TW201943805A - Coating composition in which the dispersing property of carbon nanomaterial is relatively high - Google Patents

Abstract

The present invention provides a coating composition, which the dispersing property of carbon nanomaterial is relatively high. The coating composition of the present invention includes (a) a carbon nanomaterial, (b) a binder resin, (c) a leveling agent, and (d) an organic solvent. In the coating composition, the light absorbance degree of a supernatant liquid immediately after being diluted 50 times by 2-propanol aqueous solution with 50 weight% and subjected to a centrifugation treatment for 5 minutes under the condition of 3500 rpm and 23 DEG C is 50% or more of the light absorbance degree before the centrifugation treatment. The carbon nanomaterial is preferably at least one selected from the group consisting of graphene, carbon nanotubes, and fullerenes. The binder resin is at least one selected from the group consisting of acrylic resins, polyester resins, urethane resins, melamine, and silicate resins. The leveling agent is preferably a compound having a polyester structure or a compound having a polyether structure. The organic solvent is preferably at least one selected from the group consisting of methanol, ethanol and propanol.

Description

Coating composition

The present invention relates to a coating composition. Specifically, the present invention relates to a coating composition for improving the dispersibility of a carbon nanomaterial.

Carbon nanomaterials are expected to be used as conductive coating agents because of their high conductivity, high stretchability, and low coloration. However, carbon nanomaterials have a relatively large aspect ratio and have an unsaturated coordination structure, so they have strong intermolecular interactions, and have the property of easy aggregation. In the state where the carbon nano material is agglomerated, the original conductivity and transparency cannot be exerted. Therefore, the industry requires that the carbon nano material be dispersed in a conductive coating agent.

Heretofore, it has been known that a dispersant is blended in order to improve the dispersibility of a carbon nanomaterial (Patent Document 1). However, even if a dispersant is blended, when a binder resin or other additive is added to constitute a coating composition, agglomeration occurs in many cases, and the usable binder resin or additive is restricted. It is speculated that the reason is that the binder resin and the like interact with the dispersant, and as a result, the dispersant cannot exist near the carbon nano material, and aggregation occurs.

Further, in order to improve the dispersibility of carbon nanomaterials, a dispersing treatment using ultrasonic waves is known (Patent Document 2). However, it is difficult to adjust the ultrasonic treatment. If the carbon nano material is excessively processed, the carbon nano material is broken or damaged. As a result, a new active surface is generated, and the tendency to aggregate is more likely.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-263608
[Patent Document 2] Japanese Patent Laid-Open No. 2006-16222

[Problems to be Solved by the Invention]

An object of the present invention is to provide a coating composition having a high dispersibility of a carbon nanomaterial.
[Technical means to solve the problem]

The present inventors have found that by adding a leveling agent newly, a coating composition can be obtained that maintains dispersibility even when a binder or a solvent is added, thereby completing the present invention.

That is, the present invention relates to a coating composition comprising (a) a carbon nano material, (b) a binder resin, (c) a leveling agent, and (d) an organic solvent.

In the above coating composition, a 50% 2-propanol aqueous solution was diluted 50 times by weight ratio, and the absorbance of the supernatant liquid was centrifuged at 3500 rpm and 23 ° C. for 5 minutes. It is preferably more than 50% of the absorbance before centrifugation.

In the coating composition described above, (a) the carbon nanomaterial is preferably at least one selected from the group consisting of graphene, carbon nanotubes, and fullerenes.

In the coating composition, (b) the binder resin is preferably at least one selected from the group consisting of an acrylic resin, a polyester resin, an amine ester resin, a melamine, and a silicate resin.

In the above coating composition, the (c) leveling agent is preferably a compound having a polyester structure or a compound having a polyether structure.

In the coating composition, the (d) organic solvent is preferably at least one selected from the group consisting of methanol, ethanol, and propanol.

In the above coating composition, (a) the carbon nano material is preferably graphene, (b) the binder resin is preferably an acrylic resin, and (c) the leveling agent is preferably a compound having a polyester structure.

In the above coating composition, (a) the carbon nano material is preferably a carbon nano tube, (b) the binder resin is preferably melamine, and (c) the leveling agent is preferably a compound having a polyether structure.

The present invention also relates to a method for manufacturing the coating composition, which includes the following steps (1) to (2):
(1) a step of obtaining (a) an aqueous dispersion of a carbon nanomaterial by dispersing (a) a carbon nanomaterial in water in the presence of (e) a dispersant; and (2) by A step of adding (b) a binder resin, (c) a leveling agent, and (d) an organic solvent to the (a) aqueous dispersion of carbon nanomaterial obtained in step (1) to obtain a coating composition.

In the manufacturing method of the said coating composition, it is preferable that it is 5-2400 with respect to 100 weight part of (e) dispersants used in step (1), and (c) leveling agents used in step (2). Parts by weight.
[Effect of the invention]

The coating composition of the present invention can improve the dispersibility of a carbon nanomaterial.

(1) Coating composition The present invention relates to a coating composition comprising (a) a carbon nano material, (b) a binder resin, (c) a leveling agent, and (d) an organic solvent.

In the coating composition of the present invention, in terms of dispersibility, a 50% 2-propanol aqueous solution is diluted 50-fold by weight ratio, and is subjected to centrifugation treatment at 3500 rpm and 23 ° C. 5 The absorbance of the supernatant immediately after the minute is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more of the absorbance before centrifugation. Here, the concentration of 2-propanol is a percentage by weight.

(A) Carbon nanomaterials Examples of carbon nanomaterials include carbon nanotubes, graphene, and fullerene. These carbon nanomaterials can be used alone or in combination of two or more. The content of the carbon nanomaterial in the coating composition is not particularly limited, but it is preferably 0.01 to 90% by weight, more preferably 0.1 to 50% by weight, and more preferably 0.1% to 50% by weight based on the solid content of the coating composition as a whole. 0.13 to 30% by weight. In addition, when a laminated body is formed by applying the following method on a substrate to form a coating film, the amount is preferably 0.01 to 50.0 mg / m ² , more preferably 0.1 to 10.0 mg / m on the laminated body. The amount of ² .

The type of the carbon nanotube is not particularly limited, and carbon nanotubes manufactured by various known techniques such as an arc discharge method, a laser evaporation method, and a chemical vapor deposition method (CVD method) can be appropriately selected and used. Any of a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, and a mixture containing these in any ratio may be used. In terms of excellent conductivity, a single-walled carbon nanotube is preferred.

The length of the carbon nanotube is typically 1 to 2000 μm, preferably 5 to 1000 μm, and more preferably 5 to 500 μm. If it exceeds 2000 μm, carbon nanotubes are likely to be agglomerated, broken, and damaged, which is not preferable. If the thickness is less than 1 μm, a sufficient conductive path cannot be formed, which is not preferable.

The diameter of the carbon nanotube is typically 0.1 to 50 nm, preferably 0.3 to 20 nm, and further preferably 0.5 to 10 nm. If it exceeds 50 nm, the conductivity may decrease. In addition, carbon nanotubes below 0.1 nm are not easy to manufacture.

(B) Binder resin The binder resin is not particularly limited, but is preferably selected from the group consisting of polyester resin, acrylic resin, amine ester resin, epoxy resin, polyolefin resin, melamine, and silicate resin. At least one of them. The reason is that the compatibility with other components in the coating composition is high, and the laminated body formed by using the coating composition containing these adhesives has good affinity and film-forming property to the substrate. These adhesives can be used alone or in combination of two or more.

The polyester resin is not particularly limited as long as it is a polymer compound obtained by polycondensing a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups, and examples thereof include polyethylene terephthalate Esters, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like. These can be used alone or in combination of two or more.

The acrylic resin is not particularly limited, and examples thereof include a (meth) acrylic resin and a vinyl ester resin. The acrylic resin may be, for example, a polymer containing a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphate group as a constituent monomer, and examples thereof include a polymerizable monomer having an acid group Homopolymers or copolymers of polymers, copolymers of polymerizable monomers and copolymerizable monomers having acid groups, and the like. These can be used alone or in combination of two or more.

The (meth) acrylic resin can be polymerized with a copolymerizable monomer as long as it contains a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more). In this case, (meth) acrylic resin As long as at least one of the system monomer and the copolymerizable monomer has an acid group.

Examples of the (meth) acrylic resin include (meth) acrylic monomers [(meth) acrylic acid, (meth) acrylic acid sulfoalkyl esters, and ) Acrylamide, etc.] or copolymers thereof, (meth) acrylic monomers which may have an acid group, and other polymerizable monomers which have an acid group [other polymerizable carboxylic acid, polymerizable polycarboxylic acid or acid anhydride, ethylene Aromatic aromatic sulfonic acid, etc.] and / or copolymerizable monomers [such as alkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomers, etc.]) Copolymers, other polymer monomers having acid groups, and (meth) acrylic copolymerizable monomers [e.g. alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, shrinking (meth) acrylate Glycerides, (meth) acrylonitrile, etc.] copolymers, rosin modified acrylates, special modified acrylic resins, acrylates, epoxy acrylates, urethane acrylate emulsions, etc.

Among these (meth) acrylic resins, preferred are (meth) acrylic acid- (meth) acrylate polymers (acrylic acid-methyl methacrylate copolymers, etc.), and (meth) acrylic acid- (formaldehyde) Group) acrylate-styrene copolymer (acrylic acid-methyl methacrylate-styrene copolymer, etc.) and the like.

The polyurethane is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group, and examples thereof include ester-ether-based polyurethanes, ether-based polyurethanes, and polyester-based polyurethanes. , Carbonate-based polyurethane, acrylic-based polyurethane, and the like. These can be used alone or in combination of two or more.

The epoxy resin is not particularly limited, and examples thereof include a bisphenol A type, a bisphenol F type, a phenol novolac type, a polyfunctional tetrakis (hydroxyphenyl) ethane type having multiple benzene rings, or Tris (hydroxyphenyl) methane type, biphenyl type, triphenol methane type, naphthalene type, o-phenol novolac type, dicyclopentadiene type, aminophenol type, alicyclic epoxy resin, etc. Oxyresin etc. These can be used alone or in combination of two or more.

The polyolefin resin is not particularly limited, and examples thereof include polyethylene, polypropylene, chlorinated polypropylene, maleic anhydride-modified polypropylene, maleic anhydride-modified chlorinated polypropylene, and the like. These can be used alone or in combination of two or more.

Examples of the silicate resin include an alkoxysilane obtained by condensing monomers of an alkoxysilane represented by the following formula (I) with one or more siloxane bonds (Si in one molecule). -O-Si) oligomers and the like.
SiR ¹ ₄ (I)
(Wherein R ¹ is hydrogen, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group which may have a substituent, and a phenyl group which may have a substituent; wherein at least one of the four R ¹ is a carbon number 1 to 4 alkoxy or hydroxyl)
The silicate resin is preferably one obtained by condensing two or more molecules of an alkoxysilane represented by the formula (I).

The structure of the silicate resin is not particularly limited, and may be linear or branched. Moreover, the silicate resin may use the compound represented by Formula (I) alone, or may use 2 or more types together.

Examples of the silicate resin include a silicon alkoxide acrylic resin, a silicon alkoxide epoxy resin, a silicon alkoxide vinyl resin, a silicon alkoxide methacrylic resin, a silicon alkoxide thiol resin, and silicon. Silanol-based resins such as alkoxide amine-based resins, silicon alkoxide isocyanate-based resins, silicon alkoxide-based resins, and silicon alkoxide-based resins that do not have a functional group other than a silicon alkoxide group.

Specific constituents of the silicate resin include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-methacrylic acid Propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryl Oxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Acrylic methoxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-amine Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-dimethyl Butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-iso Cyanopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methylphenoxysilane, N-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxy Silane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra Tetraalkoxysilane such as propoxysilane, tetrabutoxysilane, or alkoxysilicate oligomer such as tetraphenoxysilane, methyl silicate oligomer, ethyl silicate oligomer, etc. Wait. Among these, a tetraalkoxysilane, a tetraphenoxysilane, and an alkoxysilicate oligomer are preferable.

The weight average molecular weight of the silicate resin is not particularly limited, but it is preferably greater than 150 and 4,000, more preferably greater than 240 and 3,000, and still more preferably 330 to 2500.

The content of the binder resin is not particularly limited, but it is preferably 30 to 98% by weight, more preferably 40 to 90% by weight, and still more preferably 50 to 80% by weight based on the solid content of the coating composition as a whole. If the content of the binder resin is less than 30% by weight, the strength of the laminate may be weakened. On the other hand, if it exceeds 98% by weight, the proportion of carbon nanomaterials in the laminate may be relatively small. Therefore, the conductivity of the laminated body cannot be sufficiently ensured.

(C) Leveling agent By blending the leveling agent, the coating property of the substrate of the coating composition of the present invention becomes good. On the other hand, as described below, (a) carbon nanomaterials need to be subjected to a dispersion treatment in advance, and a dispersant that stabilizes the dispersion state of (a) carbon nanomaterials is used during the dispersion treatment, but the following problems are prone to occur: During the process of manufacturing the coating composition, the dispersant interacts with other components such as the binder resin, so that the dispersant no longer exists near the carbon nanomaterial, and as a result, the dispersion stability of the coating composition is reduced. The leveling agent is added in order to obtain good coating properties of the substrate, and it interacts with the carbon nanomaterial to compensate for the dispersion function. As a result, the dispersion stability of the coating composition is improved. As a leveling agent, the one with higher hydrophilicity has excellent dispersibility in a water-organic solvent, so the HLB value is preferably 9 or more, more preferably 10 or more, and even more preferably 12 or more. The HLB value can be calculated by the following calculation method.
Griffin method: [(Molecular weight of the hydrophilic part) ÷ (Molecular weight of the entire body)] × 20

Specific leveling agents include polyester leveling agents, polyether leveling agents, fluorine leveling agents, polysiloxane leveling agents, and acrylic leveling agents. Among these, the polyester-based leveling agent with an ester bond and the polyether-based leveling agent with an ether bond easily interact with carbon nanomaterials, and the performance of dispersing carbon nanomaterials in water-alcohol is better than that of carbon nanomaterials. High, so it is better.

Examples of the polyester-based leveling agent include polyester modified polydimethylsiloxane containing acrylylene groups, polyester modified polydimethylsiloxane, and polyester polyols.

Examples of the polyether-based leveling agent include cellulose ether; polytriglucose; polyethylene glycol: polyether-modified polydimethylsiloxane, polyether-modified silicone, and polyetherester. Hydroxyl polydimethylsiloxane, polyether modified polysiloxane containing polyacrylyl groups and other polysiloxane modified polyether; polyglycerol; polyether polyol, polyoxyethylene-polyoxypropylene Condensates, alkyl ether derivatives such as polyoxyethylene alkyl phenyl ethers, lauryl alkoxylates, and alkyl ether sulfates. These leveling agents can be used alone or in combination of two or more.

Examples of the fluorine-based leveling agent include perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, perfluorobutanesulfonic acid, and fluorine-containing groups. An oligomer of a hydrophilic group and a lipophilic group, a carboxylate containing a perfluoroalkyl group, a phosphate containing a perfluoroalkyl group and a phosphate group, and the like. These leveling agents can be used alone or in combination of two or more.

Examples of the polysiloxane-based leveling agent include reactive polysiloxanes in which reactive groups such as amine groups, epoxy groups, hydroxyl groups, and carboxyl groups are introduced, and alkyl groups and esters are introduced in addition to polysiloxanes. Non-reactive polysiloxanes such as non-reactive groups such as alkyl, aralkyl, phenyl, and polyether groups. These leveling agents can be used alone or in combination of two or more.

Examples of the acrylic leveling agent include an acrylic copolymer composed of polysiloxane and acrylic acid. These leveling agents can be used alone or in combination of two or more.

As the leveling agent, the same material as the dispersing agent described below may also be used, and it is preferable to use a leveling agent having an HLB value lower than that of the dispersing agent.

The content of the leveling agent is not particularly limited, but is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight, and still more preferably 1 to 10% by weight based on the entire solid component of the coating composition. If the content of the leveling agent is less than 0.01% by weight, there is a tendency that the dispersion stability and coating properties of the substrate are insufficient. On the other hand, if it exceeds 40% by weight, the film strength becomes insufficient and coating may occur. The tendency of uneven cloth.

(D) Organic solvent The organic solvent has a function of improving the affinity of the coating composition to the substrate. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; and ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Glycols; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetates such as alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monomethyl ether , Propylene glycol ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate; ethers such as diethyl ether, diisopropyl ether, methyl third butyl ether, tetrahydrofuran; acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; toluene, xylene (o-, m-, or para-xylene), hexane, heptane and other hydrocarbons; ethyl acetate, acetic acid Ester such as butyl ester, ethyl acetate, methyl orthoacetate, ethyl orthoformate: halogens, N-methylformamide, N , N-dimethylformamidine, γ-butyrolactone, N-methylpyrrolidone, and other amine compounds; 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerol and other hydroxyl-containing compounds; dimethylsulfinium and other compounds with sulfo groups; halogens , Isophorone, propylene carbonate, acetone, acetonitrile, mixed solvents of water and these organic solvents (aqueous organic solvents), mixed solvents of two or more organic solvents, etc. In terms of the dispersion stability of carbon nanomaterials and the applicability to a substrate, among these, a mixed solvent of organic solvents with each other, a mixed solvent of water and organic solvents are more preferable, and alcohols with each other are more preferable. Mixed solvents, mixed solvents of water and alcohols. The mixed solvent of alcohols is preferably a solvent obtained by appropriately mixing methanol, ethanol, and 2-propanol. As a mixed solvent of water and alcohol, a combination of water and methanol, water and ethanol, and water and 2-propanol is preferable. When a mixed solvent of water and an organic solvent is used, the concentration of the organic solvent is preferably 30 to 90% by weight, and more preferably 40 to 80% by weight. Moreover, in order to improve coating properties, it is also effective to add ethylene glycols, propylene glycols, amidine compounds, and the like.

It is preferable that the organic solvent does not remain in the multilayer body formed using the coating composition. In addition, in this specification, there is no special distinction between those who completely dissolve all components of the coating composition (that is, "solvent") and those that disperse insoluble components (that is, "dispersion medium").

From the viewpoint of coatability or liquid stability, the solid content component in the coating composition is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.5 to 5% by weight. This concentration can be adjusted according to the amount of the coating composition added to the organic solvent or a mixed solvent of water and the organic solvent.

As specific examples of the coating composition, the following coating compositions can be cited: (a) the carbon nanomaterial is graphene, (b) the binder resin is an acrylic resin, and (c) the leveling agent is a polyester having a polyester structure. Compound. Examples of the coating composition include (a) a carbon nanotube material as a carbon nanotube, (b) a binder resin as melamine, and (c) a leveling agent as a compound having a polyether structure.

(Other ingredients)
The coating composition may further contain a conductive polymer, a cross-linking agent, a catalyst, an antioxidant, a defoaming agent, a rheology control agent, a neutralizer, a tackifier, and a foaming agent.

Examples of the conductive polymer include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, polynaphthalene, and derivatives thereof. These can be used alone or in combination of two or more. Among them, a conductive polymer containing at least one thiophene ring in the molecule is preferable in terms of easily forming a highly conductive molecule by including a thiophene ring in the molecule. The conductive polymer may form a complex with a dopant such as a polyanion.

Among conductive polymers containing at least one thiophene ring in the molecule, poly (3,4-disubstituted thiophene) is more preferable in terms of excellent conductivity and chemical stability. When the conductive polymer is a poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a polyanion (dopant), it can be made at low temperature and short. A rough conductor is formed within time, and productivity is also excellent. The polyanion is a dopant of a conductive polymer, and its content is described below.

As the poly (3,4-disubstituted thiophene), poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferred. As poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene), it is preferably represented by the following formula (I):

Polythiophene in cationic form composed of the indicated repeating structural units.
Here, R ¹ and R ² each independently represents a hydrogen atom or alkyl group of C _1-4, or represent C _1-4 alkylene in the case when the junction of R ¹ and R ² bond. The C _1-4 alkyl group is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl, and third butyl. In the case where R ¹ and R ^{2 are} bonded, the alkylene group of C _1-4 is not particularly limited, and examples thereof include methylene, 1,2-ethylene, and 1,3-ethylene. Propyl, 1,4-butylene, 1-methyl-1,2-ethyl, 1-ethyl-1,2-ethyl, 1-methyl-1,3-propyl, 2-methyl-1,3-propane etc. Among these, methylene, 1,2-ethylidene, and 1,3-propylidene are preferable, and 1,2-ethylidene is more preferable. On the C _1-4 alkyl and the C _1-4 alkylene, such as hydrogen and a portion of which may be substituted. As the polythiophene with alkyl of _1-4 C Tensile, particularly preferably poly (3,4-ethylenedioxy thiophene).

The weight average molecular weight of the conductive polymer is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 1,500 to 20,000.

The dopant is not particularly limited, but a polyanion is preferred. The polyanion can form a complex by forming an ion pair with the polythiophene (derivative), so that the polythiophene (derivative) can be stably dispersed in water. The polyanion is not particularly limited, and examples thereof include carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, and polymethacrylic acid), sulfonic acid polymers (for example, polystyrene sulfonic acid) , Polyethylene sulfonic acid, polyisoprene sulfonic acid, etc.). In addition, the carboxylic acid polymers and sulfonic acid polymers may also be vinyl carboxylic acids and vinyl sulfonic acids and other polymerizable monomers, such as aromatics such as acrylates, styrene, vinyl naphthalene, and the like. Copolymer of vinyl compounds. Among these, polystyrenesulfonic acid is particularly preferred.

The weight average molecular weight of the polystyrenesulfonic acid is preferably 20,000 to 500,000, and more preferably 40,000 to 200,000. When a polystyrenesulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive polymer with respect to water may decrease. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

As a composite of a conductive polymer and a polyanion, a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is preferable in terms of particularly excellent conductivity.

The conductivity of the conductive polymer is preferably 0.01 S / cm or more, and more preferably 1 S / cm or more.

When the coating composition contains a conductive polymer, the content of the conductive polymer is preferably 5 to 2000 parts by weight, and more preferably 10 to 1,000 parts by weight based on 100 parts by weight of the solid content of the carbon nanomaterial. .

The thermosetting adhesive resin can be crosslinked by adding a crosslinking agent, and the antistatic performance can be improved. The crosslinking agent is not particularly limited, and examples thereof include crosslinking agents such as melamine, polycarbodiimide, polyoxazoline, polyepoxy, polyisocyanate, and polyacrylate. These crosslinking agents may be used alone or in combination of two or more.

When the coating composition contains a crosslinking agent, its content is not particularly limited, but it is preferably 30% by weight or less, and more preferably 20% by weight or less in the coating composition.

When the coating composition contains a thermosetting adhesive resin and a cross-linking agent, the catalyst for cross-linking the thermosetting adhesive resin is not particularly limited, and examples thereof include a photopolymerization initiator or Thermal polymerization initiators and the like.

(2) Manufacturing method of coating composition The manufacturing method of coating composition includes the following steps:
Step (1), obtaining (a) an aqueous dispersion of carbon nanomaterial by subjecting (a) the carbon nanomaterial to a dispersion treatment in water in the presence of (e) a dispersant; and step (2), A coating composition is obtained by adding (b) a binder resin, (c) a leveling agent, and (d) an organic solvent to the (a) carbon nanomaterial water dispersion obtained in step (1).

In step (1), by dispersing the (a) carbon nanomaterial in water in the presence of the (e) dispersant, the carbon nanomaterial and the dispersant interact to obtain a carbon nanomaterial. Water dispersion. Examples of the dispersion treatment method include vibration mills, planetary mills, ball mills, bead mills, sand mills, jet mills, roll mills, homogenizers, ultrasonic homogenizers, high-pressure homogenizers, and ultrasonic devices. Dispersion performed. In the case where aggregates remain after the dispersion treatment, centrifugal separation can be performed to remove the precipitated aggregates.

The (e) dispersant is not particularly limited as long as it can disperse the carbon nanomaterial in water, and examples thereof include a cationic dispersant, an anionic dispersant, a zwitterionic dispersant, a nonionic dispersant, and a polymer system. Dispersant.

Examples of the cationic dispersant include alkylamine salts having an alkyl group having 8 to 22 carbon atoms such as stearylamine acetate, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide. And other quaternary ammonium salts.

Examples of the anionic dispersant include sodium alkyl sulfate having 8 to 18 carbons such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate having 8 to 18 carbons such as sodium polyoxyethylene lauryl sulfate, and Naphthalenesulfonic acids such as sodium oxycholate, sodium dodecylbenzenesulfonate, alkylbenzenesulfonates having 8 to 18 carbon atoms, fatty acid salts, sodium salts of β-naphthalenesulfonic acid formalin condensates Formalin condensate.

Examples of the zwitterionic dispersant include an alkyl betaine having an alkyl group having 8 to 22 carbon atoms, and an alkyl amine oxide having an alkyl group having 8 to 18 carbon atoms.

Examples of the nonionic dispersant include polyoxyethylene alkyl ethers having an alkyl group having 1 to 20 carbon atoms, block copolymers composed of ethylene oxide and propylene oxide, and those having a carbon number of 1 to 20 Polyoxyalkylene derivatives such as alkylphenol polyglycol ethers of alkyl groups, polycarboxylic acid ester ethers having 2 to 4 carbonized alkylene groups, and sorbitan fats such as sorbitan tristearate Acid ester.

Examples of the polymer-based dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl butyral, hydroxy cellulose, hydroxyalkyl cellulose having an alkyl group having 1 to 8 carbon atoms, and carboxymethyl Polymeric dispersants such as cellulose derivatives such as cellulose and carboxypropyl cellulose, starch, gelatin, acrylic copolymers, polycarboxylic acids or their derivatives, and polystyrene sulfonic acids or their salts.

Among these, polyvinylpyrrolidone, polyvinyl butyral, polyoxyalkylene derivatives, polystyrenesulfonic acid, cellulose derivatives, polycarboxylic acids, acrylic copolymers, and alkanes are preferred. Benzene sulfonates are more preferably polyvinylpyrrolidone, polyvinyl butyral, polyoxyalkylene derivatives, polycarboxylic acids, and acrylic copolymers. These dispersants can be used in combination of two or more kinds. In addition, a dispersant having one or more branched chains and a branched molecular weight of 15 or more is preferable because the molecular chain expands in all directions and the dispersibility is improved.

As for the dispersant, the HLB value is preferably 12 or more, and more preferably 14 or more, for reasons of excellent dispersion stability.

In step (1), (e) the dispersant is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 7 parts by weight, and more preferably 100 parts by weight of the aqueous dispersion of the carbon nanomaterial (a). It is used in an amount of 0.05 to 5 parts by weight. If the amount of the (e) dispersant used is less than 0.001 parts by weight, the (a) carbon nanomaterial may not be sufficiently dispersed, and thus high dispersion stability may not be obtained. When the use amount of the (e) dispersant exceeds 10 parts by weight, foaming may occur during the dispersing treatment, thereby hindering the dispersing treatment.

In step (2), (b) a binder resin, (c) a leveling agent, and (d) an organic solvent are added to the (a) carbon nanomaterial water dispersion obtained in step (1). Thus, a coating composition was obtained. As described above, during the dispersing treatment in step (1), there may be foaming and the use amount of the (e) dispersant is limited. Therefore, the following problem is likely to occur: after the dispersing treatment, for example, (e) The dispersant may interact with components added later such as a binder, and dissociate from the vicinity of the (a) carbon nanomaterial, resulting in a decrease in dispersion stability. By adding (a) an aqueous dispersion of a carbon nanomaterial in step (1) and blending a leveling agent, even when the dispersant interacts with components such as a binder to dissociate from the vicinity of the carbon nanomaterial, The leveling agent can also interact with the carbon nano material to compensate for the dispersing function, so that a coating composition having excellent dispersion stability and storage stability can be obtained. The method for adding (b) the binder resin, (c) the leveling agent, and (d) the organic solvent is not particularly limited, and may be simultaneously added to the aqueous dispersion of the (a) carbon nanomaterial obtained in step (1). Add three ingredients or add them separately. When added separately, the order of addition is not particularly limited.

The amount of (c) the leveling agent used in step (2) is preferably 5 to 2400 parts by weight, more preferably 50 to 1200 parts by weight, relative to 100 parts by weight of the (e) dispersant used in step (1). And more preferably 100 to 600 parts by weight. If it is less than 5 parts by weight, the dispersion stability or the substrate coatability tends to be insufficient. If it exceeds 2400 parts by weight, there is a tendency that the film strength is adversely affected.

(3) The laminated body is formed by applying the coating composition of the present invention to at least one side of a substrate to form a coating film, thereby obtaining a laminated body. The coating composition may be directly applied to the substrate, or another layer such as an undercoat layer may be previously provided on the substrate, and then the layer may be applied.

Examples of the material of the base material include glass, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin, and polymer Polyolefin resins such as polypropylene (PP) resins, polystyrene resins, cycloolefin resins, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyetheretherketone (PEEK) resins, and polyfluorene (PSF) resins , Polyether fluorene (PES) resin, polycarbonate (PC) resin, polyfluorene resin, polyimide resin, acrylic resin, triethyl cellulose (TAC) resin, etc. These materials can be used alone or in combination of two or more.

The thickness of the substrate is not particularly limited, but is preferably 10 to 10,000 μm, and more preferably 25 to 5000 μm. From the viewpoint of transparency, the total light transmittance of the base film is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

The coating film can be obtained by applying a coating composition on at least one side of a substrate and then performing a heat treatment. The method for applying the coating composition to at least one side of the substrate is not particularly limited, and a known method can be used. For example, a roll coating method, a bar coating method, a dip coating method, or spin coating can be used. Method, casting method, nozzle coating method, doctor blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor blade coating method, slit coating method, letterpress ( Letterpress) printing method, stencil (screen) printing method, lithographic (offset) printing method, gravure printing method, jet printing method, inkjet printing method, tampon printing method, etc.

Before coating the coating composition on at least one side of the substrate, the surface of the substrate may be surface-treated in advance as necessary. Examples of the surface treatment include corona treatment, plasma treatment, ITRO treatment, and flame treatment.

The heat treatment when forming the coating film is not particularly limited, and it may be performed by a known method, for example, a blower oven, an infrared oven, a vacuum oven, or the like. When the coating composition contains a solvent, the solvent is removed by heat treatment.

The temperature condition of the heat treatment when forming the coating film is not particularly limited, but is preferably 150 ° C or lower, more preferably 50 to 140 ° C, and still more preferably 60 to 130 ° C. If the temperature of the heat treatment exceeds 150 ° C, the material of the substrate used is limited, for example, a PET film, a polycarbonate film, an acrylic film, and the like that are generally used for a transparent electrode film cannot be used. The processing time of the heat treatment is not particularly limited, but is preferably 0.1 to 60 minutes, and more preferably 0.5 to 30 minutes.

The thickness of the coating film is not particularly limited, but is preferably 1 to 1000 nm, more preferably 2 to 500 nm, and still more preferably 5 to 400 nm.

The surface resistivity of the coating film is not particularly limited, but is preferably 10 ² to 10 ¹¹ Ω / □, more preferably 10 ³ to 10 ¹⁰ Ω / □, and even more preferably 10 ⁴ to 10 ⁹ Ω / □.

The refractive index of the coating film is not particularly limited, but is preferably 1.4 to 1.7, and more preferably 1.5 to 1.6.

The haze value of the laminate is not particularly limited, but is preferably 5.0% or less, more preferably 4.0% or less, and still more preferably 3.0% or less. When the haze value exceeds 5.0%, the transparency of the laminated body may be deteriorated. Furthermore, the lower the haze value, the better, so the lower limit is not particularly limited, and it is, for example, 0.01%. The haze value can be measured in accordance with JIS K7136.

The total light transmittance of the laminated body is not particularly limited, but is preferably 85% or more, and more preferably 87% or more. If the total light transmittance is less than 85%, transparency may be insufficient (appearance is poor). Furthermore, the upper limit of the total light transmittance is 100%. The total light transmittance can be measured in accordance with JIS K7136.

In addition to the coating film, the laminated body may have an adhesive layer on the substrate. The adhesive layer is preferably disposed on the surface of the substrate that is not in contact with the coating film. The adhesive layer is formed using an adhesive composition containing an adhesive. Although it does not specifically limit as an adhesive agent, A well-known person can be used, For example, the (meth) acrylic resin obtained by homopolymerizing or copolymerizing various (meth) acrylate monomers, ethylene, etc. are mentioned, for example. / Polyvinyl acetate copolymer resins, polysiloxane resins such as silicone rubber with a dimethylsilane skeleton, polyurethane resins, natural rubber, and styrene obtained by adding polyols to polyisocyanates- Isoprene-styrene block copolymer (SIS block copolymer), styrene-butadiene-styrene block copolymer (SBS block copolymer), styrene-ethylene · butene-styrene Block copolymers (SEBS block copolymers), styrene-butadiene rubber, polybutadiene, polyisoprene, polyisobutylene, butyl rubber, chloroprene rubber and other rubber-based resins. Among these, (meth) acrylic resins, silicone resins, and polyurethane resins which are excellent in chemical stability, have a high degree of freedom in the design of chemical structures, and are easy to adjust in adhesion. Furthermore, a (meth) acrylic resin and a polyurethane resin are also preferable at the point which is especially excellent in transparency.

As a method for forming the adhesive layer, a conventionally known method can be used, and examples thereof include a method of applying an adhesive composition containing an adhesive to a substrate, and performing crosslinking or heating and drying; and crosslinking or heating and drying A method for transferring an adhesive layer to a substrate. Furthermore, the adhesive composition may contain a crosslinking agent in addition to the adhesive.

As a method of applying the adhesive composition, a conventionally known method can be used. Specifically, for example, a roll coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray method, an air knife can be used. Coating method, etc.

(4) Surface protective film The laminated body of the present invention can be preferably used as a conductive film having low coloring and requiring transparency. Examples of such applications include surface protection films, polarizing plates, masking tapes, releasable labels, packaging materials for semiconductors, electronic parts, etc., surface protection films, polarizing plate applications, electrophotographic recording materials, and magnetic recording materials. 4. Transparent conductive film, antistatic film, etc. for transparent touch panel or electroluminescent display, flat panel display such as liquid crystal display.

For example, when the laminated body of the present invention is used as a surface protective film, the surface protective film may be a film for protecting an optical film such as a polarizing plate or a light guide plate from damage or contamination. For example, in the manufacture of liquid crystal panels, optical components (films) such as polarizing plates and light guide plates are laminated and assembled in a state with a protective film, and after the inspection step is performed in a state with a protective film, Eventually peeled and discarded. When used for a surface protection film, it is preferable that a laminated body has an adhesive layer.

The adhesive force of the surface protection film is different according to the adherend, and the suitable range is different. For example, when the adherend is a glass substrate such as an alkali-free glass, the adhesive force is preferably 0.05 to 10 N / 25. mm.

For the surface protection film, the release paper (separator) can also be attached to the surface of the adhesive layer if necessary. Examples of the material of the release paper include paper and a plastic film. However, in terms of excellent surface smoothness, a plastic film is preferably used. Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, and polyterephthalic acid. Ethylene film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

In the release paper, the surface contacting the adhesive layer can be subjected to release using a silicone, fluorine-based, long-chain alkyl-based, fatty acid ammonium-based release agent, silica powder, and the like. Mold agent treatment.

The surface protection film can be preferably used, for example, as a surface protection film for a liquid crystal panel, an organic EL display, a plasma display, a polarizing plate, a light diffusion sheet, a lens film, etc., and can mechanically and electrically protect these adhered films. body.
[Example]

Hereinafter, the present invention will be described with examples, but the present invention is not limited to the following examples. Hereinafter, "%" means "weight%" unless otherwise specified.

(1) Materials used (1-1) Base film / PET film (manufactured by Toray Co., Ltd., Lumirror T60)
(1-2) Carbon Nanomaterials and Carbon Nanotubes 1 (manufactured by Manufacturing Example 1, solid content rate 1.1%)
Carbon Nanotube 2 (manufactured by Manufacturing Example 2, solid content rate 1.1%)
Carbon Nanotube 3 (manufactured by Manufacturing Example 3, solid content rate 1.1%)
Carbon nanotube 4 (manufactured by manufacturing example 4, solid content rate 1.1%)
Graphene (manufactured in Production Example 5, solid content rate 1.1%)
(1-3) Leveling agent and polyether-based leveling agent (made by Clariant, product name: Emulsogen LCN070, HLB: 13)
· Polyether leveling agent (manufactured by Sanyo Chemical Industry Co., Ltd., product name: Emulmin240, HLB: 16)
· Polyester leveling agent (manufactured by Sanyo Chemical Industry Co., Ltd., product name: IonetMO-600, HLB: 14)
· Fluorine leveling agent (manufactured by DuPont, Capstone FS-3100, HLB: 9.8)
· Polysiloxane based leveling agent (manufactured by Toray Dow Corning, 8029 Additive)
(1-4) Adhesive resin and melamine (manufactured by DIC Corporation, Beckamine M-3, 77% solid content content)
· Polyurethane (manufactured by Daiichi Industries Pharmaceutical Co., Ltd., Superflex 830HS, solid content rate 35%, glass transition temperature 68 ° C)
· Polyester (manufactured by Toa Synthesis Co., Ltd., AronmeltPES-2405A30, solid content rate 30%, glass transition temperature 40 ° C)
· Acrylic resin (manufactured by Toa Synthesis Co., Ltd., Jurymer FC-80, solid content rate 30%, glass transition temperature 50 ° C)
Silicate resin (manufactured by COLCOAT Co., Ltd., Ethyl Silicate 40, solid content rate 40%)
(1-5) Catalyst · cumenesulfonic acid (manufactured by Imperial Chemical Co., Ltd., product name: Taycatox500)
(1-6) Organic solvents and ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
· 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
· Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(2) Evaluation method (2-1) Surface resistivity According to the surface resistivity and the measurable range of the device, the surface resistivity of the coating film immediately after film formation is selected and evaluated by the following method.
In the case where the surface resistivity is 1.0 × 10 ⁶ (Ω / □) to 1.0 × 10 ⁸ (Ω / □): Use HirestaUP (MCP-HT450 type) UA probe manufactured by Mitsubishi Chemical Co., Ltd. at 10 V The applied voltage was measured.
In the case where the surface resistivity exceeds 1.0 × 10 ⁸ (Ω / □): Use a UA probe of HirestaUP (MCP-HT450) manufactured by Mitsubishi Chemical Corporation and measure at an applied voltage of 250 V.

(2-2) Total light transmittance and haze According to JIS K7136 and using a haze meter (manufactured by Suga Testing Machine Co., Ltd., HZ-2), the total light transmittance and haze of the laminated body after manufacturing Determination.

(Manufacturing Example 1) Production of Carbon Nanotube Water Dispersion 0.1 parts by weight of a carbon nanotube (manufactured by Zeonnanotech Co., Ltd., product name: ZEONANO SG101) with an average length of 300 μm and a diameter of about 4 nm was used as a dispersant. Non-ionic dispersant (manufactured by BASF, product name: Pluronic F108, HLB: 24 or more) 0.6 parts by weight, 30 parts by weight of ethanol, and 70 parts by weight of pure water were placed in a glass beaker, and an ultrasonic homogenizer (hielscher) (Product name: "HP50H") was subjected to a dispersion treatment at 50 W and a frequency of 30 kHz for 30 minutes to obtain a carbon nanotube dispersion 1 having a solid content of 1.1%.

(Manufacturing Example 2) Production of Carbon Nanotube Water Dispersion 0.1 parts by weight of carbon nanotubes (manufactured by Zeonnanotech Co., Ltd., product name: ZEONANO SG101) with an average length of 300 μm and a diameter of about 4 nm were used as a dispersant. Non-ionic dispersant (manufactured by BASF, product name: Genapol PF 80, HLB: 19) 0.6 parts by weight and 100 parts by weight of pure water were placed in a glass beaker, and an ultrasonic homogenizer (manufactured by Hielscher, product name " HP50H ") was subjected to a dispersion treatment at 50 W and a frequency of 30 kHz for 30 minutes, thereby obtaining a carbon nanotube dispersion 2 having a solid content of 1.1%.

(Manufacturing Example 3) Production of Carbon Nanotube Water Dispersion One part by weight of a double-walled carbon nanotube (manufactured by Aldrich Co., Ltd., product number: 755168) with an average length of 10 μm and a diameter of about 4 nm was used as a dispersant. 10 parts by weight of anionic dispersant (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: sodium dodecylbenzenesulfonate), and 989 parts by weight of pure water were placed in a glass beaker and passed through an ultrasonic homogenizer (Manufactured by Hielscher, product name "HP50H") was subjected to a dispersion treatment at 50 W and a frequency of 30 kHz for 30 minutes, thereby obtaining a carbon nanotube dispersion 3 having a solid content of 1.1%.

(Manufacturing Example 4) Production of Carbon Nanotube Water Dispersion 0.1 parts by weight of a carbon nanotube (manufactured by Zeonnanotech Co., Ltd., product name: ZEONANO SG101) with an average length of 300 μm and a diameter of about 4 nm was used as a dispersant. Polymer-based dispersant (manufactured by Japan Catalyst Co., Ltd., product name: Polyvinylpyrrolidone K-30, HLB: 15) 0.6 parts by weight and 100 parts by weight of pure water were placed in a glass beaker, and an ultrasonic homogenizer (manufactured by Hielscher, The product name "HP50H") was subjected to a dispersion treatment at 50 W and a frequency of 30 kHz for 30 minutes, thereby obtaining a carbon nanotube dispersion 4 having a solid content of 1.1%.

(Manufacturing Example 5) The same operation as in Manufacturing Example 1 was carried out except that graphene (itec company, product number: iGRAFEN-αs, average particle diameter: 10 μm) was used instead of the carbon nano tube. A graphene aqueous dispersion having a solid content of 1.1% was obtained.

(Examples 1 to 15, Comparative Examples 1 to 2)
In Examples 1 to 15 and Comparative Examples 1 to 2, carbon nanomaterials such as the carbon nano tube water dispersion of Production Examples 1 to 4 or the graphene water dispersion of Production Example 5 were used, a leveling agent, and a bonding agent. The agent resin and the catalyst are mixed in a weight ratio (solid content ratio) described in Table 1 and diluted with an organic solvent described in Table 1 so that the solid content ratio becomes 1%, thereby producing a coating composition. In Examples 12 to 14, the mixed organic solvents described in Table 1 were used.

In Table 1, the carbon nanomaterials include the weight including the dispersant. The coating composition was applied to one side of a base film by a bar coating method, and dried at 120 ° C. for 2 minutes using a blow dryer to form a coating film, thereby obtaining a laminated body. The film thickness of the coating film was adjusted to 40 nm by appropriately selecting the solid content of the coating composition and the number of the bar coater.

For the obtained laminated body, the surface resistivity, total light transmittance, and haze were evaluated by the methods described above. The results are shown in Table 1.

The coating compositions produced in Examples 1 to 15 and Comparative Examples 1 to 2 were diluted 50 times by weight ratio with a 50% by weight 2-propanol aqueous solution, and then the content was measured with an ultraviolet-visible spectrophotometer (Japanese spectrophotometer). Co., Ltd., model V-670) Determine the absorbance (A) of the diluted solution at a wavelength of 648 nm. Thereafter, a centrifugal separator (manufactured by Kubota Manufacturing Co., Ltd., model: KUBOTA-4000) was subjected to centrifugation at 3500 rpm and 23 ° C. for 5 minutes. Similarly, the absorbance (B) of the supernatant after centrifugation was measured. The rate of change in absorbance before and after centrifugation is determined by the following formula.
Change rate of absorbance before and after centrifugation (%) = (B / A) × 100


[Table 1]

In Table 1, "OVER" in Comparative Examples 1 and 2 means OVER RANGE, and indicates that the surface resistivity is 14th power or more.

As shown in Table 1, the change rate of the absorbance of the laminates of Examples 1 to 15 before and after centrifugation was 50% or more, and the carbon nanomaterial was dispersed in the coating composition. As a result, the antistatic properties and transparency were also shown to be relatively low. High value.

The dispersibility of the carbon nanomaterial of the coating composition of Comparative Example 1 without the leveling agent is relatively low. Due to the centrifugal separation operation, the aggregate formed by the carbon nanomaterials settling down, so the rate of change in absorbance before and after centrifugation Down to 30%. In addition, when coating with a bar coater, the aggregate formed by agglomeration of the carbon nano material fell into the groove of the bar coater, resulting in a sufficient amount of carbon nano material not remaining on the coating film, which As a result, the laminated body of Comparative Example 1 obtained had low conductivity. Furthermore, due to the influence of a small amount of agglomerates remaining on the coating film, the haze was also shown to be a high value of 4%.

The laminated body of Comparative Example 2 obtained from a coating composition containing no carbon nanomaterials did not have antistatic properties.

no

no

Claims (10)

A coating composition includes (a) a carbon nano material, (b) a binder resin, (c) a leveling agent, and (d) an organic solvent. The coating composition according to claim 1, wherein the coating composition is diluted 50 times by weight with a 50% 2-propanol aqueous solution, and is subjected to a centrifugal separation treatment at 3500 rpm and 23 ° C. for 5 minutes immediately. The absorbance of the supernatant is more than 50% of the absorbance before the centrifugation. The coating composition according to claim 1 or 2, wherein (a) the carbon nanomaterial is at least one selected from the group consisting of graphene, carbon nanotubes, and fullerenes. The coating composition according to any one of claims 1 to 3, wherein (b) the binder resin is selected from the group consisting of an acrylic resin, a polyester resin, an amine ester resin, a melamine, and a silicate resin At least one of the group. The coating composition according to any one of claims 1 to 4, wherein (c) the leveling agent is a compound having a polyester structure or a compound having a polyether structure. The coating composition according to any one of claims 1 to 5, wherein (d) the organic solvent is at least one selected from the group consisting of methanol, ethanol, and propanol. The coating composition according to any one of claims 1 to 6, wherein (A) the carbon nano material is graphene; (B) the binder resin is an acrylic resin; (C) The leveling agent is a compound having a polyester structure. The coating composition according to any one of claims 1 to 6, wherein (A) Carbon nanomaterials are carbon nanotubes; (B) the binder resin is melamine; (C) The leveling agent is a compound having a polyether structure. A method for manufacturing a coating composition according to any one of claims 1 to 8, comprising the following steps (1) to (2): (1) a step of obtaining (a) an aqueous dispersion of a carbon nanomaterial by dispersing (a) a carbon nanomaterial in water in the presence of (e) a dispersant; and (2) Coating is obtained by adding (b) a binder resin, (c) a leveling agent, and (d) an organic solvent to the (a) aqueous dispersion of the carbon nanomaterial obtained in step (1). Composition steps. The manufacturing method according to claim 9, wherein the amount of the (c) leveling agent used in step (2) is 5 to 2400 weights relative to 100 parts by weight of the (e) dispersant used in step (1). Serving.