch Screen Panel).In addition, with regard to the transparency electrode of the inorganic, metal oxides such as deposition ITO, owing to lacking flexibility, therefore the electrode being applied to flexible display (Flexible Display) is difficult to, but with regard to the electroconductibility coating fluid composition with electromagnetic wave shielding function of the present invention, due to softness, therefore the electrode for flexible display (Flexible Display) can be applied in after, thus flexible display market can be dominated, and then the electromagnetic wave shieldings such as big area TV (TV), computer monitor picture can be applied to.
Accompanying drawing explanation
Fig. 1 is the example that introducing has the 2-HEA/2-HEMA acrylic acid series organic binder bond of hydroxyl (-OH), is the figure of the bonding mechanism that glass and 2-HEA/2-HEMA acrylic acid series organic binder bond are shown.
Embodiment
Below, describe in detail according to preferred embodiment of the present invention with reference to accompanying drawing.But following embodiment enables those skilled in the art understand fully and provide, and it can be deformed into multiple different shape, and scope of the present invention is not limited to the embodiment that describes below.
The present invention relates to the electroconductibility coating fluid composition of hertzian wave (EMI) shielding being used in transparency electrode, the present invention in order to solve the too much cost of technology caused by the dry type coating method of inorganic, metal oxide such as deposition ITO etc. consumption, guarantee the problem such as starting material, price increase, there is provided a kind of bonding force to glass or film excellent, and also there is while there is electromagnetic wave shielding performance the electroconductibility coating fluid composition of high transparent and high conductivity characteristic.
Electroconductibility coating fluid composition of the present invention can low-temperature stiffening, can be coated with in wet mode, and therefore productivity is excellent, less can consume the cost of technology.
If electroconductibility coating fluid composition is according to a preferred embodiment of the invention carried out wet, then show high conductivity, therefore can also embody the electromagnetic wave shielding performance of more than predeterminated level in addition.
Electroconductibility coating fluid composition according to a preferred embodiment of the invention comprises: PEDOT/PSS electroconductive polymer aqueous dispersions (aqueous dispersion), solvent, acrylic acid series organic binder bond and inorganic system tackiness agent.
Due to by synthesis and the bonding force excellence of glass, the acrylic acid series organic binder bond of alcohol dissolubility and using, because this ensure that the best solubility of glass cementation power and PEDOT/PSS electroconductive polymer aqueous dispersions, thus the coating fluid composition realizing high transparent and high conductivity is made to become possibility.
The electroconductibility coating fluid composition with electromagnetic wave shielding function according to a preferred embodiment of the invention, comprises: the acrylic acid series organic binder bond of 1.0 ~ 20.0 % by weight; For embody high conductivity 10.0 ~ 65.0 % by weight PEDOT/PSS electroconductive polymer aqueous dispersions; For disperseing or dissolve the solvent of 25.0 ~ 65.0 % by weight and the inorganic system tackiness agent of 0.1 ~ 7.0 % by weight of PEDOT/PSS electroconductive polymer.
Above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid (PSS) in Polyglycolic acid fibre (PEDOT), preferably, the mol ratio of above-mentioned Polyglycolic acid fibre (PEDOT) and above-mentioned polystyrolsulfon acid (PSS) is 1:1 ~ 5.
Aforesaid propylene acid is organic binder bond by not having the first acrylic monomer of hydroxyl (-OH) and being polymerized relative to second acrylic monomer with hydroxyl (-OH) that above-mentioned first acrylic monomer of 100 weight parts is 10 ~ 200 weight parts the acrylic acid polymer formed and forming.
Above-mentioned first acrylic monomer can comprise and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide, above-mentioned second acrylic monomer can comprise and is selected from Propylene glycol monoacrylate (Hydroxy-Propyl Acrylate), HEMA, more than one material in vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
Relative to overall content 100 weight part of above-mentioned first acrylic monomer and above-mentioned second acrylic monomer, aforesaid propylene acid is Diisopropyl azodicarboxylate or the benzoyl peroxide that organic binder bond can comprise 0.1 ~ 10 weight part of the initiated polymerization for making above-mentioned first acrylic monomer and above-mentioned second acrylic monomer further.
Above-mentioned solvent can comprise more than one the first solvent be selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, ethyl acetate and butylacetate.
Relative to above-mentioned first solvent of 100 weight parts, above-mentioned solvent can comprise more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
Above-mentioned inorganic system tackiness agent can comprise and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane (Methacryloxypropyltrimethoxysilane), silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
Above-mentioned electroconductibility coating fluid composition can comprise further for surface evening surface modulation with 0.1 ~ 3.0 % by weight additive.
The manufacture method with the electroconductibility coating fluid composition of electromagnetic wave shielding function according to a preferred embodiment of the invention, comprise: (a) puts into while solvent carries out stirring in a reservoir, temperature is risen to the step of 100 ~ 150 DEG C, b () will not have the first acrylic monomer of hydroxyl (-OH), have the second acrylic monomer of hydroxyl (-OH) and the Diisopropyl azodicarboxylate for initiated polymerization of 0.1 ~ 10 weight part or benzoyl peroxide that are 10 ~ 200 weight parts relative to above-mentioned first acrylic monomer of 100 weight parts mix, and drip the step in said vesse, c () is when being maintained 100 ~ 150 DEG C by the temperature in said vesse, above-mentioned first acrylic monomer and above-mentioned second acrylic monomer is made to carry out the step of polyreaction and acrylic acid synthesizing system organic binder bond, and (d) is mixed for the solvent that makes PEDOT/PSS electroconductive polymer disperse or dissolve, aforesaid propylene acid is organic binder bond and inorganic system tackiness agent, and drip to the product of mixing the step that PEDOT/PSS electroconductive polymer aqueous dispersions carrying out stirs.
Wherein, in above-mentioned (d) step, the aforesaid propylene acid preferably mixing 1.0 ~ 20.0 % by weight be organic binder bond, 10.0 ~ 65.0 % by weight above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions, 25.0 ~ 65.0 % by weight for above-mentioned solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved and 0.1 ~ 7.0 % by weight above-mentioned inorganic system tackiness agent.
Above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid (PSS) in Polyglycolic acid fibre (PEDOT), and the mol ratio of above-mentioned Polyglycolic acid fibre (PEDOT) and above-mentioned polystyrolsulfon acid (PSS) is preferably 1:1 ~ 5.
Above-mentioned first acrylic monomer can comprise and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide, above-mentioned second acrylic monomer can comprise and is selected from Propylene glycol monoacrylate, HEMA, more than one material in vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
Above-mentioned solvent can comprise more than one the first solvent be selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, ethyl acetate and butylacetate.
Relative to above-mentioned first solvent of 100 weight parts, above-mentioned solvent can comprise more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
Above-mentioned inorganic system tackiness agent can comprise and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane (Methacryloxypropyltrimethoxysilane), silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
The manufacture method of above-mentioned electroconductibility coating fluid composition, can mix the surface modulation additive for surface evening of 0.1 ~ 3.0 % by weight further in above-mentioned (d) step.
The electroconductibility coated film with electromagnetic wave shielding function is according to a preferred embodiment of the invention the coated film making it harden to glass or film coated above-mentioned electroconductibility coating fluid composition, has the surface resistivity of 50 ~ 250 Ω/ scopes.
Below, electroconductibility coating fluid composition is according to a preferred embodiment of the invention further illustrated.
Electroconductibility coating fluid composition according to a preferred embodiment of the invention, preferably comprise the acrylic acid series organic binder bond of 1.0 ~ 20.0 % by weight, for embody high conductivity 10.0 ~ 65.0 % by weight PEDOT/PSS electroconductive polymer aqueous dispersions, 25.0 ~ 65.0 % by weight for solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved and 0.1 ~ 7.0 % by weight inorganic system tackiness agent.
Above-mentioned electroconductibility coating fluid composition can comprise the surface modulation additive for surface evening of 0.1 ~ 3.0 % by weight further.
Above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid (PSS) in Polyglycolic acid fibre (PEDOT), wherein, the mol ratio of Polyglycolic acid fibre (PEDOT) and polystyrolsulfon acid (PSS) is 1:1 ~ 5 degree, be more preferably 1:2.5 degree, and the excellent dispersion to water, thermotolerance and air stability are very excellent.As commercial product, the representational Clevios series having Germany to congratulate Li Shi (Heraeus) company.
Preferably, in electroconductibility coating fluid composition, contain the above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions of 10.0 ~ 65.0 % by weight.If above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions containing quantity not sufficient 10.0 % by weight, then may there is the problem being difficult to realize high conductivity, if more than 65.0 % by weight, then along with the increase of electroconductive polymer with tint permanence, light transmission rate may be caused to reduce and mist degree (haze) such as to uprise at the problem of optical characteristics aspect, and likely in electroconductibility coating fluid composition, dispersion problem occur.
When only using PEDOT/PSS electroconductive polymer aqueous dispersions and general binding agent to form transparency electrode, the surface resistance due to transparency electrode is 10 3~ 10 4Ω/ degree, very high, thus existence is difficult to the problem being used in indicating meter transparency electrode.In order to reduce the surface resistance of the transparency electrode formed by these PEDOT/PSS electroconductive polymers, can consider to add dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol (Ethylene glycol), glycerine (Glycerin), Sorbitol Powder (Sorbitol), methane amide (FA), N-METHYLFORMAMIDE (NMFA), N, dinethylformamide (DMF), ethanamide (AA), N-methylacetamide (NMAA), N-N,N-DIMETHYLACETAMIDE (DMA), the scheme of the solvent that the specific inductivity such as tetrahydrofuran (THF) (THF) and n-N-methyl-2-2-pyrrolidone N-(NMP) are high, but with regard to using as the electroconductibility coating fluid composition being used in transparency electrode, remain inadequate, and due to the binding agent non-compatibility problem being used in coating fluid composition, therefore there is the problem that surface resistivity becomes higher.Consider these points, a kind of acrylic acid series organic binder bond is used in the present invention, it comprises acrylic acid polymer, and this acrylic acid polymer is by not having the first acrylic monomer of hydroxyl (-OH) and being formed relative to the second acrylic monomer polymerization with hydroxyl (-OH) that above-mentioned first acrylic monomer of 100 weight parts is 10 ~ 200 weight parts.
Aforesaid propylene acid is that organic binder bond can synthesize by the following method: suitably coordinate first acrylic monomer (monomer) without hydroxyl (-OH) and second acrylic monomer with hydroxyl (-OH), add ether system, alcohol system, fragrant hydrocarbon system, ketone system, ester system, acid amides system equal solvent separately or mixedly here, carry out solution polymerization by free radical (free radical) polymerization.Consider consistency, the acrylic acid series organic binder bond of the alcohol dissolubility of glass attachment excellence, preferably make viscosity be no more than 50,000cps, and use solvent adjustment to become to make solid content be 10 ~ 80% degree, more preferably, it is suitable for making solid content be about 30 ~ 60%.
Be that above-mentioned first acrylic monomer of organic binder bond synthesis can use and is selected from methyl acrylate (MA) as being used in aforesaid propylene acid, ethyl propenoate (EA), isopropyl acrylate (iso-PA), butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA), isopropyl methacrylate (iso-PMA), butyl methacrylate (BMA), lauryl methacrylate(LMA) (LMA), vinylformic acid (AA), methacrylic acid (MAA), methylene-succinic acid (IA), acrylamide (AAm), n-n-methylolacrylamide (nMAAm), diacetone acrylamide (DAAm), glycidyl methacrylate (GMA), vinylbenzene (ST/SM), Vinyl toluene (VT), more than one material in vinyl-acetic ester (VAc) and vinyl cyanide (AN).
In order to the excellent and acrylic acid series organic binder bond of alcohol dissolubility of the adhesion property closing pair glass, more than one the material be selected from Propylene glycol monoacrylate (HPA), HEMA (2-HEMA), vinylformic acid 2-hydroxyl ethyl ester (2-HEA) and Rocryl 410 (HPMA) can be used as second acrylic monomer with hydroxyl (-OH).
With regard to above-mentioned first acrylic monomer without hydroxyl (-OH) and there is hydroxyl (-OH) the second acrylic monomer with regard to, preferably mix with the weight ratio of 1:0.1 ~ 2 and be polymerized.That is, relative to above-mentioned first acrylic monomer 100 weight part without hydroxyl (-OH), preferably mix the above-mentioned of 10 ~ 200 weight parts and there is the second acrylic monomer of hydroxyl (-OH) and be polymerized.
Diisopropyl azodicarboxylate (AIBN) can be used as the polymerization starter used during acrylic acid synthesizing system organic binder bond, but when needing to carry out graft polymerization, preferably use benzoyl peroxide (BPO).Although above-mentioned Diisopropyl azodicarboxylate (AIBN) price is cheap, there is the shortcoming reduced the solvency power of solvent.Due to above-mentioned polymerization starter decomposition temperature normally with 10 hr half-life for benchmark represents, therefore decomposition rate and active different according to temperature of reaction, so should be noted that in selection.With regard to above-mentioned polymerization starter, relative to overall content 100 weight part of above-mentioned first acrylic monomer and above-mentioned second acrylic monomer, preferably mix 0.1 ~ 10 weight part.
Preferably, aforesaid propylene acid containing 1.0 ~ 20 % by weight in electroconductibility coating fluid composition is organic binder bond, contain few if aforesaid propylene acid is organic binder bond, then reduce the bonding force with glass, contain many if aforesaid propylene acid is organic binder bond, particle then owing to being coated with rear electroconductive polymer can not be arranged in coated film on the surface equably, thus may reduce high conduction performance.
In order to improve and the adhibit quality of above-mentioned glass or film and weather resistance, the inorganic system tackiness agent used can use methyltrimethoxy silane (Metyltrimethoxysilane), Union carbide A-162 (Methyltriethoxysilane), Trimethoxy silane (Trimethoxysilane), triethoxyl silane (Triethoxysilane), tetraethoxysilane (Tetraethoxysilane), γ-aminopropyl triethoxysilane (γ-aminopropyltriethoxysilane), aminopropyltriethoxy diethoxy silane (Aminopropylmethyldiethoxysilane), aminopropyltriethoxy dimethoxysilane (Aminopropylmethyldimethoxysilane), γ-glycidoxypropyltrietandysilane andysilane (γ-glycidoxypropyltriethoxysilane), gamma-methyl allyl acyloxypropyl trimethoxysilane (γ-methacryloxypropyltrimethoxysilane), silicon fluoride (fluorine silane), vinyltriethoxysilane (Vinyltriethoxysilane), vinyltrimethoxy silane (Vinyltrimethoxysilane), dimethylchlorosilane (Dimethylchlorosilane), trimethylchlorosilane (Trimethylchlorosilane), diphenyl dichlorosilane (Diphenyldichlorosilane) or its mixture etc.Preferably, containing the above-mentioned inorganic system tackiness agent of 0.1 ~ 7.0 % by weight in electroconductibility coating fluid composition, if the content of above-mentioned inorganic system tackiness agent is more than 7.0 % by weight, although the bonding force with glass then can be improved, but harden for a long time under needing hot conditions more than 100 DEG C, so high conduction performance may be reduced because of the deterioration of electroconductive polymer.
As the surface modulation additive for surface evening, can use and become commercialization also just at the flow agent as BYK300 of commercially available BYK company.Preferably, in electroconductibility coating fluid composition, contain the above-mentioned surface modulation additive of 0.1 ~ 3.0 % by weight.
Be the solvability of organic binder bond and the dispersiveness of PEDOT/PSS or solvability and the first solvent used can use the ether systems such as propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether as in order to obtain aforesaid propylene acid; The alcohol systems such as methyl alcohol, Virahol, ethanol, butanols; The fragrant hydrocarbon systems such as the ketone such as methyl ethyl ketone, acetone system, toluene, dimethylbenzene; In addition the ester such as ethyl acetate, butylacetate series solvent or its mixture can be used.
Further, preferably, use if add and use together with PEDOT/PSS electroconductive polymer aqueous dispersions, that surface resistivity can be reduced, that specific inductivity is high the second solvent.Above-mentioned second solvent can be dimethyl sulfoxide (DMSO) (DMSO), ethylene glycol (Ethylene glycol), glycerine (Glycerin), Sorbitol Powder (Sorbitol), methane amide (FA), N-METHYLFORMAMIDE (NMFA), N, dinethylformamide (DMF), ethanamide (AA), N-methylacetamide (NMAA), N-N,N-DIMETHYLACETAMIDE (DMA), tetrahydrofuran (THF) (THF), n-N-methyl-2-2-pyrrolidone N-(NMP), more than one material in Nitromethane 99Min. (nitromethane) and acetonitrile (Acetonitril).
According to a preferred embodiment of the invention have in the electroconductibility coating fluid composition of electromagnetic wave shielding function, except above-mentioned constituent, in the scope not departing from object of the present invention, additives such as comprising defoamer can be added.Preferably, in electroconductibility coating fluid composition containing disappear 0.1 ~ 7.0 % by weight the additive such as infusion.
Below, the manufacture method with the electroconductibility coating fluid composition of electromagnetic wave shielding function is according to a preferred embodiment of the invention further illustrated.
First, the method for acrylic acid synthesizing system organic binder bond is described.
Put into while solvent carries out stirring in a reservoir, temperature is risen to 100 ~ 150 DEG C.Above-mentioned solvent can be used alone or as a mixture ether system, alcohol system, fragrant hydrocarbon system, ketone system, ester system, acid amides series solvent etc.
By have hydroxyl (-OH) the first acrylic monomer, be that have second acrylic monomer of hydroxyl (-OH) and the Diisopropyl azodicarboxylate for initiated polymerization of 0.1 ~ 10 weight part or benzoyl peroxide of 10 ~ 200 weight parts mixes relative to above-mentioned first acrylic monomer of 100 weight parts, and to drip in said vesse.
Considering consistency, the acrylic acid series organic binder bond of the alcohol solubility of glass attachment excellence when synthesizing, preferably making viscosity be no more than 50,000cps, and use solvent adjustment to become to make solid content be 10 ~ 80% degree, more preferably, it is suitable for making solid content be about 30 ~ 60%.
Above-mentioned first acrylic monomer can comprise and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide, above-mentioned second acrylic monomer can comprise and is selected from Propylene glycol monoacrylate, HEMA, more than one material in vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
When the temperature in said vesse is maintained 100 ~ 150 DEG C, above-mentioned first acrylic monomer and above-mentioned second acrylic monomer is made to carry out polyreaction and acrylic acid synthesizing system organic binder bond.
Have a look the reaction mechanism of the synthesis about acrylic acid series organic binder bond below.Form the first free radical by the sensitization of polymerization starter (initiator), it is promptly added on monomer molecule and forms the second free radical.Be added to the reaction of propagation (propagation reaction) on monomer at generation first free radical during, grow polymer (Polymer) chain, thus form the second new free radical.Reaction of propagation (propagation reaction) is carried out quickly.In the polyreaction of formation having caused the second free radical, the speed of reaction of propagation is faster than the speed of initiation reaction.Final step is the termination reaction (termination) that chainpropagation stops, and at this moment chemical combination (combination) (coupling) and disproportionation (disproportionation) occur on plyability ground.
(1) initiation reaction (initiation)
Catalyzer → R'
R'+ monomer-M → RM'
(2) reaction of propagation (propagation)
RM' n-1+M→RM' n
(3) termination reaction (termination)
RM' n+M' p→RM n+pR
Due to the performance of acrylic acid series organic binder bond that is synthesized according to the composition of binding agent and molecular weight, molecular weight distribution etc. by considerable influence, therefore answer the reaction conditions such as concentration, temperature of reaction, solvent (Solvent) of the amount of selective polymerization initiator and kind, monomer.By with by the selection of monomer and combination and the resin determined forms the top condition of these factors selected of coming together, thus the acrylic acid series organic binder bond of various proterties can be synthesized.
Fig. 1 is for introducing the example of the 2-HEA/2-HEMA acrylic acid series organic binder bond of hydroxyl (-OH), and the bonding mechanism of glass and 2-HEA/2-HEMA acrylic acid series organic binder bond is shown, the hydrogen bond of glass and 2-HEA/2-HEMA acrylic acid series organic binder bond is shown.
With reference to figure 1, the silanol base (Si-OH) of glass surface and the hydroxyl (-OH) of acrylic acid series organic binder bond be synthesized improve the bonding force of organism and inorganics by hydrogen bonding, thus improve bonding force.Further, improve the Combination with PEDOT/PSS electroconductive polymer aqueous dispersions while introducing the hydroxyl (-OH) of acrylic acid series organic binder bond, thus even can expect the raising of high conduction performance.
Be that organic binder bond and inorganic system tackiness agent mix by the solvent being used for making PEDOT/PSS electroconductive polymer disperse or dissolve, aforesaid propylene acid, and drip PEDOT/PSS electroconductive polymer aqueous dispersions to the product of mixing and stir, obtain electroconductibility coating fluid composition thus.
Now, preferably, the aforesaid propylene acid mixing 1.0 ~ 20.0 % by weight be organic binder bond, 10.0 ~ 65.0 % by weight above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions, 25.0 ~ 65.0 % by weight for above-mentioned solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved and 0.1 ~ 7.0 % by weight above-mentioned inorganic system tackiness agent.
Further, the surface modulation additive for surface evening of 0.1 ~ 3.0 % by weight can now also be mixed further.
Above-mentioned PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid (PSS) in Polyglycolic acid fibre (PEDOT), and the mol ratio of above-mentioned Polyglycolic acid fibre (PEDOT) and above-mentioned polystyrolsulfon acid (PSS) is preferably 1:1 ~ 5.
Above-mentioned solvent can comprise more than one the first solvent be selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, ethyl acetate and butylacetate.
Relative to above-mentioned first solvent of 100 weight parts, above-mentioned solvent can comprise more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
Above-mentioned inorganic system tackiness agent can comprise and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
Above-mentioned electroconductibility coating fluid composition coated glass or film and harden, can obtain and there is electroconductibility coated film that surface resistivity is 50 ~ 250 Ω/ scopes, that have electromagnetic wave shielding function.
The method being coated with (coating) is carried out as by electroconductibility coating fluid composition according to a preferred embodiment of the invention, as long as the method usually known in the art, would not be restricted especially, and according to the shape of glass or film, can not be particularly limited in methods such as spin coating (spin coating), Control During Paint Spraying by Robot (robot spray coating), dip-coating (dip coating), flow coats (flow coating), as long as and usually by the method used, then any method can be used.In addition, these methods mixed use also harmless, and the thickness of the transparency electrode coating layer formed by such mode (electroconductibility coated film) is 0.1 ~ 30 micron (μm), preferably 0.2 ~ 10 micron of (μm) degree is suitable.
For the glass of the electroconductibility coating fluid composition that can be suitable for according to a preferred embodiment of the invention, as long as transparent supporter, then can use any material, especially, preferably can be used as the soda-lime glass (sodalime glass) of display applications.
Such glass preferably has the transmitance of more than 85%, is more preferably the transmitance with more than 90%.The mist degree of glass is preferably less than 2%, more preferably the scope of less than 1%, and specific refractory power is preferably the scope of 1.5 ~ 1.8.The thickness of glass is 1 ~ 5mm degree is suitable, more preferably, 0.5 ~ 1.5mm is suitable, if this is because the thickness of glass is too thick, then weight becomes heavy, if the thickness of glass is too thin, then can not bear thin film transistor (TFT:Thin Film Transistor) or colour filter (Color filter) manufacturing process of high temperature when manufacturing TSP.
Below, illustrate according to preferred embodiment of the present invention.But following embodiment provides to make the present invention be understood fully by those skilled in the art of the present technique, several different shape can be deformed into, and scope of the present invention is not limited to the embodiment that describes below.
The synthesis > of < acrylic acid series organic binder bond
In four-hole boiling flask, put into the butyl glycol ether (BC) of 48g, when stirring with 500rpm, temperature is increased to 130 DEG C.The Diisopropyl azodicarboxylate (AIBN) of the 2g as polymerization starter and the monomer of 50g that is mixed with methyl methacrylate (MMA), vinylformic acid (AA) and vinylformic acid 2-hydroxyl ethyl ester (2-HEA) with the ratio of such as following table 1 and formed are mixed, and dripped (dropping) in above-mentioned four-hole boiling flask via 3 hours.Terminate if drip (dropping), then react 4 hours when the temperature in above-mentioned four-hole boiling flask being maintained 130 DEG C, and terminate reaction by reducing temperature to 40 DEG C, synthesized acrylic acid series organic binder bond thus.
Table 1
The situation of acrylic acid series organic binder bond 1 is the binding agent only using general acrylic monomer and synthesize, and the situation of acrylic acid series organic binder bond 2 uses first acrylic monomer without hydroxyl (-OH) and as having the vinylformic acid 2-hydroxyl ethyl ester of the second acrylic monomer of hydroxyl (-OH) and the binding agent synthesized.
Below, specifically provide according to embodiments of the invention, and embodiment 1 ~ embodiment 3 that the present invention provides below being also limited to.Further, the comparative example that can compare with embodiments of the invention is provided more easily to grasp the characteristic of embodiment 1 ~ embodiment 3.It should be explicitly made clear at this point, comparative example 1 ~ comparative example 3 described later proposes to merely compare with the characteristic of embodiment, is not prior art of the present invention.
< embodiment 1 ~ 3 and comparative example 1 ~ 3>
As the composition ratio below shown in table 2, solvent (the first solvent and the second solvent) and inorganic system tackiness agent is put into the acrylic acid series organic binder bond 1 synthesized and acrylic acid series organic binder bond 2 (reference table 1), and stir 40 minutes with the speed of 1000rpm, make aforesaid propylene acid be that organic binder bond and inorganic system tackiness agent mix completely with solvent.When continuing to stir, PEDOT/PSS electroconductive polymer aqueous dispersions is dripped (dropping) with the speed of 5g/min, finally puts into surface modulation additive and manufactured coating fluid composition with the degree that the speed of 1000rpm mixes about 1 hour equably.
Table 2
Transparent soda-lime glass (0.7mm is coated on by #20 (numbering) bar type coating (Bar coating) (thickness of the coated film of wet (wet): 45 μm) by the electroconductibility coating fluid composition manufactured according to embodiment 1 ~ embodiment 3 with according to the coating fluid composition that comparative example 1 ~ comparative example 3 manufactures, NSG company) one on the surface after, within 5 minutes, removing water and solvent completely by carrying out sclerosis in the warm air drying baking oven of 100 DEG C, thus form coated film.
In order to comparative evaluation utilizes the physical property of the electroconductibility coating fluid composition manufactured according to embodiment 1 ~ embodiment 3 and the coated film utilizing the coating fluid composition according to comparative example 1 ~ comparative example 3 manufacture and formed, perform following experiment.
(1) surface resistivity is measured
The Loresta EP MCP-610 surface resistivity tester of Mitsubishi Chemical Ind is used to measure surface resistivity under 10V.
(2) electromagnetic wave shielding is measured
Entrusting the American-European electronic technology institute as generally acknowledging office, under 1GHz frequency, measuring electromagnetic shielding effect (dB).
(3) light transmission rate and mist degree (Haze)
Utilize spectrophotometer (NIPPON DENSHOKU, NDH-5000), using as the soda-lime glass (0.7mm of glass being used in coating, NSG company, light transmission rate (T.T): 92%, mist degree (Haze): 0.8%) as substrate (base), measures relative total transmitance (Total Transmittance) and mist degree (Haze).
(4) sticking power is measured
Tack measurement utilizes NITTO-31B to measure.Tack test-results is according to the change of surface resistivity and divide into as follows with or without coated film departs from.
1. less than 25 Ω/: good, 2. 25 ~ 50 Ω/: common, 3. depart from more than 50 Ω/ and coated film: bad
(5) resistance to heat durability
According under temperature 80 DEG C of conditions through the change of 500 hours rear surface resistance and with or without coated film depart from and divide into as follows.
1. less than 25 Ω/: good, 2. 25 ~ 50 Ω/: common, 3. depart from more than 50 Ω/ and coated film: bad
(6) temperature resistance moisture-resistant weather resistance
According at temperature 60 C and under relative humidity 90% condition through the change of 250 hours rear surface resistance and divide into as follows with or without coated film departs from.
1. less than 25 Ω/: good, 2. 25 ~ 50 Ω/: common, 3. depart from more than 50 Ω/ and coated film: bad
(7) coating fluid keeping stability
According to the precipitation of keeping coating fluid after 10 days under the condition of complete blocking light and at 25 DEG C whether with coating after surface resistivity change and divide into as follows.
1. less than 25 Ω/: good, 2. 25 ~ 50 Ω/: common, 3. depart from more than 50 Ω/ and coated film: bad
Table 3
As shown in the result of above-mentioned table 3, for the coated film utilizing the electroconductibility coating fluid composition two manufactured according to embodiment 1 ~ embodiment 3 to be formed, not only maintain the performance that surface resistivity is 50 ~ 250 Ω/, there is electromagnetic wave shielding performance, and it is excellent with the sticking power of glass, there is the mist degree of less than 1%, the light transmission rate of more than 90%, the excellences such as resistance to heat durability and wet heat durability, even also ensure the keeping stability of electroconductibility coating fluid composition, thus show the physical property of the electroconductibility coating fluid composition being suitable as electromagnetic wave shielding performance.
On the contrary, for the situation of the coating fluid composition manufactured according to comparative example 1 ~ comparative example 2, employ acrylic acid series organic binder bond 1, and acrylic acid series organic binder bond 1 is the binding agent utilizing general acrylic monomer to synthesize when not having the second acrylic monomer of hydroxyl (-OH), the bonding force of this binding agent and glass is bad, and for the situation of the coating fluid composition manufactured according to comparative example 2, organoalkoxysilane is employed as inorganic system tackiness agent, thus improve sticking power a little, but when evaluating sticking power, surface resistivity be changed to 25 ~ 50 Ω/ degree, the good sticking power less than 25 Ω/ cannot be obtained.And, because the acrylic acid series organic binder bond 1 used does not have hydroxyl (-OH), so decline with the solubility of the methyl alcohol used as the first solvent (reference table 2) and PEDOT/PSS electroconductive polymer aqueous dispersions, thus surface resistivity is up to 250 Ω/more than, and the keeping stability of coating fluid composition is also bad, be therefore not suitable as electroconductibility coating fluid composition.
For the situation of the coating fluid composition manufactured according to comparative example 3, the acrylic acid series organic binder bond 2 of the content abundance of hydroxyl (-OH) is employed in binding agent, although therefore show with the bonding force of glass excellent, but because the content of electroconductive polymer is abundant not, therefore surface resistivity is up to 400 Ω/more than, and electromagnetic wave shielding performance is not enough, and the degradation of resistance to heat durability and wet heat durability.
Above, adopt the preferred embodiments of the present invention to be described in detail, but the invention is not restricted to above-described embodiment, and several distortion can be carried out by those skilled in the art of the present technique in the scope of technological thought of the present invention.

Claims (9)

1. there is an electroconductibility coating fluid composition for electromagnetic wave shielding function, it is characterized in that, comprise:
The acrylic acid series organic binder bond of 1.0 ~ 20.0 % by weight;
The PEDOT/PSS electroconductive polymer aqueous dispersions of 10.0 ~ 65.0 % by weight;
The solvent of disperse or dissolve for making PEDOT/PSS electroconductive polymer 25.0 ~ 65.0 % by weight; And
The inorganic system tackiness agent of 0.1 ~ 7.0 % by weight,
Wherein, described PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid in Polyglycolic acid fibre, and the mol ratio of described Polyglycolic acid fibre and described polystyrolsulfon acid is 1:1 ~ 5,
Described acrylic acid series organic binder bond is by not having the first acrylic monomer of hydroxyl and carrying out being polymerized the acrylic acid polymer formed relative to second acrylic monomer with hydroxyl (-OH) that described first acrylic monomer of 100 weight parts is 10 ~ 200 weight parts and form
Described inorganic system tackiness agent comprises and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
2. the electroconductibility coating fluid composition with electromagnetic wave shielding function according to claim 1, it is characterized in that, described first acrylic monomer comprises and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide,
Described second acrylic monomer comprises more than one the material be selected from Propylene glycol monoacrylate, HEMA, vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
3. the electroconductibility coating fluid composition with electromagnetic wave shielding function according to claim 1, it is characterized in that, described solvent comprises more than one the first solvent be selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, ethyl acetate and butylacetate.
4. the electroconductibility coating fluid composition with electromagnetic wave shielding function according to claim 3, it is characterized in that, relative to described first solvent of 100 weight parts, described solvent comprises more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
5. there is a manufacture method for the electroconductibility coating fluid composition of electromagnetic wave shielding function, it is characterized in that, comprise:
A () puts into solvent when carrying out stirring in a reservoir, temperature is risen to the step of 100 ~ 150 DEG C;
(b) by do not have hydroxyl the first acrylic monomer, be that have second acrylic monomer of hydroxyl and the Diisopropyl azodicarboxylate being used for initiated polymerization of 0.1 ~ 10 weight part or benzoyl peroxide of 10 ~ 200 weight parts mixes relative to described first acrylic monomer of 100 weight parts, and drip the step in described container;
C when temperature in described container is maintained 100 ~ 150 DEG C by (), described first acrylic monomer and described second acrylic monomer is made to carry out the step of polyreaction and acrylic acid synthesizing system organic binder bond; And
D () is mixed for the solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved, described acrylic acid series organic binder bond and inorganic system tackiness agent, and drip to the product of mixing the step that PEDOT/PSS electroconductive polymer aqueous dispersions carrying out stirs,
Wherein, in described (d) step, the described acrylic acid series organic binder bond of mixing 1.0 ~ 20.0 % by weight, the described PEDOT/PSS electroconductive polymer aqueous dispersions of 10.0 ~ 65.0 % by weight, 25.0 ~ 65.0 % by weight for described solvent that PEDOT/PSS electroconductive polymer is dispersed or dissolved and 0.1 ~ 7.0 % by weight described inorganic system tackiness agent
Described PEDOT/PSS electroconductive polymer aqueous dispersions is the aqueous dispersions being mixed with polystyrolsulfon acid in Polyglycolic acid fibre, and the mol ratio of described Polyglycolic acid fibre and described polystyrolsulfon acid is 1:1 ~ 5,
Described inorganic system tackiness agent comprises and is selected from methyltrimethoxy silane, Union carbide A-162, Trimethoxy silane, triethoxyl silane, tetraethoxysilane, γ-aminopropyl triethoxysilane, aminopropyltriethoxy diethoxy silane, aminopropyltriethoxy dimethoxysilane, γ-glycidoxypropyltrietandysilane andysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane, silicon fluoride, vinyltriethoxysilane, vinyltrimethoxy silane, dimethylchlorosilane, more than one material in trimethylchlorosilane and diphenyl dichlorosilane.
6. the manufacture method with the electroconductibility coating fluid composition of electromagnetic wave shielding function according to claim 5, it is characterized in that, described first acrylic monomer comprises and is selected from methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, n-n-methylolacrylamide, diacetone acrylamide, glycidyl methacrylate, vinylbenzene, Vinyl toluene, more than one material in vinyl-acetic ester and vinyl cyanide,
Described second acrylic monomer comprises more than one the material be selected from Propylene glycol monoacrylate, HEMA, vinylformic acid 2-hydroxyl ethyl ester and Rocryl 410.
7. the manufacture method with the electroconductibility coating fluid composition of electromagnetic wave shielding function according to claim 5, it is characterized in that, described solvent comprises and is selected from propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, glycol ether-2-ethyl hexyl ether, methyl alcohol, Virahol, ethanol, butanols, methyl ethyl ketone, acetone, toluene, dimethylbenzene, more than one the first solvent in ethyl acetate and butylacetate.
8. the manufacture method with the electroconductibility coating fluid composition of electromagnetic wave shielding function according to claim 7, it is characterized in that, relative to described first solvent of 100 weight parts, described solvent comprises more than one second solvent be selected from dimethyl sulfoxide (DMSO), ethylene glycol, glycerine, Sorbitol Powder, methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), n-N-methyl-2-2-pyrrolidone N-, Nitromethane 99Min. and acetonitrile of 1.0 ~ 20.0 weight parts further.
9. one kind has the electroconductibility coated film of electromagnetic wave shielding function, it is characterized in that, described coated film is by the electroconductibility recorded in claim 1 coating fluid composition being coated the coated film that glass or film are hardened, having the surface resistivity of 50 ~ 250 Ω/ scopes.
CN201410340282.XA 2013-07-18 2014-07-17 Manufacturing method of conductive coating solution composition capable of shielding electromagnetic interference Expired - Fee Related CN104293009B (en)

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