Water-based coating agents, cured products, and laminates

Abstract

To provide an aqueous coating agent, a cured product and a laminated product.SOLUTION: There is provided an aqueous coating agent which comprises a polymer, a crosslinking agent and water, wherein the polymer contains a (meth)acrylic acid ester unit containing an alkyl group having 12 to 18 carbon atoms and (meth)acrylic acid and / or its salt unit, the content of the (meth)acrylic acid ester unit containing an alkyl group having 12 to 18 carbon atoms is 15 to 80 mass% based on 100 mass% of the polymer and the content of the (meth)acrylic acid unit is 5 to 20 mass% based on 100 mass% of the polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to water-based coating agents, cured products, and laminates. [Background technology]

[0002] Plastic substrates such as ABS, PET, and polycarbonate are used in various industrial products, including electronic devices and automotive parts. To impart functionality to these plastic substrates, surface treatment is carried out using coating agents. In recent years, water-based coating agents have been in demand from the perspective of protecting the global environment. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-017592 [Overview of the project] [Problems that the invention aims to solve]

[0004] The problem that this invention aims to solve is to provide a water-based coating agent for producing laminates with good peelability, water repellency, solvent resistance, and appearance. [Means for solving the problem]

[0005] This disclosure provides the following items: (Item 1) A water-based coating agent, The aforementioned aqueous coating agent comprises a polymer and a crosslinking agent and water. The polymer comprises C12-18 alkyl group-containing (meth)acrylic acid ester units and (meth)acrylic acid and / or salt units thereof. The content of C12-18 alkyl group-containing (meth)acrylic acid ester units relative to 100% by mass of polymer is 15% to 80% by mass. An aqueous coating agent in which the content of (meth)acrylic acid units is 5% to 20% by mass based on 100% by mass of the polymer. (Item 2) The aqueous coating agent according to the above item, comprising a conductive polymer-polyanion complex consisting only of polythiophene and a polymer containing a sulfoanion group. (Item 3) A cured product of the aqueous coating agent according to any one of the above items. (Item 4) A laminate comprising the cured product according to the above item.

[0006] In the present disclosure, the above-described one or more features may be provided in combination in addition to the explicitly stated combinations. [Effect of the Invention]

[0007] By using the aqueous coating agent of the present disclosure, a laminate having good peel strength, water repellency, solvent resistance, and appearance can be produced. [Embodiments for Carrying Out the Invention]

[0008] Throughout the present disclosure, the ranges of numerical values such as physical property values and contents can be appropriately set (for example, selected from the values described in each of the following items). Specifically, when values such as A3, A2, and A1 (where A3 > A2 > A1) are given for a numerical value α, the range of the numerical value α includes 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 less than A2, greater than A2 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, etc.

[0009] As long as the problems to be solved by the present invention are solved, each component, condition, numerical value, etc. are not particularly limited.

[0010] "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.

[0011] "γ ratio (A / B)" refers to the γ ratio calculated using the formula "A ÷ B". Examples of γ ratios include mass ratios and molar ratios.

[0012] "Non-volatile content" refers to the total mass of components other than organic solvents and water. In one embodiment, "non-volatile content of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C and a constant weight is reached.

[0013] "(meth)acrylic" means "acrylic and / or methacrylic". "(meth)acrylate" means "acrylate and / or methacrylate". "(meth)acryloyl" means "acryloyl and / or methacryloyl".

[0014] "C..." means "of the number of carbon atoms." For example, "C1-6 alkyl group" means an alkyl group with 1 to 6 carbon atoms. "C6 alkyl group" means an alkyl group with 6 carbon atoms.

[0015] Examples of alkyl groups include linear alkyl groups, branched alkyl groups, and cycloalkyl groups.

[0016] Examples of linear alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group.

[0017] A "branched alkyl group" refers to a group that does not have a cyclic structure, in which at least one hydrogen atom of a linear alkyl group is substituted by an alkyl group. Examples of branched alkyl groups include i-propyl group, diethylpentyl group, trimethylbutyl group, trimethylpentyl group, and trimethylhexyl group.

[0018] Examples of cycloalkyl groups include monocyclic cycloalkyl groups, crosslinked ring cycloalkyl groups, and fused ring cycloalkyl groups. Furthermore, a group in which at least one hydrogen atom of a cycloalkyl group is substituted by an alkyl group is also considered a cycloalkyl group.

[0019] 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.

[0020] Examples of monocyclic cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl groups.

[0021] Examples of crosslinked ring cycloalkyl groups include tricyclodecyl groups, adamantyl groups, norbornyl groups, and the like.

[0022] Alkyl groups also include combinations of linear alkyl groups, branched alkyl groups, and cycloalkyl groups. Examples of such combinations include cycloalkylalkyl groups.

[0023] 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.)

[0024] Examples of alkylene groups include linear alkylene groups, branched alkylene groups, and cycloalkylene groups.

[0025] Examples of linear alkylene groups include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decamethylene.

[0026] Examples of branched alkylene groups include diethylpentylene group, trimethylbutylene group, trimethylpentylene group, and trimethylhexylene group.

[0027] Examples of cycloalkylene groups include monocyclic cycloalkylene groups, crosslinked ring cycloalkylene groups, and fused ring cycloalkylene groups. Furthermore, one or more hydrogen atoms in the cycloalkylene group may be substituted by a linear or branched alkyl group.

[0028] Examples of monocyclic cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

[0029] Examples of crosslinking ring cycloalkylene groups include tricyclodecylene, adamantylene, and norbornylene groups.

[0030] Examples of fused ring cycloalkylene groups include the bicyclodecylene group.

[0031] Furthermore, alkylene groups include combinations of linear alkylene groups, branched alkylene groups, and cycloalkylene groups. Examples of these combinations include cycloalkylene alkylene groups and alkylenecycloalkylene alkylene groups.

[0032] The alkylene group of a cycloalkylene is represented by the following formula. -R calkylene -Ralkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0033] The alkylene cycloalkylene alkylene group is represented by the following formula. -R alkylene -R calkylene -R alkylene - (In the formula, R calkylene represents a cycloalkylene group. R alkylene represents an alkylene group.)

[0034] The aromatic group (aryl group, arylene group) may or may not be substituted. Examples of the substituent of the aromatic group include an alkyl group, a thioalkyl group, a thioaryl group, a carbonylaryl group, and the like.

[0035] Examples of the aryl group include a monocyclic aryl group, a condensed-ring aryl group, and the like.

[0036] Examples of the monocyclic aryl group include a phenyl group, a tolyl group, a mesityl group, and the like.

[0037] Examples of the condensed-ring aryl group include a naphthyl group, and the like.

[0038] Examples of the arylene group include a monocyclic arylene group, a condensed-ring arylene group, and the like.

[0039] Examples of the monocyclic arylene group include a phenylene group, a tolylene group, and the like.

[0040] Examples of the condensed-ring arylene group include a naphthylene group, and the like.

[0041] [Water-based coating agent: also referred to as coating agent] The present disclosure relates to a water-based coating agent, wherein the water-based coating agent contains a polymer, a crosslinking agent, and water, The polymer comprises C12-18 alkyl group-containing (meth)acrylic acid ester units and (meth)acrylic acid and / or salt units thereof. The content of C12-18 alkyl group-containing (meth)acrylic acid ester units relative to 100% by mass of polymer is 15% to 80% by mass. This invention relates to a water-based coating agent in which the content of (meth)acrylic acid units per 100% by mass of polymer is 5% to 20% by mass.

[0042] <polymer> Polymers can be used individually or in combination of two or more types.

[0043] (C12-18 alkyl group-containing (meth)acrylate ester) C12-18 alkyl group-containing (meth)acrylic acid esters can be used alone or in combination of two or more.

[0044] Examples of C12-18 alkyl group-containing (meth)acrylic acid esters include C12-18 linear alkyl group-containing (meth)acrylic acid esters, C12-18 branched alkyl group-containing (meth)acrylic acid esters, and C12-18 cycloalkyl group-containing (meth)acrylic acid esters.

[0045] Examples of C12-18 alkyl group-containing (meth)acrylic acid esters include lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, and stearyl (meth)acrylate.

[0046] Examples of mass% content (C12-18 alkyl group-containing (meth)acrylic acid ester units / polymer) include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 54% by mass, 52% by mass, 50% by mass, 49% by mass, 47% by mass, 45% by mass, 44% by mass, 42% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, and 15% by mass. In one embodiment, the above content is preferably 15% by mass to 80% by mass, and more preferably 20% by mass to 80% by mass.

[0047] In one embodiment, the mass% content (C12-18 alkyl group-containing (meth)acrylic acid ester units / polymer) is preferably less than 35% by mass. The reason for this preference is, for example, that the cured product becomes colorless and transparent.

[0048] ((meth)acrylic acid and / or its salts) (Meth)acrylic acid and / or its salts may be used alone or in combination of two or more.

[0049] Examples of (meth)acrylic acid salts include organic salts of (meth)acrylic acid and inorganic salts of (meth)acrylic acid.

[0050] Examples of organic salts include organic amine salts.

[0051] Examples of amine salts include primary amine salts, secondary amine salts, and tertiary amine salts.

[0052] Examples of primary amine salts include monoalkylamine salts, monoarylamine salts, and monoalkanolamine salts.

[0053] Examples of monoalkylamine salts include methylamine salts, ethylamine salts, propylamine salts, and butylamine salts.

[0054] Examples of monoarylamine salts include aniline salts, toluidine salts, trimethylaniline salts, anisidine salts, and trifluoromethylaniline salts.

[0055] Examples of monoalkanolamine salts include ethanolamine salts and propanolamine salts.

[0056] Examples of secondary amine salts include dialkylamine salts, diarylamine salts, and diarylanolamine salts.

[0057] Examples of dialkylamine salts include dimethylamine salt, diethylamine salt, dipropylamine salt, dibutylamine salt, methylethylamine salt, ethylpropylamine salt, and propylbutylamine salt.

[0058] Examples of diarylamine salts include diphenylamine salts.

[0059] Examples of dialkanolamine salts include diethanolamine salt, dipropanolamine salt, and ethanolpropanolamine salt.

[0060] Examples of tertiary amine salts include trialkylamine salts, triarylamine salts, dialkylmonoarylamine salts, and trialcanolamine salts.

[0061] Examples of trialkylamine salts include trimethylamine salt, triethylamine salt, tripropylamine salt, tributylamine salt, dimethylethylamine salt, and methylethylpropylamine salt.

[0062] Examples of triarylamine salts include triphenylamine salts.

[0063] Examples of dialkylmonoarylamine salts include dimethylphenylamine salt and diethylphenylamine salt.

[0064] Examples of trialcanolamine salts include triethanolamine salt and trippropanolamine salt.

[0065] Examples of inorganic salts include ammonium salts and alkali metal salts.

[0066] Examples of alkali metal salts include lithium salts, sodium salts, potassium salts, and so on.

[0067] In one embodiment, from the viewpoint of improving substrate adhesion and cured product strength, (meth)acrylic acid and / or its salts are preferably ammonium salts of (meth)acrylic acid and organic amine salts of (meth)acrylic acid.

[0068] Examples of mass% content ((meth)acrylic acid units / polymer) include 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, and 5% by mass. In one embodiment, the above content is preferably 5% by mass to 20% by mass. Note that the mass% content ((meth)acrylic acid units / polymer) does not include the weight of the salt.

[0069] Examples of neutralization rates include 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, and 20%. In one embodiment, the neutralization rate is preferably between 20% and 100%.

[0070] (C1-11 alkyl group-containing (meth)acrylate ester) C1-11 alkyl group-containing (meth)acrylic acid esters can be used alone or in combination of two or more.

[0071] Examples of C1-11 alkyl group-containing (meth)acrylic acid esters include C1-11 linear alkyl group-containing (meth)acrylic acid esters, C1-11 branched alkyl group-containing (meth)acrylic acid esters, and C1-11 cycloalkyl group-containing (meth)acrylic acid esters.

[0072] Examples of C1-11 alkyl group-containing (meth)acrylic acid esters 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.

[0073] Examples of mass% content (C1-11 alkyl group-containing (meth)acrylic acid ester units / polymer) include 60% by mass, 55% by mass, 50% by mass, 49% by mass, 48% by mass, 47% by mass, 46% 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, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 60% by mass, and more preferably 0% by mass to 50% by mass.

[0074] (Hydroxyl group-containing (meth)acrylic monomer) Hydroxyl group-containing (meth)acrylic monomers can be used alone or in combination of two or more.

[0075] Examples of hydroxyl group-containing (meth)acrylic monomers include monomers represented by the following formula. [ka] (In the formula, R 21 R represents a hydrogen atom or a methyl group. 22 NHR 2’ OR 2’ Represents R 2’ (This represents an alkyl group containing a hydroxyl group.)

[0076] A "hydroxyl group-containing alkyl group" refers to an alkyl group in which one or more hydrogen atoms are substituted by hydroxyl groups. Examples of hydroxyl group-containing alkyl groups include hydroxyl group-containing linear alkyl groups, hydroxyl group-containing branched alkyl groups, and hydroxyl group-containing cycloalkyl groups.

[0077] Examples of hydroxyl group-containing (meth)acrylic monomers include hydroxyl group-containing (meth)acrylic esters and hydroxyl group-containing (meth)acrylamides.

[0078] Examples of hydroxyl group-containing (meth)acrylic esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and glycerin mono(meth)acrylate.

[0079] Examples of hydroxyl group-containing (meth)acrylamides include N-(2-hydroxyethyl)(meth)acrylamide, N-(1-methyl-2-hydroxyethyl)(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-(2-hydroxypropyl)(meth)acrylamide.

[0080] Examples of mass% content (hydroxyl group-containing (meth)acrylic monomer units / polymer) include 60% by mass, 55% by mass, 50% by mass, 49% by mass, 48% by mass, 47% by mass, 46% 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, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 60% by mass, and more preferably 0% by mass to 50% by mass.

[0081] (Monomers other than those listed above: also called other monomers) The polymer may optionally contain monomer units other than those described above (other monomers). Other monomers may be used alone or in combination of two or more. In this disclosure, "other monomers" means monomers that do not fall under any of the following categories: C12-18 alkyl group-containing (meth)acrylic acid esters, (meth)acrylic acid and / or salts thereof, C1-11 alkyl group-containing (meth)acrylic acid esters, or hydroxyl group-containing (meth)acrylic monomers.

[0082] Other monomers include, for example, C19 or higher alkyl group-containing (meth)acrylic acid esters, styrene, alkenyl (meth)acrylates, (meth)acrylamides, (meth)acrylonitriles, and polyfunctional (meth)acrylates.

[0083] Examples of mass percentage content (other monomer units / polymer) include less than 10% by mass, less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.1% by mass, 0% by mass, etc.

[0084] Mass% (other monomer units / any one of the following: C12-18 alkyl group-containing (meth)acrylic acid ester, (meth)acrylic acid and / or its salt, C1-11 alkyl group-containing (meth)acrylic acid ester, or hydroxyl group-containing (meth)acrylic monomer) can be, for example, less than 10% by mass, less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.1% by mass, 0% by mass, etc.

[0085] Examples of molar percentage content (other monomer units / polymers) include less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, etc.

[0086] Mole percent (other monomer units / any one of the following: C12-18 alkyl group-containing (meth)acrylic acid ester, (meth)acrylic acid and / or its salt, C1-11 alkyl group-containing (meth)acrylic acid ester, or hydroxyl group-containing (meth)acrylic monomer) can be, for example, less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, etc.

[0087] (Polymer properties) Examples of number-average molecular weights (polymers) include 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, and 5,000. In one embodiment, the above number-average molecular weight is preferably 5,000 to 50,000.

[0088] Examples of weight-average molecular weights (polymers) include 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, and 20,000. In one embodiment, the above weight-average molecular weight is preferably between 20,000 and 100,000.

[0089] Examples of measurement conditions for weight-average molecular weight and number-average molecular weight include the following: • Measuring instrument: GPC (model number: HLC-8420) manufactured by Tosoh Corporation • Columns: Product name "PLgel MIXED-C" (manufactured by Agilent Technology) x 2 ·Eluent:THF Column temperature: 40°C Calibration curve: Monodisperse polystyrene • Detector: RI • Polymer concentration: 0.2% by mass • Measurement method: Measurement after filter filtration.

[0090] Examples of glass transition temperatures (Tg) for polymers include 80°C, 78°C, 77°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, 0°C, -5°C, -8°C, and -10°C. In one embodiment, the glass transition temperature is preferably between -10°C and 80°C.

[0091] 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

[0092] Examples of hydroxyl values ​​(polymers) include 300 mg KOH / g, 275 mg KOH / g, 250 mg KOH / g, 225 mg KOH / g, 200 mg KOH / g, 175 mg KOH / g, 150 mg KOH / g, 125 mg KOH / g, 100 mg KOH / g, 90 mg KOH / g, 75 mg KOH / g, 50 mg KOH / g, and so on. In one embodiment, the above hydroxyl values ​​are preferably 50 mg KOH / g to 300 mg KOH / g.

[0093] The hydroxyl value is measured by a method compliant with JIS K0070 (neutralization titration method).

[0094] When the amount of monomer used in polymer production can be accurately determined and the polymerization rate is high, the hydroxyl value can be calculated using the following formula. Hydroxyl value = [(Total amount of hydroxyl group-containing monomers in 1g of total monomers × Number of hydroxyl groups in one molecule of hydroxyl group-containing monomer) / Molecular weight of hydroxyl group-containing monomer] × 56.11 (Molecular weight of KOH) × 1000...(1)

[0095] Examples of acid values ​​(unneutralized polymer) include 160 mg KOH / g, 150 mg KOH / g, 140 mg KOH / g, 130 mg KOH / g, 120 mg KOH / g, 110 mg KOH / g, 100 mg KOH / g, 90 mg KOH / g, 80 mg KOH / g, 70 mg KOH / g, 60 mg KOH / g, 50 mg KOH / g, 40 mg KOH / g, 35 mg KOH / g, and the like. In one embodiment, the above acid values ​​are preferably 35 mg KOH / g to 160 mg KOH / g.

[0096] The acid value is measured according to the method compliant with JIS K0070 (neutralization titration method).

[0097] When the amount of monomer used in polymer production can be accurately determined and the polymerization rate is high, the acid value can be calculated using the following formula. Acid value = [(Mass of carboxyl group-containing monomers in 1g of total monomers × Number of carboxyl groups in one molecule of carboxyl group-containing monomer) / Molecular weight of carboxyl group-containing monomer] × 56.11 (Molecular weight of KOH) × 1000...(1)

[0098] (Method for producing polymers) Examples of polymer manufacturing methods include radical polymerization.

[0099] Examples of radical polymerization initiators include inorganic peroxides, organic peroxides, and azo compounds. Radical polymerization initiators can be used alone or in combination of two or more.

[0100] Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, and potassium persulfate.

[0101] Examples of organic peroxides include benzoyl peroxide, dicumyl peroxide, and lauryl peroxide.

[0102] Examples of azo compounds include 2,2'-azobisisobutyronitrile and dimethyl-2,2'-azobisisobutyrate.

[0103] The amount used (radical polymerization initiator / total monomer components) is preferably 0.1 to 5 parts by mass.

[0104] In polymer manufacturing, chain transfer agents may be used as optional. Chain transfer agents may be used alone or in combination of two or more.

[0105] Examples of chain transfer agents include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer.

[0106] The amount used (chain transfer agent / total monomer components) is preferably 0 to 5 parts by mass.

[0107] Examples of mass percentage content (polymer / coating agent non-volatile content) include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, and 50% by mass. In one embodiment, the above content is preferably 50% by mass to 80% by mass.

[0108] <Crosslinking agent> Crosslinking agents can be used alone or in combination of two or more types.

[0109] Examples of crosslinking agents include aziridine crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, and isocyanate crosslinking agents.

[0110] Examples of mass percentage content (non-volatile content of crosslinking agent / coating agent) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 20% by mass. In one embodiment, the above content is preferably 20% by mass to 50% by mass.

[0111] (Aziridine crosslinking agent) Aziridine crosslinking agents can be used alone or in combination of two or more.

[0112] "Aziridine crosslinking agent" refers to a compound having two or more aziridinyl groups.

[0113] Examples of aziridinyl groups include the group represented by the following formula (1). [ka] (In formula (1), R 1 and R 2 R represents a hydrogen atom or a C1-6 alkyl group. 1 and R 2 (They may be different.)

[0114] Examples of aziridine crosslinking agents include difunctional aziridine compounds, trifunctional aziridine compounds, and tetrafunctional aziridine compounds.

[0115] Examples of bifunctional aziridine compounds include neopentyl glycol di(β-aziridinylpropionate).

[0116] Examples of trifunctional aziridine compounds include the compound represented by the following formula (2), glycerol-tris[3-(1-aziridinyl)propionate], 2,4,6-tris(1-aziridinyl)-1,3,5-triazine, 2,4,6-tris[2-methyl-(1-aziridinyl)]-1,3,5-triazine, and tri-(1-aziridinyl)phosphine oxide. [ka] (In formula (2), X represents a C1-6 alkyl group or a hydroxyl group-containing C1-3 alkyl group. 1 and R 2 R represents a hydrogen atom or a C1-6 alkyl group. 1 and R 2 They may be different. 3 (This represents a hydrogen atom or a methyl group.)

[0117] When X is a C1-6 alkyl group, the compound of formula (2) is, for example, trimethylolpropane-tris[3-(1-aziridinyl)propionate], trimethylolpropane-tris[3-(1-(2-methyl)aziridinylpropionate)], trimethylolpropane-tris[3-(1-(2-ethyl)aziridinylpropionate)], trimethylolpropane- Tris[3-(1-(2-propyl)aziridinylpropionate)], Trimethylolpropane-Tris[3-(1-(2-butyl)aziridinylpropionate)], Trimethylolpropane-Tris[3-(1-(2-pentyl)aziridinylpropionate)], Trimethylolpropane-Tris[3-(1-(2-hexyl)aziridinylpropionate)], Trimethylolpropane-tris[3-(1-(2,3-dimethyl)aziridinylpropionate)], trimethylolpropane-tris[3-(1-(2,3-diethyl)aziridinylpropionate)], trimethylolpropane-tris[3-(1-(2,3-diethyl)aziridinylpropionate)], trimethylolpropane-tris[3-(1-(2,3-diethyl)aziridinylpropionate)], trimethylolpropane-tris[3-(1-(2,3-diethyl) Examples include (ropil)aziridinylpropionate), trimethylolpropane-tris[3-(1-(2,3-dibutyl)aziridinylpropionate)], trimethylolpropane-tris[3-(1-(2,3-dipentyl)aziridinylpropionate)], and trimethylolpropane-tris[3-(1-(2,3-hexyl)aziridinylpropionate)].

[0118] When X is a C1-3 hydroxyalkyl group, the compounds of formula (2) are, for example, pentaerythritol-tris[3-(1-aziridinyl)propionate], pentaerythritol-tris[3-(1-(2-methyl)aziridinylpropionate)], pentaerythritol-tris[3-(1-(2-ethyl)aziridinylpropionate)], pentaerythritol-tris[3-(1-(2-propyl)aziridinylpropionate)], pentaerythritol-tris[3-(1-(2-butyl)aziridinylpropionate)], pentaerythritol-tris[3-(1-(2-pentyl)aziridinylpropionate)], and pentaerythritol-tris[3-(1-(2-hexyl)aziridinylpropionate)]. Pentaerythritol-Tris[3-(1-(2,3-dimethyl)aziridinylpropionate)], Pentaerythritol-Tris[3-(1-(2,3-diethyl)aziridinylpropionate)], Pentaerythritol-Tris[3-(1-(2,3-diethyl)aziridinylpropionate)], Pentaerythritol-Tris[3-(1-(2,3-diethyl)aziridinylpropionate)], Pentaerythritol-Tris[3-(1-(2,3-diethyl) Examples include (Ropil)aziridinylpropionate), pentaerythritol-tris[3-(1-(2,3-dibutyl)aziridinylpropionate)], pentaerythritol-tris[3-(1-(2,3-dipentyl)aziridinylpropionate)], and pentaerythritol-tris[3-(1-(2,3-hexyl)aziridinylpropionate)].

[0119] Examples of tetrafunctional aziridine compounds include the compound represented by the following formula (3), tetraaziridinyl metaxylenediamine, tetraaziridinyl methyl paraxylenediamine, and the like.

[0120] [ka] (In formula (3), R 1 and R 2 R represents a hydrogen atom or a C1-6 alkyl group. 1 and R 2 They may be different. 3(This represents a hydrogen atom or a methyl group.)

[0121] Examples of compounds represented by formula (3) include pentaerythritol-tetra(1-aziridinylpropionate), pentaerythritol-tetra[2-hexyl-(1-aziridinyl)propionate], and pentaerythritol-tetra[2,3-dihexyl-(1-aziridinyl)propionate].

[0122] Examples of mass% content (aziridine crosslinking agent / coating agent nonvolatile content) 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, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 50% by mass.

[0123] (Melamine crosslinking agent) Melamine crosslinking agents can be used alone or in combination of two or more.

[0124] Examples of melamine crosslinking agents include melamine resins containing constituent units derived from the following melamine compounds. [ka] (In the formula, R m1 ~R m6 Each of these is independently selected from a hydrogen atom, a methylol group, a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, and an isobutoxymethyl group.

[0125] In one embodiment, the average degree of polymerization of the melamine resin is preferably 1.1 to 10.

[0126] The melamine resin is preferably a methylated melamine resin or a butylated melamine resin, and more preferably a full-ether type methylated melamine resin, a full-ether type butylated melamine resin, or a full-ether type methyl-butylated melamine resin.

[0127] "Methylated melamine" is the above R m1 ~R m6 This refers to a melamine compound in which at least one of the groups is a methoxymethyl group. "Full ether-type methylated melamine" is defined as above R m1 ~R m6 This refers to a melamine compound in which all components are methoxymethyl groups. "Methylated melamine resin" refers to a resin composed solely of structural units derived from methylated melamine. "Full ether type methylated melamine resin" refers to a resin composed solely of structural units derived from full ether type methylated melamine.

[0128] "Butylated melamine" is the above R m1 ~R m6 This refers to a melamine compound in which at least one of the following groups is either an n-butoxymethyl group or an isobutoxymethyl group. "Full ether-type butylated melamine" refers to the above R m1 ~R m6 This refers to melamine compounds in which all of the groups are either n-butoxymethyl groups or isobutoxymethyl groups. "Butylated melamine resin" refers to a resin composed solely of structural units derived from butylated melamine. "Full ether type butylated melamine resin" refers to a resin composed solely of structural units derived from full ether type butylated melamine.

[0129] "Full ether-type methyl-butylated melamine" is the above R m1 ~R m6 This refers to a melamine compound in which at least one of the groups is a methoxymethyl group, and the remaining groups are either n-butoxymethyl groups or isobutoxymethyl groups. "Full ether-type methyl-butylated melamine resin" refers to a resin composed solely of structural units derived from full ether-type methyl-butylated melamine.

[0130] Commercially available melamine resin products include, for example, Cymel 300, Cymel 301, Cymel 303LF, Cymel 350, Cymel 370N, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, Cymel 701, Cymel 266, Cymel 267, Cymel 285, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 272, Cymel 212, Cymel 253, and Mel 254, Saimel 202, Saimel 207, Mycoat 506 (all manufactured by Ornex Japan Co., Ltd.), Nikarac MW-30M, Nikarac MW-30, Nikarac MW-30HM, Nikarac MW-390, Nikarac MW-100LM, Nikarac MX-750LM, Nikarac MW-22, Nikarac MS-21, Nikarac MS-11, Nikarac MW-24X, Nikarac MS-001, Nikarac MX- 002, Nikarac MX-730, Nikarac MX-750, Nikarac MX-708, Nikarac MX-706, Nikarac MX-042, Nikarac MX-035, Nikarac MX-45, Nikarac MX-43, Nikarac MX-417, Nikarac MX-410 (all manufactured by Sanwa Chemical Co., Ltd.), Uban 20SB, Uban 20SE60, Uban 21R, Uban 22R, Uban 122, Uban 125, Examples include Yuban 220, Yuban 225, Yuban 228, Yuban 2020 (all manufactured by Mitsui Chemicals, Inc.), Amidia J-820-60, Amidia L-109-65, Amidia L-117-60, Amidia L-127-60, Amidia 13-548, Amidia G-821-60, Amidia L-110-60, Amidia L-125-60, Amidia L-166-60B (all manufactured by DIC Corporation).

[0131] Examples of mass% content (melamine crosslinking agent / coating agent nonvolatile content) 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, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 50% by mass.

[0132] (Oxazoline crosslinking agent) Oxazoline crosslinking agents can be used alone or in combination of two or more.

[0133] Examples of oxazoline crosslinking agents include oxazoline oligomer crosslinking agents and oxazoline polymer crosslinking agents.

[0134] Examples of oxazoline oligomer crosslinking agents include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), 2,2'-octamethylene-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolidinylcyclohexane) sulfide, and bis(2-oxazolidinylnorbornane) sulfide.

[0135] Examples of oxazoline polymer crosslinking agents include polymers of oxazoline containing carbon-carbon double bonds.

[0136] Examples of carbon-carbon double bond-containing oxazolines include 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, and 2-vinyl-4-methyl-2-oxazoline.

[0137] Examples of commercially available oxazoline crosslinking agents include Epocross WS-300, WS-500, and WS-700 (manufactured by Nippon Shokubai Co., Ltd.).

[0138] Examples of mass% content (oxazoline crosslinking agent / coating agent nonvolatile content) 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, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 50% by mass.

[0139] (Carbodiimide crosslinking agent) Carbodiimide crosslinking agents can be used alone or in combination of two or more.

[0140] Examples of carbodiimide crosslinking agents include poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(tolylcarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(1,6-hexamethylenecarbodiimide), and poly(1,4-tetramethylaminecarbodiimide). Examples include tramethylenecarbodiimide, poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(1,3,5-triethylphenylenecarbodiimide), poly(4,4'-methylenebiscyclohexylcarbodiimide), poly(1,3-diisopropylphenylenecarbodiimide), poly(1-methyl-3,5-diisopropylphenylenecarbodiimide), and poly(isopropylphenylenecarbodiimide).

[0141] Examples of mass% content (non-volatile content of carbodiimide crosslinking agent / coating agent) 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, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 50% by mass.

[0142] (Isocyanate crosslinking agent) Isocyanate crosslinking agents can be used alone or in combination of two or more.

[0143] Examples of isocyanate crosslinking agents include polyisocyanates.

[0144] "Polyisocyanate" refers to a compound having two or more isocyanate groups (-N=C=O).

[0145] Examples of polyisocyanates include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biuret, isocyanurate, allophanate, and adduct derivatives.

[0146] Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethyl diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0147] Examples of branched aliphatic polyisocyanates include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0148] Examples of alicyclic polyisocyanates include monocyclic alicyclic polyisocyanates, crosslinked cyclic alicyclic polyisocyanates, and condensed cyclic alicyclic polyisocyanates.

[0149] Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0150] Examples of cross-linked alicyclic polyisocyanates include tricyclodecile diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0151] Examples of condensed alicyclic polyisocyanates include bicyclodecile diisocyanate.

[0152] Examples of aromatic polyisocyanates include monocyclic aromatic polyisocyanates and fused-ring aromatic polyisocyanates.

[0153] Examples of monocyclic aromatic polyisocyanates include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyli isocyanate, 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0154] Examples of condensed ring aromatic polyisocyanates include 1,5-naphthylene diisocyanate.

[0155] Blocked isocyanates may also be used. A "blocked isocyanate" refers to a compound in which the isocyanate group of a polyisocyanate is protected with a blocking agent.

[0156] Examples of mass% content (isocyanate crosslinking agent / coating agent nonvolatile content) 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, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 50% by mass.

[0157] <Water> Water can be used alone or in combination of two or more elements.

[0158] Examples of water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.

[0159] Examples of mass% content (water / coating agent) include 99.9% by mass, 99.5% by mass, 98% 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, and so on. In one embodiment, the above content is preferably 40% by mass to 99.9% by mass, and more preferably 40% by mass to 80% by mass.

[0160] Examples of mass% content (water / total solvent) include 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, and 10% by mass. In one embodiment, the above content is preferably 10% by mass to 90% by mass.

[0161] <Conductive polymer-polyanion complex> The coating agent may optionally include a conductive polymer-polyanion complex consisting solely of polythiophene and a sulfoanion group-containing polymer. The conductive polymer-polyanion complex may be used alone or in combination of two or more types.

[0162] Examples of polythiophenes include poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(3,4-butenedioxythiophene).

[0163] Examples of polymers containing sulfonionic groups include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, ethyl sulfonic acid poly(meth)acrylate, butyl sulfonic acid poly(meth)acrylate, poly-2-(meth)acrylamide-2-methylpropanesulfonic acid, polyisoprene sulfonic acid, and their salts.

[0164] In one embodiment, the conductive polymer-polyanion complex is preferably poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT-PSS) and / or a salt thereof.

[0165] Examples of commercially available PEDOT / PSS products include "Clevios P" (manufactured by Heraeus) and "Orgacon" (manufactured by Agfa-Gevaert Japan Co., Ltd.).

[0166] Examples of mass% content (conductive polymer-polyanion complex / coating agent non-volatile content) include 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 20% by mass.

[0167] <Conductivity enhancer> The coating agent may optionally contain a conductivity enhancer. The conductivity enhancer may be used alone or in combination of two or more types.

[0168] Examples of conductivity enhancers include ethylene glycol, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, glycerin, sorbitol, polyethylene glycol, and the like.

[0169] Examples of the parts by mass content (conductivity improver / conductive polymer) include 1000 parts by mass, 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 100 parts by mass, 90 parts by mass, 80 parts by mass, 70 parts by mass, 60 parts by mass, 50 parts by mass, 40 parts by mass, 30 parts by mass, 20 parts by mass, 10 parts by mass, 0 parts by mass, etc. In one embodiment, the above content is preferably 0 to 1000 parts by mass.

[0170] <Curing catalyst> The coating agent may optionally include a curing catalyst. The curing catalyst may be used alone or in combination of two or more types.

[0171] Examples of curing catalysts include acid catalysts.

[0172] Examples of acid catalysts include inorganic acids, organic acids, and thermal acid generators.

[0173] Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

[0174] Examples of organic acids include organic carboxylic acids, organic sulfonic acids, and organic phosphoric acids.

[0175] Examples of organic carboxylic acids include oxalic acid, acetic acid, and formic acid.

[0176] 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.

[0177] 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.

[0178] Examples of thermal acid generators include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts.

[0179] Examples of mass% content (non-volatile content of curing catalyst / coating agent) include 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 5% by mass.

[0180] <organic solvents> The coating agent may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0181] Examples of organic solvents include alcohol solvents.

[0182] Examples of alcoholic solvents include methanol, ethanol, 1-propanol, isopropanol, and butanol.

[0183] Examples of mass% content (organic solvent / coating agent) include 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 60% by mass.

[0184] Examples of mass% content (organic solvent / total solvent) include 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 90% by mass, and more preferably 10% by mass to 90% by mass.

[0185] Examples of mass percentage content (organic solvents other than alcohol / coating agent) include 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, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 10% by mass.

[0186] Examples of nonvolatile components (coating agent) include 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.5% by mass, 0.2% by mass, and 0.1% by mass. In one embodiment, the nonvolatile components are preferably 0.1% by mass to 20% by mass.

[0187] <Additives> The above coating agent may optionally include an agent (additive) that does not fall under any of the following categories: polymer, crosslinking agent, water, conductive polymer-polyanion complex, curing catalyst, or organic solvent.

[0188] Examples of additives include binders, defoamers, anti-slip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants, leveling agents, polybutadiene, polyisoprene, polychloroprene, polypentadiene, polybutene, polyisobutylene, polystyrene, isoprene-butadiene copolymers, styrene-isoprene copolymers, polyolefins, silicone resins, amines, carboxylic acid anhydrides, and long-chain alkyl group-containing alcohols.

[0189] Examples of the parts by mass content (additive / coating agent) include 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.

[0190] The mass content (additives / any one of the polymer, crosslinking agent, water, conductive polymer-polyanion complex, curing catalyst, or organic solvent) may be, for example, less than 1 mass, less than 0.1 mass, less than 0.01 mass, or 0 mass.

[0191] The coating agent can be manufactured by dispersing and mixing the polymer, crosslinking agent, water, conductive polymer-polyanion complex, curing catalyst, organic solvent, and additives.

[0192] Applications (coating agents) include, for example, water-based peeling coating agents, water-based antiblocking coating agents, water-based antistatic coating agents, water-based thermosetting coating agents, water-based thermosetting peeling coating agents, water-based thermosetting antiblocking coating agents, and water-based thermosetting antistatic coating agents.

[0193] [Cured product] This disclosure relates to a cured product of the aqueous coating agent.

[0194] In one embodiment, the cured product may be, for example, a thermosetting product. The curing conditions may be, for example, the conditions described later.

[0195] [Laminates] This disclosure relates to a laminate including the cured product.

[0196] In one embodiment, the laminate has a cured coating on one or both sides of the substrate.

[0197] The amount of cured material in the laminate is preferably 0.01 g / m². 2 ~10g / m 2 Examples include, more preferably, 0.05 g / m 2 ~5g / m 2 These are some examples.

[0198] <Base material> Examples of substrates include polyester, polycarbonate, polystyrene, polyimide, polyolefin, polyepoxy resin, triacetylcellulose resin, ABS resin, AS resin, norbornene-based resin, and the like.

[0199] Examples of polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

[0200] Coating methods include, for example, spray coating, roll coating, reverse roll coating, gravure coating, knife coating, bar coating, and dot coating.

[0201] Examples of curing methods include heating.

[0202] 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]

[0203] 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.

[0204] Manufacturing Example 1: Polymer Manufacturing A five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was filled with 138 parts of isopropyl alcohol as a solvent and heated to 82°C. 20 parts of stearyl methacrylate, 23 parts of 2-hydroxyethyl methacrylate, 10 parts of acrylic acid, 47 parts of methyl methacrylate, and 0.5 parts of azobisisobutyronitrile as an initiator were added dropwise, and the mixture was incubated at 82°C for 10 hours. After cooling to room temperature, 12 parts of isopropyl alcohol were added to obtain a polymer solution with a non-volatile content of 40%.

[0205] Unless otherwise specified, other examples were carried out in the same manner as above, except for the modifications shown in the table below.

[0206] [Table 1]

[0207] SMA: Stearyl methacrylate LA: Lauryl acrylate LMA: Lauryl methacrylate AA: Acrylic acid MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate

[0208] <Acid value> The acid value was calculated using the following formula. Acid value = [(Mass of carboxyl group-containing monomers in 1g of total monomers × Number of carboxyl groups in one molecule of carboxyl group-containing monomer) / Molecular weight of carboxyl group-containing monomer] × 56.11 (Molecular weight of KOH) × 1000...(1)

[0209] Example 1 A water-based coating agent with a non-volatile content of 0.7% was obtained by mixing 14.4 parts of the polymer solution from Production Example 1, 2.2 parts of a crosslinking agent, 63.3 parts of a conductive polymer, 0.09 parts of a curing catalyst, 0.64 parts of a neutralizing agent, 525 parts of isopropyl alcohol, and 655 parts of water. The water-based coating agents of the Examples and Comparative Examples were coated onto a polyethylene terephthalate film (film thickness 50 μm, Toray Industries, Inc.'s "Lumirror T60") using a bar coater #7 to achieve a theoretical film thickness of 0.1 μm after drying. The coated material was then dried at 120°C for 1 minute to obtain a laminate.

[0210] Unless otherwise specified, other examples were carried out in the same manner as above, except for the modifications shown in the table below.

[0211] [Table 2]

[0212] Ammonia water: 28% ammonia water TEA: Triethylamine Aziridine: Product name "Chemitite PZ-33", manufactured by Nippon Shokubai Co., Ltd., 100% non-volatile content. Melamine: Product name "Cymel 303LF", manufactured by Allnex, 100% non-volatile content. Oxazoline: Product name "Epocross WS-300", manufactured by Nippon Shokubai Co., Ltd., non-volatile content 10% PEDOT-PSS: Product name "ORGACON ICP1010", manufactured by Agfa Materials Japan Co., Ltd., non-volatile content 1.2% EG: Ethylene glycol PTS: Paratoluenesulfonic acid, 100% non-volatile content IPA: Isopropyl alcohol

[0213] <Peeling force> Polyester adhesive tape (Nitto Denko Corporation 31B tape: 25mm wide) was applied to the laminated material using a 2kg roller under pressure, and the material was stored at 23°C for 30 minutes. Next, the tape was pulled at a 180° angle at a peeling speed of 0.3m / min., and the force required to peel it off (mN / 25mm) was measured.

[0214] <Water contact angle> The water contact angle on the laminate surface was measured using a contact angle meter (device name: "Contact Angle Meter LSE-B100W", manufactured by NIC Co., Ltd.) after dropping one drop (approximately 2 μL) of deionized water, and measuring the angle 1 second later. A high contact angle indicates high water repellency.

[0215] <Exterior> The appearance of the water-based coating agent was visually inspected. ○: No aggregates ×: Contains aggregates

[0216] <Solvent resistance> The solvent resistance of the cured film was evaluated by rubbing the surface of the laminate with a cotton swab soaked in ethanol 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. △: Changes in appearance occur after 2 to 29 rubs. ×: There is a change in appearance after rubbing it once.

[0217] Evaluation example: 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 Mitsubishi Chemical Analytech Co., Ltd.) Applied voltage: 100V Temperature: 23℃ Humidity: 50%

[0218] [Table 3]

Claims

1. A water-based coating agent, The aforementioned aqueous coating agent comprises a polymer, a crosslinking agent, and water. The polymer comprises C12-18 alkyl group-containing (meth)acrylic acid ester units and (meth)acrylic acid and / or salt units thereof. The content of C12-18 alkyl group-containing (meth)acrylic acid ester units relative to 100% by mass of polymer is 15% by mass to 80% by mass. The content of (meth)acrylic acid units per 100% by mass of polymer is 5% by mass to 20% by mass. The content of C1-11 alkyl group-containing (meth)acrylic acid ester units relative to 100% by mass of the polymer is less than 5% by mass. The C1-11 alkyl group-containing (meth)acrylic acid ester is a C3-11 cycloalkyl group-containing (meth)acrylic acid ester, The acid value of the aforementioned polymer is 70 mg KOH / g to 160 mg KOH / g. The weight-average molecular weight of the aforementioned polymer is greater than 30,000. The aforementioned crosslinking agent is one or more selected from the group consisting of aziridine crosslinking agents, melamine crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, and isocyanate crosslinking agents. Water-based coating agent.

2. The aqueous coating agent according to claim 1, comprising a conductive polymer-polyanion complex consisting solely of a polythiophene and a sulfoanion group-containing polymer.

3. A water-based coating agent, The aqueous coating agent comprises a polymer, a crosslinking agent, water, and a conductive polymer-polyanion complex consisting only of a polymer containing polythiophene and a sulfoanionic group. The polymer comprises C12-18 alkyl group-containing (meth)acrylic acid ester units and (meth)acrylic acid and / or salt units thereof. The content of C12-18 alkyl group-containing (meth)acrylic acid ester units relative to 100% by mass of polymer is 15% by mass to 80% by mass. The content of (meth)acrylic acid units per 100% by mass of polymer is 5% by mass to 20% by mass. The content of C1-11 alkyl group-containing (meth)acrylic acid ester units relative to 100% by mass of the polymer is less than 5% by mass. The C1-11 alkyl group-containing (meth)acrylic acid ester is a C3-11 cycloalkyl group-containing (meth)acrylic acid ester, The acid value of the polymer is 70 mg KOH / g to 160 mg KOH / g. Water-based coating agent.

4. A cured product of a water-based coating agent according to any one of claims 1 to 3.

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

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