Antistatic coating agents, cured products, and laminates

Abstract

To provide an antistatic coating agent, a cured product, and a laminate. [Solution] An antistatic coating agent comprising a carboxylate anion group-containing (meth)acrylic resin and a heteroatom-containing conductive polymer, wherein the mass ratio (heteroatom-containing conductive polymer / carboxylate anion group-containing (meth)acrylic resin) is 0.05 to 1.

Description

[Technical Field]

[0001] This disclosure relates to antistatic coatings, cured products, and laminates. [Background technology]

[0002] Examples of antistatic coating agents include heteroatom-containing conductive polymer-containing coating agents (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2003-292655 [Overview of the project] [Problems that the invention aims to solve]

[0004] The problem that this invention aims to solve is to provide an antistatic coating agent that can produce cured products with excellent curing properties at low temperatures, a long pot life, and good antistatic properties.

[0005] "Pot life" refers to the maximum time (pot life) during which the antistatic properties can be maintained. [Means for solving the problem]

[0006] This disclosure provides the following items: (Item 1) An antistatic coating agent, The antistatic coating agent comprises a carboxylate anion group-containing (meth)acrylic resin and a heteroatom-containing conductive polymer. An antistatic coating agent having a mass ratio (the heteroatom-containing conductive polymer / the carboxylate anion group-containing (meth)acrylic resin) of 0.05 to 1. (Item 2) An antistatic coating agent as described above, comprising a polyfunctional aziridine compound. (Item 3) A cured product of an antistatic coating agent described in any one of the above items. (Item 4) A laminate containing the cured material described in the above items.

[0007] In this disclosure, one or more of the features described above may be provided in combinations other than those explicitly stated. [Effects of the Invention]

[0008] The antistatic coating agent of the present invention exhibits excellent low-temperature curing properties and a long pot life. Furthermore, the cured product shows good antistatic properties. [Modes for carrying out the invention]

[0009] Throughout this disclosure, the ranges of numerical values ​​such as physical properties and content may be set as appropriate (for example, by selecting from the values ​​listed in each of the items below). Specifically, if the numerical value α is such as A3, A2, A1 (A3 > A2 > A1), then the range of the numerical value α may be A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less.

[0010] The components, conditions, numerical values, etc., are not particularly limited, as long as the problems that this invention aims to solve are resolved.

[0011] "αβ amount (A / B)" means the amount of β (α) of A relative to 100α of B. α can be expressed as mass%, mole%, or parts by mass, for example. β amount can be expressed as content, amount used, for example. "Mass% content (A / B)" means the content (mass%) of A relative to 100% mass of B.

[0012] "γ ratio (A / B)" means the γ ratio calculated by the formula "A÷B". The γ ratio includes, for example, mass ratio, molar ratio, etc.

[0013] "Non-volatile content" means the total mass of components other than organic solvents and water. In one embodiment, "non-volatile content of A" means the total mass of the remaining components when 1 g of A is heated to a constant weight at 105°C.

[0014] "(Meth)acryl" means "acryl and / or methacryl". "(Meth)acrylate" means "acrylate and / or methacrylate". "(Meth)acryloyl" means "acryloyl and / or methacryloyl".

[0015] "C···" means "having ··· carbon atoms". For example, "C1~6 alkyl group" means an alkyl group having 1 to 6 carbon atoms. "C6 alkyl group" means an alkyl group having 6 carbon atoms.

[0016] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cycloalkyl group, etc.

[0017] Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, etc.

[0018] Examples of the branched alkyl group include an iso-propyl group, a sec-butyl group, an iso-butyl group, a tert-butyl group, a 2-ethylhexyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group, etc.

[0019] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged-ring cycloalkyl group, a condensed-ring cycloalkyl group, etc. Note that a group in which at least one hydrogen atom of the cycloalkyl group is substituted by an alkyl group is also regarded as a cycloalkyl group.

[0020] A "monocyclic ring" refers to a cyclic structure formed by covalent bonds between carbon atoms that does not have an internal bridging structure. A "condensed ring" refers to a cyclic structure in which two or more monocyclic rings share two atoms (i.e., each ring shares only one edge with the others through condensation). A "bridging ring" refers to a cyclic structure in which two or more monocyclic rings share three or more atoms.

[0021] Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl groups.

[0022] Examples of crosslinked ring cycloalkyl groups include tricyclodecyl groups, adamantyl groups, norbornyl groups, and the like.

[0023] Alkyl groups also include combinations of linear alkyl groups, branched alkyl groups, and cycloalkyl groups. Examples of such combinations include cycloalkylalkyl groups.

[0024] Cycloalkylalkyl groups are represented by the following formula. R calkyl -R alkyl - (In the formula, R calkyl R represents a cycloalkyl group. alkyl (This represents an alkyl group.)

[0025] [Antistatic coating agent: Coating agent] This disclosure relates to an antistatic coating agent, The antistatic coating agent comprises a carboxylate anion group-containing (meth)acrylic resin and a heteroatom-containing conductive polymer. This invention relates to an antistatic coating agent in which the mass ratio (of the heteroatom-containing conductive polymer / the carboxylate anion group-containing (meth)acrylic resin) is 0.05 to 1.

[0026] <Carboxylate anion group-containing (meth)acrylic resin: resin> Carboxylate anion group-containing (meth)acrylic resins can be used alone or in combination of two or more types.

[0027] The "carboxylate anion group" is -C(=O)O - This means that the carboxylate anion group is produced when a hydrogen ion is dissociated from the carboxyl group. The carboxylate anion group-containing unit is incorporated into the resin by the following method. (1) Neutralize the unsaturated carboxylic acid unit with a basic compound. (2) Using an unsaturated carboxylate as the monomer

[0028] (Unsaturated carboxylic acid (salt)) The resin contains unsaturated carboxylic acid (salt) units. Unsaturated carboxylic acid (salt) can be used alone or in combination of two or more types.

[0029] Examples of unsaturated carboxylic acids (salts) include unsaturated carboxylic acids, inorganic salts of unsaturated carboxylic acids, and organic salts of unsaturated carboxylic acids.

[0030] Examples of unsaturated carboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

[0031] Examples of salts include inorganic salts and organic salts.

[0032] Examples of inorganic salts include sodium salts, lithium salts, potassium salts, and ammonium salts.

[0033] Examples of organic salts include amine salts.

[0034] Examples of amines include primary amines, secondary amines, and tertiary amines.

[0035] Examples of primary amines include monomethylamine, monoethylamine, monobutylamine, and cyclohexylamine.

[0036] Examples of secondary amines include dimethylamine, diethylamine, and dibutylamine.

[0037] Examples of tertiary amines include trimethylamine, triethylamine, and tributylamine.

[0038] Examples of mass percentage content (unsaturated carboxylic acid (salt) units / resin) include 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 8% by mass, 5% by mass, and 3% by mass. In one embodiment, the above content is preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 15% by mass.

[0039] Examples of molar content (unsaturated carboxylic acid (salt) units / resin) include 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 8 mol%, 5 mol%, and 3 mol%. In one embodiment, the above content is preferably 3 mol% to 30 mol%.

[0040] Examples of neutralization rates (unsaturated carboxylic acid (salt)) include 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, and 50%. In one embodiment, the above neutralization rate is preferably 50% to 100%.

[0041] ((meth)acrylate alkyl ester) The resin may contain alkyl (meth)acrylate units. Alkyl (meth)acrylate units may be used alone or in combination of two or more types.

[0042] Examples of alkyl (meth)acrylates include linear alkyl (meth)acrylates, branched alkyl (meth)acrylates, and cycloalkyl (meth)acrylates.

[0043] Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decamethyl (meth)acrylate, and undecyl (meth)acrylate.

[0044] Examples of mass% content ((meth)acrylate alkyl ester units / resin) include 97% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 62% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 97% by mass, and more preferably 60% by mass to 95% by mass.

[0045] Examples of mol% content ((meth)acrylate alkyl ester units / resin) include 97 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 62 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the above content is preferably between 0 mol% and 97 mol%.

[0046] (Other monomers: Other monomers) The resin may optionally contain monomer units other than those listed above (other monomers). These other monomers may be used individually or in combination of two or more.

[0047] Other monomers include, for example, compounds containing (meth)acrylamide groups, alkyl (meth)acrylic acid esters containing hydroxyl groups, alkenylaryl compounds, unsaturated sulfonic acids, alkyl (meth)acrylic acid esters containing amino groups, polyoxyalkylene-containing monomers, chlorosilane-containing monomers, (poly)siloxane mono(meth)acrylates, fluoroalkyl (mono)acrylates, and the like.

[0048] Examples of compounds containing a (meth)acrylamide group include (meth)acrylamide, N-substituted monoalkyl(meth)acrylamide, and N-substituted dialkyl(meth)acrylamide.

[0049] Examples of N-substituted monoalkyl(meth)acrylamides include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-lauryl(meth)acrylamide, and N-cyclohexyl-substituted alkyl(meth)acrylamide.

[0050] Examples of N-substituted dialkyl(meth)acrylamides include N,N-dimethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-ditterybutyl(meth)acrylamide, N,N-ditteryoctyl(meth)acrylamide, and N,N-dicyclohexyl(meth)acrylamide.

[0051] Examples of hydroxyl group-containing alkyl (meth)acrylic acid esters include 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate.

[0052] Examples of alkenylaryl compounds include styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, and chlorovinyltoluene.

[0053] Examples of unsaturated sulfonic acids include vinyl sulfonic acid, (meth)allyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sulfonated styrene.

[0054] Examples of amino group-containing alkyl (meth)acrylic acid esters include aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, aminobutyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, N-methylaminopropyl (meth)acrylate, N-methylaminobutyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, and N,N-diethylaminobutyl (meth)acrylate.

[0055] Examples of polyoxyalkylene-containing monomers include polyoxyalkylene (meth)acrylic acid esters, polyoxyalkylene glycerin (meth)acrylic acid esters, polyoxyalkylene monoalkyl (meth)acrylic acid esters, polyoxyalkylene monoalkenyl (meth)acrylic acid esters, polyoxyalkylene (meth)allyl ethers, and polyoxyalkylene glycerin (meth)allyl ethers.

[0056] Chlorosilane-containing monomers include, for example, vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyltrichlorosilane, allyldimethylchlorosilane, allylmethyldichlorosilane, allyltrichlorosilane, 4-butenyldimethylchlorosilane, 4-butenylmethyldichlorosilane, 4-butenyltrichlorosilane, 5-pentenyldimethylchlorosilane, 5-pentenylmethyldichlorosilane, 5-pentenyltrichlorosilane, 3-methacryloxypropyldimethylchlorosilane, and 3-methacryloxypropyldimethylchlorosilane. Examples include criloxypropylmethyldichlorosilane, 3-methacryloxypropyltrichlorosilane, 3-acryloxypropyldimethylchlorosilane, 3-acryloxypropylmethyldichlorosilane, 3-acryloxypropyltrichlorosilane, 4-methacryloxybutyldimethylchlorosilane, 4-methacryloxybutylmethyldichlorosilane, 4-methacryloxybutyltrichlorosilane, 4-acryloxybutyldimethylchlorosilane, and 4-acryloxybutylmethyldichlorosilane.

[0057] Examples of commercially available (poly)siloxane mono(meth)acrylates include "Sylaplane FM-0711", "Sylaplane FM-0721", and "Sylaplane FM-0725" (manufactured by JNC Corporation).

[0058] Examples of fluoroalkyl (mono)acrylates include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2,2,2-trifluoro-1-trifluoromethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, H,1H,5H-octafluoropentyl (meth)acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate, and 2,2,3,3,4,4,5,5,5-nonafluoropentyl (meth)acrylate.

[0059] Examples of mass% content (other monomer units / resin) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass.

[0060] Examples of molar content (other monomer units / resin) include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 50 mol%.

[0061] (Physical properties, etc. (resin)) Examples of glass transition temperatures (resin) include 120°C, 115°C, 110°C, 105°C, 100°C, 95°C, 90°C, 89°C, 85°C, 80°C, 75°C, 70°C, 65°C, 60°C, 55°C, 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, 20°C, 15°C, 10°C, 5°C, 3°C, and 0°C. In one embodiment, the glass transition temperature is preferably 0°C to 120°C, and more preferably 50°C to 120°C.

[0062] The glass transition temperature is calculated using Fox's formula. Fox's formula: 1 / Tg = (Wa / Tga) + (Wb / Tgb) + ... + (Wn / Tgn) Tg: Glass transition temperature (K) of copolymer Wa: Mass % of monomer A Tga: Glass transition temperature (K) of the homopolymer of monomer A Wb: Mass percentage of monomer B Tgb: Glass transition temperature (K) of monomer B homopolymer Wn: Mass percentage of monomer N Tgn: Glass transition temperature (K) of monomer N homopolymer

[0063] Examples of weight-average molecular weight Mw (resin) include 200,000, 175,000, 150,000, 125,000, 100,000, 90,000, 85,000, 80,000, 75,000, 70,000, 65,000, 60,000, 55,000, 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, etc. In one embodiment, the above weight-average molecular weight is preferably 10,000 to 200,000.

[0064] Examples of the number-average molecular weight Mn (resin) include 100,000, 85,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, and 5,000. In one embodiment, the above number-average molecular weight is preferably 5,000 to 100,000.

[0065] Measurement conditions (weight-average molecular weight and number-average molecular weight) include, for example, the following conditions. Model: Product name "HLC-8220" (manufactured by Tosoh Corporation) Columns: Product name "PLgel MIXED-C" (manufactured by Agilent Technology) x 2 Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Measurement temperature: 40℃ Detector: RI Standard: Monodisperse polystyrene Resin concentration: 0.2%

[0066] The amount of carboxylate anion groups (in the resin) is preferably 0.0003 mol / g to 0.005 mol / g, and more preferably 0.001 mol / g to 0.003 mol / g. "Amount of carboxylate anion groups" refers to the number of moles (calculated value) of carboxylate anion groups contained in 1 g of resin (calculated on non-volatile content).

[0067] (Manufacturing method (resin)) Examples of manufacturing methods (for resins) include radical polymerization.

[0068] Radical polymerization initiators can be used alone or in combination of two or more. Examples of radical polymerization initiators include inorganic peroxides, organic peroxides, and azo compounds.

[0069] Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, and potassium persulfate.

[0070] Examples of organic peroxides include benzoyl peroxide, dicumyl peroxide, and lauryl peroxide.

[0071] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and dimethyl-2,2'-azobisisobutyrate.

[0072] The amount used (radical polymerization initiator / total monomer components) is preferably 1 to 10 parts by mass.

[0073] In the manufacturing process (of resins), chain transfer agents may be used as optional. Chain transfer agents may be used alone or in combination of two or more types.

[0074] Examples of chain transfer agents include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer.

[0075] The amount used (chain transfer agent / total monomer components) is preferably about 0 to 5 parts by mass.

[0076] The polymerization temperature is preferably between 60°C and 180°C.

[0077] The polymerization time is preferably between 1 and 20 hours.

[0078] Examples of mass percentage content (carboxylate anion group-containing (meth)acrylic resin / coating agent non-volatile content) include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, etc. In one embodiment, the above content is preferably 50% by mass to 80% by mass.

[0079] <Heteroatom-containing conductive polymer> Heteroatom-containing conductive polymers can be used alone or in combination of two or more.

[0080] A "heteroatom" refers to an atom other than a carbon or hydrogen atom.

[0081] Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0082] Examples of heteroatom-containing conductive polymers include poly(thiophene), poly(thiophenevinylene), poly(pyrrole), poly(furan), and poly(aniline).

[0083] Examples of poly(thiophene) include poly(thiophene), poly(alkylthiophene), poly(monalkoxythiophene), poly(dialkoxythiophene), and poly(alkylenedioxythiophene).

[0084] Examples of poly(alkylthiophenes) include poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3,4-dimethylthiophene), and poly(3,4-dibutylthiophene).

[0085] Examples of poly(monoalkoxythiophenes) include poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), and poly(3-octadecyloxythiophene).

[0086] Examples of poly(dialkoxythiophene) include poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), and poly(3,4-didodecyloxythiophene).

[0087] Examples of poly(alkylenedioxythiophene) include poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(3,4-butenedioxythiophene).

[0088] Examples of poly(thiofenvinylene) include poly(thiofenvinylene), poly(alkylthiofenvinylene), poly(monoalkoxythiofenvinylene), poly(dialkoxythiofenvinylene), and poly(alkylenedioxythiofenvinylene).

[0089] Examples of poly(alkylthiofenvinylene) include poly(3-methylthiofenvinylene), poly(3-ethylthiofenvinylene), poly(3-propylthiofenvinylene), poly(3-butylthiofenvinylene), poly(3-hexylthiofenvinylene), poly(3-heptylthiofenvinylene), poly(3-octylthiofenvinylene), poly(3-decylthiofenvinylene), poly(3-dodecylthiofenvinylene), poly(3-octadecylthiofenvinylene), poly(3,4-dimethylthiofenvinylene), and poly(3,4-dibutylthiofenvinylene).

[0090] Examples of poly(monoalkoxythiofenvinylene) include poly(3-methoxythiofenvinylene), poly(3-ethoxythiofenvinylene), poly(3-butoxythiofenvinylene), poly(3-hexyloxythiofenvinylene), poly(3-heptyloxythiofenvinylene), poly(3-octyloxythiofenvinylene), poly(3-decyloxythiofenvinylene), poly(3-dodecyloxythiofenvinylene), and poly(3-octadecyloxythiofenvinylene).

[0091] Examples of poly(dialkoxythiofenvinylene) include poly(3,4-dimethoxythiofenvinylene), poly(3,4-diethoxythiofenvinylene), poly(3,4-dipropoxythiofenvinylene), poly(3,4-dibutoxythiofenvinylene), poly(3,4-dihexyloxythiofenvinylene), poly(3,4-diheptyloxythiofenvinylene), poly(3,4-dioctyloxythiofenvinylene), poly(3,4-didecyloxythiofenvinylene), and poly(3,4-didodecyloxythiofenvinylene).

[0092] Examples of poly(alkylenedioxythiofenvinylene) include poly(3,4-ethylenedioxythiofenvinylene), poly(3,4-propylenedioxythiofenvinylene), and poly(3,4-butenedioxythiofenvinylene).

[0093] Examples of poly(pyrrole) include poly(pyrrole), poly(alkylpyrrole), poly(monalkoxypyrrole), poly(dialkoxypyrrole), and poly(alkylenedioxypyrrole).

[0094] Examples of poly(alkylpyrrole) include poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-propylpyrrole), poly(3-butylpyrrole), poly(3-hexylpyrrole), poly(3-heptylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3-octadecylpyrrole), poly(3,4-dimethylpyrrole), and poly(3,4-dibutylpyrrole).

[0095] Examples of poly(monoalkoxypyrrole) include poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), poly(3-heptyloxypyrrole), poly(3-octyloxypyrrole), poly(3-decyloxypyrrole), poly(3-dodecyloxypyrrole), and poly(3-octadecyloxypyrrole).

[0096] Examples of poly(dialkoxypyrrole) include poly(3,4-dimethoxypyrrole), poly(3,4-diethoxypyrrole), poly(3,4-dipropoxypyrrole), poly(3,4-dibutoxypyrrole), poly(3,4-dihexyloxypyrrole), poly(3,4-diheptyloxypyrrole), poly(3,4-dioctyloxypyrrole), poly(3,4-didecyloxypyrrole), and poly(3,4-didodecyloxypyrrole).

[0097] Examples of poly(alkylenedioxypyrrole) include poly(3,4-ethylenedioxypyrrole), poly(3,4-propylenedioxypyrrole), and poly(3,4-butenedioxypyrrole).

[0098] Examples of poly(furans) include poly(furan), poly(alkylfuran), poly(monoalkoxyfuran), poly(dialkoxyfuran), and poly(alkylenedioxyfuran).

[0099] Examples of poly(alkylfurans) include poly(3-methylfuran), poly(3-ethylfuran), poly(3-propylfuran), poly(3-butylfuran), poly(3-hexylfuran), poly(3-heptylfuran), poly(3-octylfuran), poly(3-decylfuran), poly(3-dodecylfuran), poly(3-octadecylfuran), poly(3,4-dimethylfuran), and poly(3,4-dibutylfuran).

[0100] Examples of poly(monoalkoxyfurans) include poly(3-methoxyfuran), poly(3-ethoxyfuran), poly(3-butoxyfuran), poly(3-hexyloxyfuran), poly(3-heptyloxyfuran), poly(3-octyloxyfuran), poly(3-decyloxyfuran), poly(3-dodecyloxyfuran), and poly(3-octadecyloxyfuran).

[0101] Examples of poly(dialkoxyfurans) include poly(3,4-dimethoxyfuran), poly(3,4-diethoxyfuran), poly(3,4-dipropoxyfuran), poly(3,4-dibutoxyfuran), poly(3,4-dihexyloxyfuran), poly(3,4-diheptyloxyfuran), poly(3,4-dioctyloxyfuran), poly(3,4-didecyloxyfuran), and poly(3,4-didodecyloxyfuran).

[0102] Examples of poly(alkylenedioxyfuran) include poly(3,4-ethylenedioxyfuran), poly(3,4-propylenedioxyfuran), and poly(3,4-butenedioxyfuran).

[0103] Examples of poly(aniline) include poly(aniline), poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aniline sulfonic acid), and poly(3-aniline sulfonic acid).

[0104] In one embodiment, the heteroatom-containing conductive polymer may optionally contain a dopant.

[0105] Examples of dopants include Lewis acids, proton acids, electrolyte anions, and anionic polymers.

[0106] Lewis acids include, for example, PF5, AsF5, and SbF5.

[0107] Examples of protonic acids include HF, HCl, and H2SO4.

[0108] Electrolyte anions include, for example, Cl - , Br - Examples include sulfonions.

[0109] Examples of anionic polymers include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, ethyl sulfonic acid polyacrylate, butyl sulfonic acid polyacrylate, poly-2-acrylamido-2-methylpropanesulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic carboxylic acid, polymethacrylate carboxylic acid, poly-2-acrylamido-2-methylpropanecarboxylic acid, polyisoprene carboxylic acid, and polyacrylic acid.

[0110] In one embodiment, the heteroatom-containing conductive polymer is preferably poly(alkylenedioxythiophene), and more preferably poly(3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS).

[0111] The mass percentage content (heteroatom-containing conductive polymer / coating agent non-volatile content) is, for example, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.5% by mass, 0.1% by mass, etc. In one embodiment, the above content is preferably 0.1% by mass to 30% by mass.

[0112] The mass ratio (the heteroatom-containing conductive polymer / the carboxylate anion group-containing (meth)acrylic resin) is, for example, 1, 0.90, 0.80, 0.70, 0.60, 0.50, 0.40, 0.39, 0.35, 0.30, 0.25, 0.20, 0.15, 0.14, 0.12, 0.10, 0.09, 0.07, 0.05, etc. In one embodiment, the above mass ratio is preferably 0.05 to 1, and more preferably 0.05 to 0.40.

[0113] <Polyfunctional aziridine compound><\(0000423\)>In one embodiment, the coating agent may optionally contain a polyfunctional aziridine compound. The polyfunctional aziridine compound can be used alone or in combination of two or more.

[0114] "Polyfunctional aziridine compound" means a compound having two or more of the following aziridinyl groups.

Chemical formula

[0115] Examples of the polyfunctional aziridine compound include a bifunctional aziridine compound, a trifunctional aziridine compound, a tetrafunctional aziridine compound, etc.

[0116] Examples of bifunctional aziridine compounds include neopentyl glycol di(β-aziridinyl propionate), 4,4'-isopropylidene diphenol di(β-aziridinyl propionate), 4,4'-methylenediphenol di(β-aziridinyl propionate), 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, and 1,1'-isosoloylbis(2-methylaziridine).

[0117] Examples of trifunctional aziridine compounds include those represented by formula (1) below. [ka] (In formula (1), X represents one of the following: a hydrogen atom, a C1-6 alkyl group, or a C1-3 hydroxyalkyl group. 1 ~R 2 Each of these independently represents a hydrogen atom or a C1-6 alkyl group. 3 (This represents a hydrogen atom or a methyl group.)

[0118] Formula (1) (X = hydrogen atom) is, for example, glycerol-tris(1-aziridinylpropionate), glycerol-tris[2-methyl-(1-aziridinyl)]propionate, glycerol-tris[2-ethyl-(1-aziridinyl)]propionate, glycerol-tris[2-butyl-(1-aziridinyl)]propionate), glycerol-tris[2-propyl-(1-aziridinyl)]propionate, glycerol-tris[2-pentyl-(1-aziridinyl)]propionate, glycerol-tris[2-hexyl-(1-aziridinyl)]propionate Examples include tris[2,3-dimethyl-(1-aziridinyl)]propionate, glycerol-tris[2,3-diethyl-(1-aziridinyl)]propionate, glycerol-tris[2,3-dibutyl-(1-aziridinyl)]propionate, glycerol-tris[2,3-dipropyl-(1-aziridinyl)]propionate, glycerol-tris[2,3-dipentyl-(1-aziridinyl)]propionate, and glycerol-tris[2,3-dihexyl-(1-aziridinyl)]propionate.

[0119] Formula (1) (X=C1~6 alkyl group) is, for example, trimethylolpropane-tris(1-aziridinylpropionate) (trimethylolpropane-tris[3-(aziridin-1-yl)propionate]), trimethylolpropane-tris[2-methyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2-ethyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2-butyl-(1-aziridinyl)]propionate), trimethylolpropane-tris[2-propyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2-pentyl-(1-aziridinyl)]propionate, trimethylol Examples include propane-tris[2-hexyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2,3-dimethyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2,3-diethyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2,3-dibutyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2,3-dipropyl-(1-aziridinyl)]propionate, trimethylolpropane-tris[2,3-dipentyl-(1-aziridinyl)]propionate, and trimethylolpropane-tris[2,3-dihexyl-(1-aziridinyl)]propionate.

[0120] Formula (1) (X = C1-3 hydroxyalkyl group) is, for example, tetramethylolmethane-tris(1-aziridinylpropionate), tetramethylolmethane-tris[2-methyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2-ethyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2-butyl-(1-aziridinyl)]propionate), tetramethylolmethane-tris[2-propyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2-pentyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2-hexyl-( Examples include 1-aziridinyl)propionate, tetramethylolmethane-tris[2,3-dimethyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2,3-diethyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2,3-dibutyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2,3-dipropyl-(1-aziridinyl)]propionate, tetramethylolmethane-tris[2,3-dipentyl-(1-aziridinyl)]propionate, and tetramethylolmethane-tris[2,3-dihexyl-(1-aziridinyl)]propionate.

[0121] Examples of tetrafunctional aziridine compounds include the following formula (2), tetraaziridinylmetoxylendiamine, tetraaziridinylmethylparaxylenediamine, and tetramethylpropanetetraaziridinylpropionate. [ka] (In formula (2), R 1 ~R 2 Each of these independently represents a hydrogen atom or a C1-6 alkyl group. 3 (This represents a hydrogen atom or a methyl group.)

[0122] Formula (2) is, for example, pentaerythritol-tetra(1-aziridinylpropionate), pentaerythritol-tetra[2-methyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2-ethyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2-butyl-(1-aziridinyl)]propionate), pentaerythritol-tetra[2-propyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2-pentyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2-hexyl-(1-aziridinyl)] Examples include ]propionate, pentaerythritol-tetra[2,3-dimethyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2,3-diethyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2,3-dibutyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2,3-dipropyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2,3-dipentyl-(1-aziridinyl)]propionate, pentaerythritol-tetra[2,3-dihexyl-(1-aziridinyl)]propionate, etc.

[0123] In one embodiment, the polyfunctional aziridine compound is preferably a trifunctional aziridine compound or a tetrafunctional aziridine compound, and more preferably glycerol-tris(1-aziridinylpropionate), trimethylolpropane-tris(1-aziridinylpropionate), tetramethylolmethane-tris(1-aziridinylpropionate), or pentaerythritol-tetra(1-aziridinylpropionate).

[0124] In one embodiment, the amount of aziridinyl groups (of the polyfunctional aziridine compound) is preferably 0.001 mol / g to 0.02 mol / g, and more preferably 0.003 to 0.01. "Amount of aziridinyl groups" refers to the number of moles of aziridinyl groups contained in 1 g of the polyfunctional aziridine compound.

[0125] The molar ratio [number of moles [carboxylate anion group (carboxylate anion group-containing (meth)acrylic resin)] / number of moles [aziridinyl group (polyfunctional aziridine compound)]] is preferably 0.1 to 10, and more preferably 0.3 to 5.

[0126] Examples of mass% content (polyfunctional aziridine compound / coating agent non-volatile content) include 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 35% by mass.

[0127] <Hyperatom-containing organic solvent (molecular weight 61 or higher)> In one embodiment, the coating agent may optionally include a heteroatom-containing organic solvent (molecular weight 61 or higher). The heteroatom-containing organic solvent (molecular weight 61 or higher) may be used alone or in combination of two or more types.

[0128] "Heteroatom-containing organic solvent (molecular weight 61 or higher)" refers to an organic solvent that contains heteroatoms and has a molecular weight of 61 or higher.

[0129] "Organic solvents" refer to organic compounds with a melting point of 30°C or lower at atmospheric pressure.

[0130] Examples of heteroatom-containing organic solvents (molecular weight 61 or higher) include polyol organic solvents, glycol ether organic solvents, ester organic solvents, amide organic solvents, lactam organic solvents, and sulfoxide organic solvents.

[0131] Examples of polyol organic solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, glycerin, and sorbitol.

[0132] Examples of glycol ether organic solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

[0133] Examples of ester organic solvents include ethyl cellosolve acetate and propylene glycol monomethyl ether acetate.

[0134] Examples of amide organic solvents include dimethylformamide and dimethylacetamide.

[0135] Examples of lactam organic solvents include 2-pyrrolidone and N-methyl-2-pyrrolidone.

[0136] Examples of sulfoxide organic solvents include dimethyl sulfoxide.

[0137] In one embodiment, the heteroatom-containing organic solvent (molecular weight 61 or higher) is preferably a polyol organic solvent, an amide organic solvent, a lactam organic solvent, or a sulfoxide organic solvent; more preferably glycerin, ethylene glycol, propylene glycol, sorbitol, N-methyl-2-pyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylacetamide, or dimethyl sulfoxide; and even more preferably N-methyl-2-pyrrolidone, 2-pyrrolidone, or ethylene glycol. The reasons for preference include, for example, improved antistatic properties.

[0138] Examples of molecular weights (heteroatom-containing organic solvents (molecular weight 61 or higher)) include 185, 182, 180, 175, 170, 165, 160, 155, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 99, 95, 92, 90, 87, 85, 80, 78, 76, 75, 73, 70, 65, 62, 6061, etc. In one embodiment, the above molecular weights are preferably 61 to 185, and more preferably 61 to 150.

[0139] In this disclosure, when the term "molecular weight" is used, it refers to either the formula weight or the number-average molecular weight. If the structure of a compound can be uniquely represented by a specific chemical formula (i.e., the molecular weight distribution is 1), the molecular weight refers to the formula weight. On the other hand, if the structure of a compound cannot be uniquely represented by a specific chemical formula (i.e., the molecular weight distribution is greater than 1), the molecular weight refers to the number-average molecular weight.

[0140] Examples of mass% content (heteroatom-containing organic solvent (molecular weight 61 or higher) / coating agent) include 99.9% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 99.9% by mass.

[0141] <Surfactants> In one embodiment, the coating agent may optionally include a surfactant. The surfactant may be used alone or in combination of two or more.

[0142] Examples of surfactants include acetylene-based surfactants, fluorine-based surfactants, and silicone-based surfactants.

[0143] (Acetylene-based surfactant) "Acetylene-based surfactants" refer to surfactants that have a carbon-carbon triple bond.

[0144] In one embodiment, the acetylene-based surfactant is represented by the following structural formula. [ka] (In the formula, R AG1 , R AG2 , R AG3 , R AG4 Each of these independently represents an alkyl group. AG5 , R AG6 (Each of these independently represents either an ethylene group or a propylene group. a and b each independently represent a non-negative integer.)

[0145] Examples of products (acetylene-based surfactants) include Surfinol 104E, 104H, 104A, 104PA, 104S, 420, 440, 465, 485, SE, SE-F; Orfin E1004, E1010, PD-002W, PD-301A, EXP.4001, EXP.4200, EXP.4123, EXP.4300, WE-002, WE-003 (manufactured by Nisshin Chemical Industry Co., Ltd.); Acetylenel E40, E60, E100, E13T, E200 (manufactured by Kawaken Fine Chemical Co., Ltd.), Dynol 604, 607 (manufactured by Evonik), etc.

[0146] Examples of mass% content (acetylene-based surfactant / coating agent non-volatile content) include 5% by mass, 4.5% by mass, 4% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass, 1% by mass, 0.5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 5% by mass.

[0147] (Fluorine-based surfactants) Examples of fluorinated surfactants include anionic fluorine-containing surfactants, cationic fluorine-containing surfactants, amphoteric fluorine-containing surfactants, and nonionic fluorine-containing surfactants.

[0148] Examples of anionic fluorine-containing surfactants include fluorine-containing surfactants containing sodium sulfonate, and fluorine-containing surfactants containing sodium sulfonate and sodium carboxylate.

[0149] Examples of cationic fluorine-containing surfactants include quaternary ammonium salt-containing fluorine-containing surfactants.

[0150] Examples of amphoteric fluorine-containing surfactants include betaine-containing fluorine-containing surfactants.

[0151] Examples of nonionic fluorine-containing surfactants include polyoxyethylene ether-containing fluorine-containing surfactants, oligomers containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, and oligomers containing fluorine-containing groups, hydrophilic groups, lipophilic groups, and UV-reactive groups.

[0152] Examples of products (fluorine-based surfactants) include Futagent 100, 100C, 110, 150, 150CH, 300, 310, 320, 400SW, 251, 212M, 215M, 250, 222F, 245F, 208, FTX-218, DFX-18, 710FL, 710FS, 730LM, 683, 601AD, 601ADH2, 602, 650AC, and 681 (manufactured by Neos Co., Ltd.).

[0153] Examples of mass% content (fluorinated surfactant / coating agent non-volatile content) include 5% by mass, 4.5% by mass, 4% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass, 1% by mass, 0.5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 5% by mass.

[0154] (Silicone-based surfactant) "Silicone-based surfactants" refer to surfactants that have a polydimethylsiloxane skeleton.

[0155] Examples of products (silicone-based surfactants) include BYK-302, 307, 325N, 326, 327, 330, 331, 333, 342, 345, 346, 347, 348, 349, 375, 378, 3450, 3451, 3455, 3456 (manufactured by BYK), Silface SAG503A (manufactured by Nisshin Chemical Industry Co., Ltd.), and others. These are some examples.

[0156] Examples of mass% content (silicone-based surfactant / coating agent non-volatile content) include 5% by mass, 4.5% by mass, 4% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass, 1% by mass, 0.5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 5% by mass.

[0157] <Curing catalyst> In one embodiment, the coating agent may optionally include a curing catalyst. The curing catalyst may be used alone or in combination of two or more types.

[0158] Examples of curing catalysts include acid catalysts.

[0159] Examples of acid catalysts include inorganic acids, organic acids, and thermal acid generators.

[0160] Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

[0161] Examples of organic acids include organic carboxylic acids, organic sulfonic acids, and organic phosphoric acids.

[0162] Examples of organic carboxylic acids include oxalic acid, acetic acid, and formic acid.

[0163] Examples of organic sulfonic acids include methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid.

[0164] Organic phosphates include, for example, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, and phenoxy acid phosphate. Examples include ethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, and the like.

[0165] Examples of thermal acid generators include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts.

[0166] Examples of mass% content (non-volatile content of curing catalyst / coating agent) include 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 10% by mass, and more preferably 0% by mass to 5% by mass.

[0167] When a curing catalyst is included, the coating agent may optionally contain a basic compound. The purpose of this is, for example, to improve the pot life of the coating agent. The basic compound may be used alone or in combination of two or more. Examples of basic compounds include ammonia, primary amines, secondary amines, tertiary amines, alkali metal compounds, and alkaline earth metal compounds. In one embodiment, the basic compound is preferably ammonia, primary amines, secondary amines, and tertiary amines, more preferably ammonia and tertiary amines, and even more preferably ammonia, trimethylamine, triethylamine, and tributylamine.

[0168] <Water> In one embodiment, the coating agent may optionally include water. Water may be used alone or in combination of two or more.

[0169] Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.

[0170] Examples of mass% content (water / coating agent) include 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass. In one embodiment, the above content is preferably 5% by mass to 95% by mass.

[0171] <Hyperatom-containing organic solvent (molecular weight 60 or less)> In one embodiment, the coating agent may optionally include a heteroatom-containing organic solvent (molecular weight 60 or less). The heteroatom-containing organic solvent (molecular weight 60 or less) may be used alone or in combination of two or more.

[0172] Examples of heteroatom-containing organic solvents (molecular weight 60 or less) include monoalcoholic organic solvents.

[0173] Examples of monoalcoholic organic solvents include methanol, ethanol, n-propanol, and isopropanol.

[0174] Examples of mass% content (heteroatom-containing organic solvent (molecular weight 60 or less) / coating agent) include 99.9% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 99.9% by mass.

[0175] <Additives> The above coating agent may optionally contain agents (additives) that do not fall under any of the above categories.

[0176] Examples of additives include defoamers, preservatives, rust inhibitors, pH adjusters, antioxidants, and lubricants.

[0177] In one embodiment, the parts by mass content (additive / coating agent) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0178] In one embodiment, the parts by mass content (additive / carboxylate anion group-containing (meth)acrylic resin) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0179] In one embodiment, the parts by mass content (additive / heteroatom-containing conductive polymer) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0180] In one embodiment, the parts by mass content (additive / polyfunctional aziridine compound) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0181] A coating agent can be manufactured by dispersing and mixing the above agents.

[0182] Dispersion and mixing means include, for example, a stirrer, an emulsifier / disperser, an ultrasonic dispersion device, and the like.

[0183] Applications (antistatic coating agents) include, for example, thermosetting antistatic coating agents.

[0184] [Cured product] This disclosure relates to a cured product of the above-mentioned antistatic coating agent.

[0185] In one embodiment, the cured product may be, for example, a thermosetting product. The curing conditions may be, for example, the conditions described later.

[0186] [Laminates] This disclosure relates to a laminate including the cured product described above.

[0187] In one embodiment, the laminate has a cured product of a water-based release coating agent on one or both sides of the substrate.

[0188] The amount of cured material is preferably 0.01 g / m² 2 ~2g / m 2 Examples include, more preferably, 0.02 g / m 2 ~1g / m 2 These are some examples.

[0189] <Base material> Examples of substrates include polyester, polycarbonate, polystyrene, polyimide, polyolefin, polyepoxy resin, triacetylcellulose resin, ABS resin, AS resin, norbornene-based resin, polyethylene laminated paper, and the like.

[0190] Examples of polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

[0191] Coating methods include, for example, spray coating, roll coating, reverse roll coating, gravure coating, knife coating, bar coating, and dot coating.

[0192] Examples of curing methods include heating.

[0193] Heating methods include, for example, a circulating air dryer. Drying (curing) temperatures include, for example, 90°C to 170°C. Drying times include, for example, 30 seconds to 2 minutes. [Examples]

[0194] The present invention will be specifically described below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only to the claims. Unless otherwise specified below, numerical values ​​such as parts and percentages are based on mass.

[0195] Manufacturing Example 1 In a four-necked flask equipped with a nitrogen gas inlet tube, thermometer, reflux condenser, and stirrer, 10 parts acrylic acid and 90 parts methyl methacrylate were charged, and 200 parts isopropyl alcohol were added to prepare a monomer solution. To the monomer solution, 2.4 parts 2,2'-azobisisobutyronitrile was added as a polymerization initiator. The reaction system was heated to 80°C and radical polymerization was carried out for 8 hours. Then, 14 parts triethylamine and 188 parts deionized water were added to the reaction system, stirred well, and cooled to room temperature to obtain a carboxylate anion group-containing (meth)acrylic resin (20% non-volatile content, 100% neutralization rate).

[0196] Unless otherwise specified, other examples were carried out in the same manner as above, except for the modifications shown in the table below.

[0197] [Table 1] MMA: Methyl methacrylate BA: Butyl acrylate AA: Acrylic acid HEMA: Hydroxyethyl methacrylate Mw: Weight average molecular weight Tg: Glass transition temperature

[0198] The weight-average molecular weight was determined as a polystyrene equivalent value measured by gel permeation chromatography (GPC) under appropriate solvent conditions. Model: Product name "HLC-8220" (manufactured by Tosoh Corporation) Columns: Product name "PLgel MIXED-C" (manufactured by Agilent Technology) x 2 Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Measurement temperature: 40℃ Detector: RI Standard: Monodisperse polystyrene Resin concentration: 0.2%

[0199] The glass transition temperature was calculated using Fox's formula. Fox's formula: 1 / Tg = (Wa / Tga) + (Wb / Tgb) + ... + (Wn / Tgn) Tg: Glass transition temperature (K) of copolymer Wa: Mass % of monomer A Tga: Glass transition temperature (K) of the homopolymer of monomer A Wb: Mass percentage of monomer B Tgb: Glass transition temperature (K) of monomer B homopolymer Wn: Mass percentage of monomer N Tgn: Glass transition temperature (K) of monomer N homopolymer

[0200] Example 1 440 parts of the solution from Production Example 1 (88 parts in terms of non-volatile content), 1000 parts of ORGACON ICP1010 (1.2% by mass aqueous solution of PEDOT / PSS, manufactured by AGFA, equivalent to 12 parts in terms of non-volatile content), 30 parts of trimethylolpropane tris[3-(aziridin-1-yl)propionate] (TMPTAP), 1 part of p-toluenesulfonic acid monohydrate, 1 part of Dynol 607 (acetylene-based surfactant, manufactured by Nisshin Chemical), 7 parts of triethylamine, 7000 parts of deionized water, and 4500 parts of isopropyl alcohol were thoroughly mixed to produce an antistatic coating agent.

[0201] Unless otherwise specified, other examples were carried out in the same manner as above, except for the modifications shown in the table below.

[0202] [Table 2]

[0203] <Manufacturing (Laminates)> The laminate was manufactured under the following conditions. Coating method: Bar coater No. 5 Base material: PET film (product name "Lumirror T60", manufactured by Toray Industries, Inc.) Drying method: Sunny air dryer (120℃, 30 seconds)

[0204] <Curability> The solvent resistance of the cured film was evaluated by rubbing the surface of the laminate with a cotton swab soaked in methyl ethyl ketone and measuring the number of back-and-forth strokes required until the appearance of the cured surface changed. ○: No change in appearance even after rubbing 30 times. △: There is a change in appearance after rubbing 11 to 29 times. ×: There is a change in appearance after rubbing 1 to 10 times.

[0205] <Surface resistivity> The surface resistivity (Ω / □) of the coated surface of the laminate was measured under the following conditions. Resistivity meter: HighLester UP MCP-HT450, UR probe (manufactured by Nitto Seikou Analytech Co., Ltd.) Applied voltage: 10V Temperature: 23℃ Humidity: 50%

[0206] Reference example Reference Example 1 is Example 1. Reference Examples 2 and 3 are variations in which Dynol 607 from Example 1 is replaced with one of the substances listed in the table below. After coating a PET film (product name "Lumirror T60", manufactured by Toray), the surface condition of the coating film was observed.

[0207] [Table 3] Acetylene-based surfactant: Product name "Dynol 607", manufactured by Evonik. Fluorine-based surfactant: Product name "Futergent 212M", manufactured by Neos. Silicone-based surfactant 1: Product name "BYK-333", manufactured by BYK. Silicone-based surfactant 2: Product name "Silface SAG503A", manufactured by Nisshin Chemical Industry Co., Ltd.

[0208] <Coating condition> ○: The coating agent is not repelled. △: Some coating agents show signs of repellency. ×: The entire coating agent is repelled.

Claims

1. An antistatic coating agent, The antistatic coating agent comprises a carboxylate anion group-containing (meth)acrylic resin and a heteroatom-containing conductive polymer. An antistatic coating agent having a mass ratio (the heteroatom-containing conductive polymer / the carboxylate anion group-containing (meth)acrylic resin) of 0.05 to 1.

2. The antistatic coating agent according to claim 1, comprising a polyfunctional aziridine compound.

3. A cured product of the antistatic coating agent according to claim 1 or 2.

4. A laminate comprising the cured product described in claim 3.

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