CN110387162A - Coating composition - Google Patents
Coating composition Download PDFInfo
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- CN110387162A CN110387162A CN201910307167.5A CN201910307167A CN110387162A CN 110387162 A CN110387162 A CN 110387162A CN 201910307167 A CN201910307167 A CN 201910307167A CN 110387162 A CN110387162 A CN 110387162A
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- coating composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D7/40—Additives
- C09D7/47—Levelling agents
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/045—Fullerenes
Abstract
The subject of the invention is to provide a kind of coating compositions of dispersibility for improving carbon nanomaterial.Solution of the invention is a kind of coating composition, and it includes (a) carbon nanomaterial, (b) binder resin, (c) levelling agent and (d) organic solvents.
Description
Technical field
The present invention relates to coating compositions.Specifically, it is related to improving the coating compositions of the dispersibility of carbon nanomaterial
Object.
Background technique
Carbon nanomaterial is expected to since electric conductivity is high, stretch process is high, coloring is low in electric conductivity smears.
But the aspect ratio of carbon nanomaterial is big, has and is coordinated unsaturated structure, therefore intermolecular interaction is strong, has and is easy
The property of cohesion.Carbon nanomaterial can not play the characteristics such as electric conductivity, the transparency of script in the state of having occurred and agglomerating,
Therefore it is required that improving dispersibility of the carbon nanomaterial in electric conductivity smears.
So far, it is known that: the dispersed and mixed dispersing agent (patent document 1) in order to improve carbon nanomaterial.But
Even if mixed dispersing agent in many cases can if binder resin or other additives are added to constitute coating composition
It agglomerates, workable binder resin, additive have limitation.Speculate this is because binder resin etc. and dispersing agent
It interacts, as a result dispersing agent can not be present near carbon nanomaterial, to agglomerate.
In addition, in order to improve the dispersibility of carbon nanomaterial, it is known that the decentralized processing (patent document carried out using ultrasonic wave
2).But ultrasonication is difficult to adjust, carbon nanomaterial will receive cutting or destruction, result if excessively being handled
The tendency agglomerated is easier to new active face is generated.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-263608 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2006-16222 bulletin
Summary of the invention
Problems to be solved by the invention
The purpose of the present invention is to provide a kind of high coating compositions of the dispersibility of carbon nanomaterial.
Means for solving the problems
The inventors discovered that by newly adding levelling agent, even if available addition binder, solvent also maintain dispersibility
Coating composition, have thus completed the present invention.
That is, it includes (a) carbon nanomaterial, (b) binder resin, (c) levellings the present invention relates to a kind of coating composition
Agent and (d) organic solvent.
Above-mentioned coating composition is preferred: with 50% 2- aqueous propanol solution with weight ratio meter dilute 50 times, 3500rpm,
5 minutes centrifuging treatments are carried out under conditions of 23 DEG C, the absorbance of the complete supernatant of rigid centrifuging treatment is centrifuge separation
50% or more of absorbance before processing.
Above-mentioned coating composition is preferred: (a) carbon nanomaterial is selected from being made of graphene, carbon nanotube and fullerene
Group in it is at least one kind of.
Above-mentioned coating composition is preferred: (b) binder resin is selected from by acrylic resin, polyester resin, amino first
It is at least one kind of in the group of acid ester resin, melamine and silicon ester resin composition.
Above-mentioned coating composition is preferred: (c) levelling agent is for the compound with polyester construction or with polyether structure
Compound.
Above-mentioned coating composition is preferred: (d) organic solvent be in the group being made of methanol, ethyl alcohol and propyl alcohol extremely
It is a kind few.
Above-mentioned coating composition is preferred: (a) carbon nanomaterial is graphene, and (b) binder resin is acrylic resin,
(c) levelling agent is the compound with polyester construction.
Above-mentioned coating composition is preferred: (a) carbon nanomaterial is carbon nanotube, and (b) binder resin is melamine,
(c) levelling agent is the compound with polyether structure.
Moreover, it relates to the manufacturing method of above-mentioned coating composition comprising process (1)~(2) below:
(1) in the presence of (e) dispersing agent, decentralized processing is carried out to (a) carbon nanomaterial in water, thus obtains (a)
The process of the aqueous dispersion of carbon nanomaterial；With
(2) (b) binder resin, (c) stream are added into the aqueous dispersion of (a) carbon nanomaterial obtained in process (1)
Thus flat agent and (d) organic solvent obtain the process of coating composition.
The manufacturing method of above-mentioned coating composition is preferred: relative to 100 parts by weight of (e) dispersing agent used in process (1),
The amount of (c) levelling agent used in process (2) is 5 parts by weight~2400 parts by weight.
The effect of invention
The dispersibility of carbon nanomaterial can be improved in coating composition of the invention.
Specific embodiment
(1) coating composition
The present invention relates to a kind of coating compositions, and it includes (a) carbon nanomaterial, (b) binder resin, (c) levelling agents
And (d) organic solvent.
For coating composition of the invention, from the aspect of dispersibility, with 50% 2- aqueous propanol solution with
Weight ratio meter dilutes 50 times, and 5 minutes centrifuging treatments are carried out under conditions of 3500rpm, 23 DEG C, and rigid centrifuging treatment is complete
Supernatant absorbance be preferably absorbance before centrifuging treatment 50% or more, more preferably 55% or more, into one
Step preferably 60% or more.Herein, the concentration of 2- propyl alcohol is weight percent.
(a) carbon nanomaterial
As carbon nanomaterial, it can be cited for example that carbon nanotube, graphene, fullerene etc..These carbon nanomaterials can
To be used alone, can also share two or more.The content of carbon nanomaterial in coating composition is not particularly limited, phase
For all solids ingredient of coating composition, preferably 0.01 weight of weight %~90 %, more preferably 0.1 weight %~50
Weight %, further preferably 0.13 weight of weight %~30 %.In addition, being applied on substrate using aftermentioned method and forming painting
When cloth film is to manufacture laminate, the preferably up to 0.01mg/m on laminate2~50.0mg/m2Amount, more preferably reach
To 0.1mg/m2~10.0mg/m2Amount.
The type of carbon nanotube is not particularly limited, can suitably be selected using by arc discharge method, laser evaporation
The carbon nanotube of the various well-known technique manufactures such as method, chemical vapour deposition technique (CVD method).Single-walled carbon nanotube, double wall carbon nano-tubes
Pipe, multi-walled carbon nanotube and the mixture with arbitrary proportion comprising these carbon nanotubes can be used.From the side of excellent electric conductivity
Face consideration, preferably single-walled carbon nanotube.
The length of carbon nanotube is typically 1 μm~2000 μm, preferably 5 μm~1000 μm, more preferably 5 μm~500 μ
m.If being easy to happen the cohesion, cutting, destruction of carbon nanotube, it is not preferable more than 2000 μm.In addition, if less than 1 μm,
Sufficient conductive path can not be formed, it is not preferable.
The diameter of carbon nanotube be typically 0.1nm~50nm, preferably 0.3nm~20nm, more preferably 0.5nm~
10nm.If electric conductivity reduces sometimes more than 50nm.In addition, it is difficult to manufacture the carbon nanotube less than 0.1nm.
(b) binder resin
Binder resin is not particularly limited, is preferably selected from by polyester resin, acrylic resin, carbamate
It is at least one kind of in the group that resin, epoxy resin, polyolefin resin, melamine and silicon ester resin form.The reason for this is that:
It is high with the compatibility of the other compositions in coating composition, lamination is formed by using the coating composition containing these binders
Body is good for the compatibility of substrate, film forming.These binders can be used alone, and can also share two or more.
As polyester resin, as long as compound by intramolecular with 2 or more carboxyls and with 2 or more hydroxyls
The high-molecular compound that compound polycondensation obtains just is not particularly limited, it can be cited for example that polyethylene terephthalate,
Polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, poly- naphthalenedicarboxylic acid butanediol
Ester etc..They can be used alone or in combination with two or more.
It is not particularly limited as acrylic resin, it can be cited for example that (methyl) acrylic resin, vinyl esters
It is resin etc..As these acrylic resins, as long as comprising having the acid such as carboxyl, anhydride group, sulfonic group, phosphate
The polymerizable monomer of base is as the polymer for constituting monomer, it can be cited for example that the homopolymerization of the polymerizable monomer with acidic group
Object or copolymer, the polymerizable monomer with acidic group and the copolymer of co-polymerized monomer etc..They can be used alone, can also be with
It shares two or more.
(methyl) if acrylic resin comprising (methyl) acrylic monomer as main composition monomer (for example, 50
Mole % or more), then it can also be polymerize with co-polymerized monomer, as long as in this case, (methyl) acrylic monomer and altogether
At least one of poly- property monomer has acidic group.
As (methyl) acrylic resin, it can be cited for example that: (methyl) acrylic monomer [(first with acidic group
Base) acrylic acid, (methyl) sulfoethyl Arrcostab, containing sulfonic (methyl) acrylamide etc.] or its copolymer, have or
[other polymerism carboxylic acids polymerize (methyl) acrylic monomer without acidic group with other polymerizable monomers with acidic group
Property polybasic carboxylic acid or acid anhydrides, vinyl aromatic sulfonic acid etc.] and/or co-polymerized monomer [for example, (methyl) alkyl acrylate,
(methyl) glycidyl acrylate, (methyl) acrylonitrile, aromatic vinyl monomer etc.] copolymer, its with acidic group
His polymer monomer and (methyl) acrylic copolymer monomer are [for example, (methyl) alkyl acrylate, (methyl) acrylic acid hydroxyl
Arrcostab, (methyl) glycidyl acrylate, (methyl) acrylonitrile etc.] copolymer, Abietyl modified carbamate propylene
Acid esters, special modified acrylic resin, urethane acrylate, epoxy acrylate, urethane acrylate
Lotion etc..
In these (methyl) acrylic resins, preferred (methyl) acrylic acid-(methyl) acrylate polymer (propylene
Acid-methylmethacrylate copolymer etc.), (methyl) acrylic acid-(methyl) acrylic styrene copolymer (acrylic acid-first
Base acrylate-styrene copolymer etc.) etc..
As polyurethane, as long as obtaining the compound with isocyanate group with the copolymer compound with hydroxyl
High-molecular compound is just not particularly limited, it can be cited for example that ester ether system polyurethane, ether system polyurethane, the poly- ammonia of Polyester
Ester, carbonic ester system polyurethane, acrylic acid series polyurethane etc..They can be used alone or in combination with two or more.
Be not particularly limited as epoxy resin, it can be cited for example that bisphenol A-type, bisphenol-f type, phenol novolak type,
Four (hydroxy phenyl) ethane types or three (hydroxy phenyl) methane types, biphenyl type, three as the multifunctional type with multiple phenyl ring
The epoxy resin, silicone-epoxy such as phenol methane type, naphthalene type, adjacent phenolic varnish type, dicyclopentadiene type, aminobenzene phenolic, ester ring type
Resin etc..They can be used alone or in combination with two or more.
It is not particularly limited as polyolefin resin, it can be cited for example that polyethylene, polypropylene, chlorinated polypropylene, Malaysia
Anhydride-modified polypropylene, maleic anhydride modified chlorinated polypropylene etc..They can be used alone or in combination with two or more.
As silicon ester resin, the monomer that can enumerate alkoxy silane represented by for example following formula (I)s is condensed each other
Made of alkoxy silane, i.e., 1 intramolecular have 1 or more siloxanes key (Si-O-Si) oligomer etc..
SiR1 4(I)
(in formula, R1For hydrogen, hydroxyl, carbon atom number be 1~4 alkoxy, the alkyl with or without substituent group, tool
Have or the phenyl without substituent group.Wherein, 4 R1In at least one be carbon atom number be 1~4 alkoxy or hydroxyl)
Silicon ester resin is preferably substance made of 2 molecule of alkoxy silane represented by formula (I) or more condensation.
The structure of silicon ester resin is not particularly limited, and can be straight-chain, or branched.In addition, esters of silicon acis
Resin can be used alone compound represented by formula (I), can also share two or more.
As above-mentioned silicon ester resin, silicon alkoxide acrylic resin, silicon alkoxide epoxy system resin, silicon alkoxide can be enumerated
Vinyl resin, silicon alkoxide metha crylic resin, silicon alkoxide mercaptan system resin, silicon alkoxide amino system resin, silicon alkoxide
Isocyanates system resin, silicon alkoxide alkyl system's resin and silicon alkoxide system resin without the functional group other than silanol alkali etc.
Silicon alkoxide system resin.
As the specific constituent of above-mentioned silicon ester resin, 2- (3,4- epoxycyclohexyl) ethyl front three can be enumerated
Oxysilane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxypropyltrime,hoxysilane, 3- epoxy
Propoxypropyl methyldiethoxysilane, 3- epoxy propoxy propyl triethoxysilane, 3- methacryloxypropyl
Methyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloyloxypropyl methyl two
Ethoxysilane, 3- methacryloxypropyl, 3- mercapto propyl methyl dimethoxy silane, 3- sulfydryl
Propyl trimethoxy silicane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- acryloxypropyl trimethoxy
Base silane, N-2- (amino-ethyl) -3- aminopropylmethyldimethoxysilane, N-2- (amino-ethyl) -3- aminopropyl three
Methoxy silane, 3- TSL 8330,3-aminopropyltriethoxysilane, 3- triethoxysilyl-
N- (1,3- dimethyl-butylidene) propylamine, N- phenyl -3- TSL 8330, three ethoxy of 3- isocyanates propyl
Base silane, methyltrimethoxysilane, dimethyldimethoxysil,ne, trimethylmethoxysilane, methyltriethoxysilane,
Methylenedioxy phenoxy base silane, n-propyl trimethoxy silane, diisopropyl dimethoxy silane, trimethoxysilane, two
Isobutyl group dimethoxysilane, isobutyl triethoxy silane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane,
Cyclohexyl Methyl Dimethoxysilane, n-octytriethoxysilane, positive decyl trimethoxy silane, tetramethoxy-silicane, four
The tetraalkoxysilanes such as Ethoxysilane, tetrapropoxysilane, four butoxy silanes or tetraphenoxy-silicane alkane, methyl silicate are oligomeric
Trimethylsiloxysilicates oligomer such as object, silester oligomer etc..Wherein, preferably tetraalkoxysilane, tetraphenoxy-silicane alkane, alkane
Oxygroup silicic acid ester oligomer.
The weight average molecular weight of silicon ester resin is not particularly limited, and preferably greater than 150 and 4000 hereinafter, more preferably big
In 240 and 3000 hereinafter, further preferably 330~2500.
The content of binder resin is not particularly limited, relative to all solids ingredient of coating composition, preferably
30 weight of weight %~98 %, more preferably 40 weight of weight %~90 %, further preferably 50 weight of weight %~80 %.
When the content of binder resin is less than 30 weight %, the intensity of laminate weakens sometimes；On the other hand, more than 98 weight %
When, the ratio of the carbon nanomaterial in laminate relatively reduces, and is unable to fully ensure the electric conductivity of laminate sometimes.
(c) levelling agent
By mixed levelling agent, the substrate coating of coating composition of the invention becomes good.On the other hand, such as rear institute
It states, needs to implement decentralized processing in advance to (a) carbon nanomaterial, the dispersion for making (a) carbon nanomaterial is used in decentralized processing
The dispersing agent of in stable conditionization, but the other compositions such as dispersing agent and binder resin occur during forming coating composition
Interaction, dispersing agent can not be present near carbon nanomaterial, as a result, being easy to produce the dispersion stabilization of coating composition
The problem of reduction.Levelling agent in order to obtain good substrate coating and add, with carbon nanomaterial occur phase interaction
With and make up divergent function, as a result, improving the dispersion stabilization of coating composition.It is high in hydrophily as levelling agent
In the case of, the dispersion force in water-organic solvent is excellent, thus HLB value is preferably 9 or more, is more preferably 10 or more, is further
Preferably 12 or more.It is calculated it should be noted that HLB value can use calculation method below.
Griffin method: [(molecular weight of hydrophilic segment) ÷ (whole molecular weight)] × 20
As specific levelling agent, Polyester levelling agent, polyether system levelling agent, fluorine system levelling agent, silicone-based can be enumerated
Levelling agent, acrylic acid series levelling agent.Among these, the Polyester levelling agent with ester bond, the polyether system levelling agent with ehter bond
It being easy to interact with carbon nanomaterial, the performance for dispersing nano-carbon material in water-alcohol is high, therefore it is preferred that.
As Polyester levelling agent, dimethyl silicone polymer, polyester modification of the polyester modification containing acryloyl group can be enumerated
Dimethyl silicone polymer, polyester polyol etc..
As polyether system levelling agent, cellulose ether can be enumerated；Pulullan polysaccharide；Polyethylene glycol: polyether-modified poly- diformazan
It is the dimethyl silicone polymer of the ester modified hydroxyl of radical siloxane, polyether modified siloxane, polyethers, polyether-modified containing acryloyl group
The silicone modified polyethers such as dimethyl silicone polymer；Polyglycereol；Polyether polyol, Pluronic F-68, polyoxy second
Alkyl ether derivatives, the alkyl ether sulfates such as allylic alkylation phenyl ether, laurel alcohol alkoxylates etc..These levelling agents can be independent
It uses, can also share two or more.
As fluorine system levelling agent, perfluoropolyether-modified dimethyl silicone polymer, the poly- diformazan of perfluor polyester modification can be enumerated
Radical siloxane, perfluorobutane, containing containing fluorine-based hydrophilic radical lipophilic group oligomer, containing perfluoroalkyl
Carboxylate, phosphate of the base containing perfluoroalkyl phosphate etc..These levelling agents can be used alone, can also share two kinds with
On.
As silicone-based levelling agent, other than polysiloxanes etc., it can enumerate and be imported with amino, epoxy group, hydroxyl, carboxylic
The reactive polysiloxane of base isoreactivity group and the non-reaction such as be imported with alkyl, ester group, aralkyl, phenyl, polyether-based
The non-reacted polysiloxanes etc. of property group.These levelling agents can be used alone, and can also share two or more.
As acrylic acid series levelling agent, the acrylic acid series copolymer etc. being made of silicone and acrylic acid can be enumerated.These
Levelling agent can be used alone, and can also share two or more.
As levelling agent, substance identical with aftermentioned dispersing agent also can be used, but it is preferable to use have than dispersing agent
The levelling agent of low HLB value.
The content of levelling agent is not particularly limited, relative to all solids ingredient of coating composition, preferably 0.01
The weight of weight %~40 %, more preferably 0.1 weight of weight %~20 %, further preferably 1 weight of weight %~10 %.Stream
When the content of flat agent is less than 0.01 weight %, with the insufficient tendency of dispersion stabilization and substrate coating；On the other hand, surpass
When crossing 40 weight %, the tendency of crawling is become inadequate, generated with film-strength.
(d) organic solvent
Organic solvent has the function of improving coating composition for the compatibility of substrate.It is not special as organic solvent
It limits, it can be cited for example that: the alcohols such as methanol, ethyl alcohol, 2- propyl alcohol, 1- propyl alcohol；Ethylene glycol, diethylene glycol, triethylene glycol, tetrem
The glycols such as glycol；The glycol such as glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether
Ethers；The glycol ether acetic acid such as ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate
Esters；The propandiols such as propylene glycol, dipropylene glycol, tripropylene glycol；Propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol list
The propylene glycol ethers such as methyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether；The propylene glycol ether acetates such as propylene glycol methyl ether acetate
Class；The ethers such as diethyl ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK),
The ketones such as cyclohexanone；The hydro carbons such as toluene, dimethylbenzene (ortho-xylene, meta-xylene or paraxylene), hexane, heptane: acetic acid second
The esters such as ester, butyl acetate, ethyl acetoacetate, adjacent methyl acetate, adjacent Ethyl formate: halogen, N-METHYLFORMAMIDE, N, N-
The amide compounds such as dimethylformamide, gamma-butyrolacton, N-Methyl pyrrolidone；1,3- propylene glycol, 1,4- butanediol, 1,5-
The hydroxy-containing compounds such as pentanediol, 1,6-HD, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerol；
Dimethyl sulfoxide etc. has the compound of sulfo group；Halogen, isophorone, propylene carbonate, acetylacetone,2,4-pentanedione, acetonitrile, water and this
The mixed solvent (water-containing organic solvent) of organic solvents, mixed solvent of two or more organic solvent etc. a bit.From carbon nanomaterial
From the aspect of dispersion stabilization and coating on base material, the mutual mixed solvent of preferable organic solvent, water among these
With the mixed solvent of organic solvent, the mixed solvent of the mutual mixed solvent of more preferable alcohol, water and alcohols.It is mutual mixed as alcohol
Bonding solvent, solvent made of preferably properly mixing methanol, ethyl alcohol and 2- propyl alcohol.It is excellent as the mixed solvent of water and alcohols
Select the combination of water Yu methanol, water and ethyl alcohol, water and 2- propyl alcohol.Using the mixed solvent of water and organic solvent, have
The concentration of solvent is preferably 30 weight of weight %~90 %, more preferably 40 weight of weight %~80 %.In addition, in order to improve
Coating, addition glycols, propandiols, amide compound etc. are also effective.
Organic solvent is not preferably remained in the laminate formed using coating composition.It should be noted that this explanation
In book, for the substance (i.e. " solvent ") for being completely dissolved the whole components of coating composition and the substance for dispersing insoluble component
(i.e. " decentralized medium ") is denoted as " solvent " without distinguishing especially.
From the solid component in coating, liquid stability aspect, coating composition be preferably coating composition
In 0.01 weight of weight %~20 %, more preferably 0.1 weight of weight %~10 %, further preferably 0.5 weight %~5
Weight %.The concentration can be by the mixed solvent of above-mentioned organic solvent, water and above-mentioned organic solvent in coating composition
Additive amount is adjusted.
As the concrete example of coating composition, it can enumerate that (a) carbon nanomaterial is graphene, (b) binder resin is
Acrylic resin, the coating composition that (c) levelling agent is the compound with polyester construction.It is received furthermore it is possible to enumerate (a) carbon
Rice material is carbon nanotube, (b) binder resin is melamine, the painting that (c) levelling agent is the compound with polyether structure
Cloth composition.
(other compositions)
Coating composition can also further contain electroconductive polymer, crosslinking agent, catalyst, antioxidant, defoaming agent,
Rheology control agent, neutralizer, thickener, foaming agent etc..
As electroconductive polymer, it can be cited for example that polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, poly-
Naphthalene and their derivative.They can be used alone or in combination with two or more.Wherein, by including in the molecule
Thiphene ring, the high molecule of electric conductivity easy to form, from this respect, preferably conduction of the intramolecular comprising at least one thiphene ring
Property macromolecule.Electroconductive polymer can also form compound with dopants such as polyanions.
It is extremely excellent from electric conductivity and chemical stability in the molecule in the electroconductive polymer comprising at least one thiphene ring
Different aspect is set out, more preferable poly- (3,4- bis- substituted thiophene).In addition, being poly- (3,4- bis- substitution thiophenes in electroconductive polymer
Pheno) or the compound of poly- (3,4- bis- substituted thiophene) and polyanion (dopant) in the case where, can be in low temperature and short time
Interior formation asperities electric conductor, productivity are also excellent.It should be noted that polyanion is the dopant of electroconductive polymer,
Content is as described later.
As poly- (3,4- bis- substituted thiophene), particularly preferred poly- (3,4- dialkoxythiophene) or poly- (3,4- alkylidenes two
Oxygroup thiophene).As poly- (3,4- dialkoxythiophene) or poly- (3,4- alkylenedioxythiophene), preferably by formula below
(I):
[changing 1]
The polythiophene for the cationic form that the constitutional repeating unit of expression is constituted.
Herein, R1And R2Hydrogen atom or C are indicated independently of each other1-4Alkyl, alternatively, in R1And R2In conjunction with the case where following table
Show C1-4Alkylidene.As C1-4Alkyl be not particularly limited, it can be cited for example that methyl, ethyl, propyl, isopropyl, just
Butyl, isobutyl group, sec-butyl, tert-butyl etc..In addition, in R1And R2In conjunction in the case where, as C1-4Alkylidene it is not special
It limits, it can be cited for example that methylene, 1,2- ethylidene, 1,3- propylidene, Isosorbide-5-Nitrae-butylidene, 1- methyl-1,2- ethylidene, 1-
Ethyl -1,2- ethylidene, 1- methyl-1,3- propylidene, 2- methyl-1,3- propylidene etc..Among these, preferably methylene, 1,
2- ethylidene, 1,3- propylidene, more preferable 1,2- ethylidene.C1-4Alkyl and C1-4The part hydrogen of alkylidene can be taken
Generation.As with C1-4Alkylidene polythiophene, it is particularly preferred poly- (3,4- ethene-dioxythiophene).
The weight average molecular weight of electroconductive polymer is preferably 500~100000, is more preferably 1000~50000, is further
Preferably 1500~20000.
Dopant is not particularly limited, preferably polyanion.Polyanion by with polythiophene (derivative) constitute from
Son pair and form compound, so as to be dispersed stably in polythiophene (derivative) in water.As polyanion without spy
It does not limit, it can be cited for example that carboxylic acid polyalcohol class (such as polyacrylic acid, poly, polymethylacrylic acid etc.), sulfonic acid are poly-
Close species (such as polystyrolsulfon acid, polyvinylsulfonic acid, polyisoprene sulfonic acid etc.) etc..For these carboxylic acid polyalcohol classes
It can also be vinyl carboxylic acid class and vinyl sulfonic acid class and other polymerizable monomer classes (such as third with sulfonic acid polymer class
The aromatic ethenyl compounds such as olefin(e) acid esters, styrene, vinyl naphthalene) copolymer.Among these, particularly preferred polyphenyl second
Alkene sulfonic acid.
The weight average molecular weight of polystyrolsulfon acid is preferably 20000~500000, more preferably 40000~200000.If
Using polystyrolsulfon acid of the molecular weight outside the range, then polythiophene system electroconductive polymer to the dispersion stabilization of water sometimes
It reduces.It should be noted that weight average molecular weight is the value measured using gel permeation chromatography (GPC).
As the compound of electroconductive polymer and polyanion, since electric conductivity is especially excellent, thus preferably poly- (3,4-
Ethene-dioxythiophene) with the compound of polystyrolsulfon acid.
The conductivity of electroconductive polymer is preferably 0.01S/cm or more, more preferably 1S/cm or more.
In the case that coating composition includes electroconductive polymer, the content of electroconductive polymer is relative to carbon nanomaterial
100 parts by weight of solid component be preferably 5 parts by weight~2000 parts by weight, more preferably 10 parts by weight~1000 parts by weight.
By mixed crosslinking agent, Thermocurable binder resin can be made to be crosslinked, antistatic property can be improved.As friendship
Connection agent is not particularly limited, it can be cited for example that melamine series, polycarbodiimide system, poly- oxazoline system, poly- epoxy, more
The crosslinking agents such as isocyanates system, polyacrylate system.These crosslinking agents can be used alone, and can also share two or more.
In the case that coating composition contains crosslinking agent, its content is not particularly limited, in coating composition preferably
For 30 weight % or less, more preferably 20 weight % or less.
In the case that coating composition contains Thermocurable binder resin and crosslinking agent, as keeping Thermocurable viscous
The catalyst of knot agent resin crosslinking is not particularly limited, it can be cited for example that Photoepolymerizationinitiater initiater, thermal polymerization etc..
(2) manufacturing method of coating composition
The manufacturing method of coating composition includes process below:
Process (1) carries out decentralized processing to (a) carbon nanomaterial in water in the presence of (e) dispersing agent, thus
To the aqueous dispersion of (a) carbon nanomaterial；With
Process (2), into the aqueous dispersion of (a) carbon nanomaterial obtained in process (1) add (b) binder resin,
(c) levelling agent and (d) organic solvent, thus obtain coating composition.
In process (1), in the presence of (e) dispersing agent, decentralized processing is carried out to (a) carbon nanomaterial in water, by
This makes carbon nanomaterial and dispersing agent interact, and obtains the aqueous dispersion of carbon nanomaterial.It, can be with as decentralized approach
It enumerates and utilizes vibrating mill, planetary mill, ball mill, ball mill, sand mill, aeropulverizer, roller mill, homogenizer, ultrasonic wave
The dispersion of the progress such as homogenizer, high pressure homogenisers, ultrasonic unit.It, can in the case where also remaining condensate after decentralized processing
Processing is centrifuged, the condensate of precipitating is removed.
As (e) dispersing agent, be not particularly limited as long as it can be dispersed in water carbon nanomaterial, can enumerate sun from
Subtype dispersing agent, anionic dispersing agent, amphoteric ion type dispersing agent, non-ionic dispersing agent, macromolecular dispersing agent.
As cationic dispersing agent, can enumerate stearylamine acetic acid esters etc. to have carbon atom number is 8~22 alkyl
The quaternary ammonium salts such as alkylamine salt, lauryl trimethyl ammonium chloride, cetyl trimethylammonium bromide.
As anionic dispersing agent, can enumerate sodium alkyl sulfate that the carbon atom numbers such as NaLS are 8~18,
Polyoxyethylene alkyl ether sulfuric acid, NaTDC, ten of the carbon atom numbers such as sodium laureth sulfate for 8~18
It is alkylbenzene sulfonate, fatty acid salt, the beta-naphthalenesulfonic-acid formaldehyde of 8~18 alkyl that dialkyl benzene sulfonic acids sodium etc., which has carbon atom number,
The naphthalene sulfonic acid-formaldehyde condensation products such as the sodium salt of condensation product.
As amphoteric ion type dispersing agent, alkyl betaine, the tool of the alkyl for being 8~22 with carbon atom number can be enumerated
Having carbon atom number is the alkyl amine oxide of 8~18 alkyl.
As non-ionic dispersing agent, can enumerate with carbon atom number be 1~20 alkyl polyoxyethylene alkyl ether,
The poly- second two of alkyl phenol of the block copolymer, the alkyl for being 1~20 with carbon atom number that are made of ethylene oxide and propylene oxide
Polyoxyalkylene derivatives, the sorbitans three such as alcohol ether, the polycarboxylate ether of alkylidene for being 2~4 with carbon atom number are stearic
The sorbitan fatty acid esters such as acid esters.
As macromolecular dispersing agent, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, hydroxyl can be enumerated
The fibres such as base cellulose, hydroxy alkyl cellulose, carboxymethyl cellulose, the carboxy-propyl cellulose of alkyl for being 1~8 with carbon atom number
Tie up the high scores such as plain derivative, starch, gelatin, acrylic acid series copolymer, polycarboxylic acids or derivatives thereof, polystyrolsulfon acid or its salt
Subsystem dispersing agent.
Among these, preferably polyvinylpyrrolidone, polyvinyl butyral, polyoxyalkylene derivative, polystyrene sulphur
Acid, cellulose derivative, polycarboxylic acids, acrylic acid series copolymer, alkylbenzene sulfonate, more preferable polyvinylpyrrolidone, poly- second
Enol butyral, polyoxyalkylene derivative, polycarboxylic acids, acrylic acid series copolymer.These dispersing agents can be by dispersion of more than two kinds
Agent is applied in combination.In addition, for the dispersing agent for being 15 or more with the molecular weight of 1 or more branch, branch, strand
In whole Directional Extensions, dispersibility is improved, therefore it is preferred that.
For dispersing agent, for the reason that dispersion stabilization is excellent, HLB value is preferably 12 or more, more preferably 14
More than.
In process (1), (e) dispersing agent is used preferably with respect to 100 parts by weight of aqueous dispersion of (a) carbon nanomaterial
0.001 parts by weight~10 parts by weight more preferably use 0.001 parts by weight~7 parts by weight, further preferably use 0.05 parts by weight
~5 parts by weight.(e) when the dosage of dispersing agent is less than 0.001 parts by weight, (a) carbon nanomaterial can not be made fully dispersed, sometimes without
Method obtains high dispersion stability.(e) it when the dosage of dispersing agent is more than 10 parts by weight, can blister in decentralized processing, sometimes
It can inhibit decentralized processing.
In process (2), (b) binder tree is added into the aqueous dispersion of (a) carbon nanomaterial obtained in process (1)
Rouge, (c) levelling agent and (d) organic solvent, thus obtain coating composition.As described above, the decentralized processing in process (1)
When it some times happens that blistering, thus (e) dispersing agent dosage exist limitation, therefore after decentralized processing for example (e) dispersing agent with
The ingredient interaction added after binder etc., nearby dissociates from (a) carbon nanomaterial sometimes, is easy to happen dispersion stabilization
The problem of reduction.After obtaining the aqueous dispersion of (a) carbon nanomaterial in process (1), by mixed levelling agent, even if dispersing
The ingredients such as agent and binder interact near carbon nanomaterial in the case where dissociation, and levelling agent also can be with carbon nanomaterial
It interacts and makes up divergent function, therefore the coating composition of dispersion stabilization, superior storage stability can be obtained.It is right
(b) binder resin, (c) levelling agent and (d) adding method of organic solvent is not particularly limited, can be same by three kinds of ingredients
When be added in the aqueous dispersion of (a) carbon nanomaterial obtained in process (1), can also add respectively.What is added respectively
In the case of, order of addition is not particularly limited.
Relative to 100 parts by weight of (e) dispersing agent used in process (1), the amount of (c) levelling agent used in process (2)
Preferably 5 parts by weight~2400 parts by weight, more preferably 50 parts by weight~1200 parts by weight, further preferably 100 parts by weight
~600 parts by weight.When less than 5 parts by weight, dispersion stabilization, substrate coating have insufficient tendency.More than 2400
When parts by weight, has and dysgenic tendency is generated to film-strength.
(3) laminate
Coating film is formed and coating composition of the invention is applied at least one face of substrate, can be obtained
To laminate.Coating composition can be directly applied on substrate, can also by priming coat etc., other layers are set to substrate in advance
On, it is applied on the layer later.
As the material of substrate, it can be cited for example that glass, polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid
The polyester based resins such as glycol ester, modified poly ester, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, ring-type
The vinyl resins such as the polyolefin resins such as olefin-based resin, polyvinyl chloride, polyvinylidene chloride, polyether-ether-ketone (PEEK) tree
Rouge, polysulfones (PSF) resin, polyether sulfone (PES) resin, polycarbonate (PC) resin, polyamide, polyimide resin, third
Olefin(e) acid resinoid, triacetyl cellulose (TAC) resin etc..These materials can be used alone, and can also share two or more.
The thickness of substrate is not particularly limited, preferably 10 μm~10000 μm, more preferably 25 μm~5000 μm.Separately
Outside, from the aspect of the transparency, the total light transmittance of base material film is preferably 60% or more, is more preferably 70% or more, is further
Preferably 80% or more.
Coating film after coating composition is applied at least one face of substrate and can be heated
It obtains.Method as at least one face that coating composition is applied to substrate is not particularly limited, and can be used well known
Method, can be used for example rolling method, stick coating method, dip coating, spin-coating method, the tape casting, die coating method, scraper coating method, stick coating method,
Gravure coating process, curtain coating method, spray coating method, knife coating, slot coated method, relief printing plate (typography) print process, hole version (silk screen) print process,
Lithographic plate (hectograph) print process, intaglio plate (heliogravure) print process, spraying print process, ink jet printing method, pad printing method etc..
It, as needed can be in advance to the surface of substrate before coating composition is applied at least one face of substrate
Implement surface treatment.As surface treatment, it can be cited for example that sided corona treatment, corona treatment, ITRO processing, flame treatment
Deng.
The heat treatment formed when being coated with film is not particularly limited, is carried out using well known method, for example, making
It is carried out with convection oven, infrared-ray oven, vacuum drying oven etc..In the case that coating composition contains solvent, solvent passes through
Heat treatment removes.
The temperature condition of heat treatment formed when being coated with film is not particularly limited, preferably 150 DEG C or less, more excellent
It is selected as 50 DEG C~140 DEG C, further preferably 60 DEG C~130 DEG C.If the temperature of heat treatment is more than 150 DEG C, used base
The material of material is limited, and is not available such as PET film, polycarbonate membrane, acrylic film commonly used in transparent electrode film
Substrate.The processing time of heat treatment is not particularly limited, preferably 0.1 minute~60 minutes, more preferably 0.5 minute~
30 minutes.
To coating film thickness be not particularly limited, preferably 1nm~1000nm, more preferably 2nm~500nm, into
One step is preferably 5nm~400nm.
The surface resistivity of coating film is not particularly limited, preferably 102Ω/~1011Ω/, it is more preferably
103Ω/~1010Ω/, further preferably 104Ω/~109Ω/□。
The refractive index of coating film is not particularly limited, preferably 1.4~1.7, more preferably 1.5~1.6.
Mist degree (Haze) value of laminate is not particularly limited, preferably 5.0% or less, more preferably 4.0% or less,
Further preferably 3.0% or less.If haze value is more than 5.0%, the transparency of laminate is deteriorated sometimes.It needs to illustrate
It is that haze value is smaller the more preferred, therefore its lower limit is not particularly limited, for example, 0.01%.Haze value can be according to JIS
K7136 is measured.
The total light transmittance of laminate is not particularly limited, preferably 85% or more, more preferably 87% or more.If total saturating
Light rate is less than 85%, then the transparency becomes inadequate (bad order) sometimes.It should be noted that the upper limit of total light transmittance is
100%.Total light transmittance can be measured according to JIS K7136.
Other than being coated with film, laminate can also have adhesive layer on substrate.Adhesive layer is preferably configured in substrate
Not and on the face that contacts of coating film.Adhesive layer is formed using the adhesive composition containing adhesive.As adhesive
It is not particularly limited, conventionally known adhesive can be used, specifically, it can be cited for example that by various (methyl) acrylic acid
(methyl) acrylic resin obtained from ester monomer homopolymerization or copolymerization, Ethylene/vinyl acetate copolymerization are resin, have diformazan
The silicone-based resins such as the silicone rubber of radical siloxane skeleton, by polyurethane series tree obtained from polyalcohol and polyisocyanate polyaddition
Rouge, natural rubber, styrene-isoprene-styrene block copolymer (SIS block copolymer), styrene-butadiene-benzene
Ethylene block copolymer (SBS block copolymer), (the SEBS block copolymerization of styrene-ethylene butylene-styrene block copolymer
Object), butadiene-styrene rubber, polybutadiene, polyisoprene, polyisobutene, butyl rubber, the rubber series resin such as chloroprene rubber
Deng.Wherein, preferably chemical stability is especially excellent, the freedom degree of chemical structure design is high, the bonding force easy (first of adjustment
Base) acrylic resin, silicone-based resin, polyurethane series resin.In addition, the aspect especially excellent from the transparency, preferably
(methyl) acrylic resin and polyurethane series resin.
As the forming method of adhesive layer, conventionally known method can be used, it can be cited for example that following methods: will contain
The method for thering is the adhesive composition of adhesive to be applied on substrate and carrying out crosslinking or heat drying；Crosslinked or heating is dry
Dry adhesive layer is transferred to the method on substrate；Etc..It should be noted that adhesive composition is also other than adhesive
Crosslinking agent can be contained.
As the method for coating adhesive composition, conventionally known method can be used, specifically, example can be used
Such as rolling method, gravure coating process, reverse rubbing method, roller brush method, spray coating method, air knife coating method.
(4) surface protection film
Laminate of the invention can be suitable for as the purposes for requiring less colored and transparent conductive film.As this
The purposes of sample, it can be cited for example that surface protection film, polarizing film, masking tape, again exfoliated label, semiconductor, electronic component
Deng packaging material, surface protection film, polarizing film purposes, electrophotographic recording material, magnetic recording material, transparent touch-control panel
Or transparent and electrically conductive film, antistatic film used in the FPD such as electroluminescent display, liquid crystal display etc..
For example, surface protection film can be enumerated and is used in the case where laminate of the invention is used as surface protection film
Protect the optical films such as polarizing film, light guide plate from the film that damages or pollute.For example, in the manufacture of liquid crystal display panel, polarizing film is led
The optical components such as tabula rasa (film) carry out lamination, assembling with the state with protective film, in addition, also with guarantor in inspection operation
The state of cuticula carries out, and is finally peeled off later, is discarded.In the case where being used for surface protection film, laminate preferably has viscous
Close layer.
About the bonding force of surface protection film, suitable range is different according to adherend, for example, being in adherend
In the case where the glass baseplate of alkali-free glass etc, bonding force is preferably 0.05N/25mm~10N/25mm.
It, as needed can be in bonding layer surface fitting peeling paper (diaphragm) in surface protection film.The material of peeling paper
It can be cited for example that paper or plastic foil, from surface smoothness it is excellent from the aspect of, it is preferable to use plastic foil.As plastic foil,
It can be cited for example that polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, chlorine
Ethylene copolymer film, polyethylene terephthalate film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene-acetate
Vinyl ester copolymers film etc..
For peeling paper, the face that it is contacted with adhesive layer can be implemented to utilize silicone-based, fluorine system, chain alkyl
The release agent of release agent, the silica powder of system, fatty acid acyl amine system etc. etc. is handled.
Surface protection film can be suitable as such as liquid crystal display panel, organic el display, plasma scope, polarization
The surface protection film of piece, light diffusing patch, lens coating etc. can protect these adherend in a manner of mechanically and electrically.
Embodiment
Enumerate embodiment below to illustrate the present invention, but the present invention is not limited to the following embodiment.As long as hereinafter, not special
It does not record, then " % " refers to " weight % ".
(1) material is used
(1-1) base material film
PET film (Dongli Ltd.'s manufacture, Lumiror T60)
(1-2) carbon nanomaterial
Carbon nanotube 1 (production, solid component content 1.1% in Production Example 1)
Carbon nanotube 2 (production, solid component content 1.1% in Production Example 2)
Carbon nanotube 3 (production, solid component content 1.1% in Production Example 3)
Carbon nanotube 4 (production, solid component content 1.1% in Production Example 4)
Graphene (production, solid component content 1.1% in Production Example 5)
(1-3) levelling agent
Polyether system levelling agent (manufacture of Clariant company, ProductName: Emulsogen LCN070, HLB:13)
Polyether system levelling agent (Sanyo Chemical Industries, Ltd.'s manufacture, ProductName: EMULMIN 240, HLB:16)
Polyester levelling agent (Sanyo Chemical Industries, Ltd.'s manufacture, ProductName: IONNET MO-600, HLB:14)
Fluorine system levelling agent (E.I.Du Pont Company's manufacture, Capstone FS-3100, HLB:9.8)
Silicone-based levelling agent (manufacture of Toray Dow Corning company, 8029Additive)
(1-4) binder resin
Melamine (Dainippon Ink Chemicals's manufacture, BECKAMINE M-3, solid component content 77%)
Polyurethane (Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture, SUPERFLEX 830HS, solid component content 35%, glass
68 DEG C of glass transition temperature)
Polyester (Toagosei Co., Ltd's manufacture, Aron Melt PES-2405A30, solid component content 30%, glass
40 DEG C of glass transition temperature)
Acrylic resin (Toagosei Co., Ltd's manufacture, Jurymer FC-80, solid component content 30%, glass
Glass transition temperature 50 C)
Silicon ester resin (manufacture of Colcourt Co., Ltd., ethyl silicate 40, solid component content 40%)
(1-5) catalyst
Isopropyl sulfonic acid (manufacture of TAYCA company, ProductName: Taycatox 500)
(1-6) organic solvent
Ethyl alcohol (Fujiphoto and the manufacture of Wako Pure Chemical Industries company)
2- propyl alcohol (Fujiphoto and the manufacture of Wako Pure Chemical Industries company)
Methanol (Fujiphoto and the manufacture of Wako Pure Chemical Industries company)
(2) evaluation method
(2-1) surface resistivity
Surface resistivity after being just film-made about coating film, according to surface resistivity and device can measurement range, by
It selects and is evaluated in following methods.
It is 1.0 × 10 in surface resistivity6(Ω/ )~1.0 × 108In the case where (Ω/): using Mitsubishi Chemical's strain
The UA probe of the Hiresta-UP (MCP-HT450 type) of formula commercial firm manufacture, is measured with the application voltage of 10V.
It is more than 1.0 × 10 in surface resistivity8In the case where (Ω/): being manufactured using Mitsubishi chemical Co., Ltd
The UA probe of Hiresta-UP (MCP-HT450 type), is measured with the application voltage of 250V.
(2-2) total light transmittance and mist degree
Total light transmittance and mist degree after just manufacturing about laminate use haze computer (SUGA according to JIS K7136
The manufacture of TEST INSTRUMENTS company, HZ-2) it is measured.
The production of (Production Example 1) carbon nano tube water dispersoid
By 300 μm of average length, the carbon nanotube of diameter about 4nm (Zeon Nano Technology Co., Ltd. system
Make, ProductName: ZEONANO SG101) 0.1 parts by weight, non-ionic dispersing agent (BASF AG's manufacture, production as dispersing agent
The name of an article: Pluronic F108, HLB:24 or more) 0.6 parts by weight, 30 parts by weight of ethyl alcohol, 70 parts by weight of pure water loading glass beaker
In, using ultrasonic homogenizer (manufacture of hielscher company, ProductName " HP50H ") with 50W, frequency 30kHz progress 30 minutes
Thus decentralized processing obtains the nanotube dispersion 1 that solid component content is 1.1%.
The production of (Production Example 2) carbon nano tube water dispersoid
By 300 μm of average length, the carbon nanotube of diameter about 4nm (Zeon Nano Technology Co., Ltd. system
Make, ProductName: ZEONANO SG101) 0.1 parts by weight, non-ionic dispersing agent (BASF AG's manufacture, production as dispersing agent
The name of an article: Genapol PF 80, HLB:19) 0.6 parts by weight, 100 parts by weight of pure water are fitted into glass beaker, and it is equal using ultrasonic wave
Matter device (manufacture of hielscher company, ProductName " HP50H ") carries out 30 minutes decentralized processings with 50W, frequency 30kHz, thus
The nanotube dispersion 2 for being 1.1% to solid component content.
The production of (Production Example 3) carbon nano tube water dispersoid
By 10 μm of average length, diameter about 4nm double-walled carbon nano-tube (Aldrich Co., Ltd. manufacture, product number:
755168) 1 parts by weight, anionic dispersing agent (manufacture of Fujiphoto Wako Pure Chemical Industries, Ltd., production as dispersing agent
The name of an article: neopelex) 10 parts by weight, 989 parts by weight of pure water are fitted into glass beaker, utilize ultrasonic homogenizer
(manufacture of hielscher company, ProductName " HP50H ") carries out 30 minutes decentralized processings with 50W, frequency 30kHz, is thus consolidated
The nanotube dispersion 3 that body component content is 1.1%.
The production of (Production Example 4) carbon nano tube water dispersoid
By 300 μm of average length, the carbon nanotube of diameter about 4nm (Zeon Nano Technology Co., Ltd. system
Make, ProductName: ZEONANO SG101) 0.1 parts by weight, macromolecular dispersing agent (the Japanese catalyst corporation as dispersing agent
Make, ProductName: Polyvinyl pyrrolidone K-30, HLB:15) 0.6 parts by weight, 100 parts by weight of pure water loading glass burning
In cup, 30 points are carried out with 50W, frequency 30kHz using ultrasonic homogenizer (manufacture of hielscher company, ProductName " HP50H ")
Thus clock decentralized processing obtains the nanotube dispersion 4 that solid component content is 1.1%.
The production of (Production Example 5) graphene aqueous dispersion
Graphene (manufacture of ITEC company, product number: iGRAFEN- α s, 10 μ of average grain diameter are used instead of carbon nanotube
M), in addition to this, by the way that similarly operation obtains the graphene aqueous dispersion that solid component content is 1.1% with Production Example 1.
(embodiment 1~15, comparative example 1~2)
In embodiment 1~15, comparative example 1~2, by the carbon nano tube water dispersoid of Production Example 1~4 or Production Example 5
The carbon nanomaterials such as graphene aqueous dispersion, levelling agent, binder resin and the listed in Table 1 weight ratio (solid of catalyst
Ingredient ratio) it is mixed, it is diluted in such a way that solid component content is 1% with the organic solvent that table 1 is recorded, is thus made
Make coating composition.The mixed organic solvents recorded in embodiment 12~14 using table 1.
In table 1, carbon nanomaterial describes the weight including dispersing agent.Using stick coating method base material film one side coating
Coating composition, it is 2 minutes dry at 120 DEG C using blast drier, coating film is consequently formed, obtains laminate.Coating
The film thickness of film is adjusted to 40nm by proper choice of the solid component of coating composition and the number of bar coater.
For obtained laminate, surface resistivity, total light transmittance and mist degree are had rated using the above method.As a result
It is shown in table 1.
By the coating composition manufactured in embodiment 1~15, comparative example 1~2 with the 2- aqueous propanol solution of 50 weight % with
After weight ratio meter dilutes 50 times, ultraviolet-uisible spectrophotometer (Japan Spectroscopy Corporation's manufacture, model V-670) measurement is utilized
Absorbance (A) at the wavelength 648nm of dilution.Later, using centrifugal separator (Kubo field manufacturing company manufacture, model:
KUBOTA-4000 5 minutes centrifuging treatments) are carried out under conditions of 3500rpm, 23 DEG C.Similarly measure at centrifuge separation
The absorbance (B) of supernatant after reason.The absorbance change rate of centrifugation front and back is found out by following formula.
It is centrifuged absorbance change rate (%)=(B/A) × 100 of front and back
In table 1, " OVER " of comparative example 1~2 refers to OVER RANGE (going beyond the scope), indicates that surface resistivity is 14 times
It is more than side.
As shown in table 1, the laminate about embodiment 1~15, the absorbance change rate for being centrifuged front and back is 50% or more, In
Carbon nanomaterial disperses in coating composition, as a result, antistatic property and the transparency also show that high value.
About the coating composition of the comparative example 1 without levelling agent, the dispersibility of carbon nanomaterial is low, grasps in centrifuge separation
Condensation product made of carbon nanomaterial cohesion precipitates in work, therefore the absorbance change rate for being centrifuged front and back is down to 30%.Separately
Outside, when being coated with using bar coater, condensation product made of carbon nanomaterial cohesion is scraped in the slot of bar coater, in coating film
The carbon nanomaterial of sufficient amount will not be remained, as a result, the electric conductivity of the laminate of obtained comparative example 1 is low.Further, since
It is coated with the influence of a small amount of remaining condensation product in film, mist degree also shows that 4% high level.
The laminate of the comparative example 2 obtained by the coating composition without carbon nanomaterial does not have antistatic property.
Claims (10)
1. a kind of coating composition, it includes (a) carbon nanomaterial, (b) binder resin, (c) levelling agents and (d) organic molten
Agent.
2. coating composition as described in claim 1, wherein with 50% 2- aqueous propanol solution with weight ratio meter dilution 50
Times, 5 minutes centrifuging treatments, the extinction of the complete supernatant of rigid centrifuging treatment are carried out under conditions of 3500rpm, 23 DEG C
Degree is 50% or more of the absorbance before the centrifuging treatment.
3. coating composition as claimed in claim 1 or 2, wherein (a) carbon nanomaterial is selected from by graphene, carbon nanometer
It is at least one kind of in the group of pipe and fullerene composition.
4. coating composition according to any one of claims 1 to 3, wherein (b) binder resin is selected from by acrylic acid
It is at least one kind of in the group that resinoid, polyester resin, carbamate resins, melamine and silicon ester resin form.
5. coating composition as described in any one of claims 1 to 4, wherein (c) levelling agent is the change with polyester construction
Close object or the compound with polyether structure.
6. such as coating composition according to any one of claims 1 to 5, wherein (d) organic solvent is selected from by methanol, second
It is at least one kind of in the group of alcohol and propyl alcohol composition.
7. such as coating composition according to any one of claims 1 to 6, wherein
(a) carbon nanomaterial is graphene,
(b) binder resin is acrylic resin,
(c) levelling agent is the compound with polyester construction.
8. such as coating composition according to any one of claims 1 to 6, wherein
(a) carbon nanomaterial is carbon nanotube,
(b) binder resin is melamine,
(c) levelling agent is the compound with polyether structure.
9. the manufacturing method of coating composition according to any one of claims 1 to 8 comprising process (1) below~
(2):
(1) in the presence of (e) dispersing agent, decentralized processing is carried out to (a) carbon nanomaterial in water, (a) carbon is thus obtained and receives
The process of the aqueous dispersion of rice material；With
(2) (b) binder resin, (c) levelling agent are added into the aqueous dispersion of (a) carbon nanomaterial obtained in process (1)
And (d) organic solvent, thus obtain the process of coating composition.
10. manufacturing method as claimed in claim 9, wherein relative to 100 weight of (e) dispersing agent used in process (1)
Part, the amount of (c) levelling agent used in process (2) is 5 parts by weight~2400 parts by weight.
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| CN113502072A (en) * | 2021-07-09 | 2021-10-15 | 江苏云睿汽车电器系统有限公司 | Nano composite coating and preparation method thereof |
| CN113604088A (en) * | 2021-08-18 | 2021-11-05 | 四川大学 | Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method |
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| CN112480561A (en) * | 2020-11-26 | 2021-03-12 | 江西捷美软包装有限公司 | Novel material film for high-temperature cooking bag and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| JP7412087B2 (en) | 2024-01-12 |
| JP2019189857A (en) | 2019-10-31 |
| TW201943805A (en) | 2019-11-16 |
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