Active energy ray-curable resin composition, cured product, and laminate

Abstract

An active energy ray-curable resin composition containing a quaternary ammonium salt-containing polymer and a phosphoric acid ester and / or a salt of which the anion contains a polyoxyalkylene structure, the active energy ray-curable resin composition being characterized in that when the active energy ray-curable resin composition contains the phosphoric acid ester, the content of the quaternary ammonium salt-containing polymer is less than the content of the quaternary ammonium salt-containing polymer, and the content of the quaternary ammonium salt-containing polymer is less than the content of the polyoxyalkylene structure. The acid value of the active energy ray-curable resin composition is from 400 mgKOH / g to 600 mgKOH / g.

Description

Technical Field

[0001] The present disclosure relates to an active energy ray-curable resin composition, a cured product, and a laminate. Background Art

[0002] When an active energy ray-curable resin composition is used for flat panel displays, good antistatic properties are required in order to prevent malfunctions due to static electricity during assembly and operation of the display and to achieve high-definition images. [Prior art literature] [Patent Document]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-112630 Summary of the invention [Problems to be solved by the invention]

[0004] The problem to be solved by the present invention is to provide an active energy ray-curable composition for producing a cured product having good antistatic properties. [Technical means to solve the problem]

[0005] The present inventors have found that the above-mentioned problems can be solved by using specific components.

[0006] According to the present disclosure, the following items are provided. (Item 1) An active energy ray-curable resin composition, The active energy ray-curable resin composition comprises: a polymer containing a quaternary ammonium salt and a phosphate ester and / or salt, The anion of the salt includes a polyoxyalkylene structure, and when the active energy ray-curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray-curable resin composition is 400 mgKOH / g to 600 mgKOH / g. (Item 2) The active energy ray-curable resin composition according to the above item contains urethane poly(meth)acrylate. (Item 3) A cured product of the active energy ray-curable resin composition according to any one of the above items. (Item 4) A laminate comprising the cured product described in the above item. (Project A1) An active energy ray-curable resin composition, The active energy ray-curable resin composition comprises: a polymer containing a quaternary ammonium salt and a phosphate ester, The active energy ray-curable resin composition has an acid value of 400 mgKOH / g to 600 mgKOH / g. (Project A2) The active energy ray-curable resin composition according to the above item, wherein the quaternary ammonium salt-containing polymer comprises structural unit (1), structural unit (2) and structural unit (3), The structural unit (1) is derived from a monomer containing a quaternary ammonium salt, The structural unit (2) is derived from the following compound α, A-B-(C) n -D (A represents a (meth)acryloyloxy group. B represents a single bond or an alkylene group. C represents -O-C(=O)CH2CH2CH2CH2CH2- or an oxyalkylene group. D represents a hydroxyl group, an alkoxy group or an alkyl group. n represents an integer greater than 1.) The structural unit (3) is derived from an alkyl (meth)acrylate. (Item A3) The active energy ray-curable resin composition according to any one of the above items, wherein a non-volatile component mass ratio (the phosphoric acid ester / the quaternary ammonium salt-containing polymer) is 0.1 to 0.7. (Item A4) The active energy ray-curable resin composition according to any one of the above items, wherein the active energy ray-curable resin composition contains (poly)pentaerythritol poly(meth)acrylate and / or urethane poly(meth)acrylate having (poly)pentaerythritol poly(meth)acrylate as a structural unit. (Item A5) A cured product of the active energy ray-curable resin composition according to any one of the above items. (Item A6) A laminate comprising the cured product described in the above item. (Item B1) An active energy ray-curable resin composition, The active energy ray-curable resin composition comprises: a polymer containing a quaternary ammonium salt and a salt, The anion of the salt comprises a polyoxyalkylene structure. (Item B2) The active energy ray-curable resin composition according to the above item contains urethane poly(meth)acrylate. (Item B3) A cured product of the active energy ray-curable resin composition according to any one of the above items. (Item B4) A laminate comprising the cured product according to the above item.

[0007] In the present disclosure, with respect to one or more features described above, in addition to the combinations explicitly shown, further combinations may be provided. [Effects of the Invention]

[0008] By using the active energy ray-curable resin composition of the present disclosure, a cured product having excellent antistatic properties can be produced. DETAILED DESCRIPTION

[0009] In the whole of the present disclosure, the range of the numerical values ​​of each physical property value, content, etc. can be set appropriately (for example, selected from the values ​​described in the following items). Specifically, when the numerical value α is exemplified as A3, A2, and A1 (set as A3>A2>A1), the range of the numerical value α includes, for example, less than A3, less than A2, less than A3, less than A2, more than A1, more than A2, greater than A1, greater than A2, A1-A2 (more than A1 and less than A2), A1-A3, A2-A3, more than A1 and less than A3, more than A1 and less than A2, more than A2 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 less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A3, greater than A2 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 less than A3, greater than A1 and less than A2, greater than A2 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, etc.

[0010] As long as the problem to be solved by the present invention can be solved, components, conditions, numerical values, etc. are not limited to those described in the specification.

[0011] "αβ amount (A / B)" refers to the β amount (α) of A relative to B100α. Examples of α include mass %, mole %, and parts by mass. Examples of β amount include content and usage amount. Examples of αβ amount include mass % content.

[0012] "γ ratio (A / B)" refers to the γ ratio calculated by the formula "A÷B". Examples of the γ ratio include mass ratio and molar ratio.

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

[0014] “(Meth)acrylic acid” means “at least one selected from the group consisting of acrylic acid and methacrylic acid”. “(Meth)acrylate” means “at least one selected from the group consisting of acrylate and methacrylate”. “(Meth)acryloyl” means “at least one selected from the group consisting of acryloyl and methacryloyl”.

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

[0016] [Active energy ray-curable resin composition: composition] The present invention relates to an active energy ray-curable resin composition. The active energy ray-curable resin composition comprises: a polymer containing a quaternary ammonium salt and a phosphate ester and / or salt, The anion of the salt includes a polyoxyalkylene structure, and when the active energy ray-curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray-curable resin composition is 400 mgKOH / g to 600 mgKOH / g.

[0017] <Quaternary ammonium salt-containing polymer: polymer> The quaternary ammonium salt-containing polymer may be used alone or in combination of two or more.

[0018] In one embodiment, the polymer containing a quaternary ammonium salt comprises a structural unit (1), a structural unit (2) and a structural unit (3), wherein the structural unit (1) is derived from a monomer containing a quaternary ammonium salt, The structural unit (2) is derived from the following compound α, A-B-(C) n -D (A represents a (meth)acryloyloxy group. B represents a single bond or an alkylene group. C represents -O-C(=O)CH2CH2CH2CH2CH2- or an oxyalkylene group. D represents a hydroxyl group, an alkoxy group or an alkyl group. n represents an integer greater than 1.) The structural unit (3) is derived from an alkyl (meth)acrylate.

[0019] (Structural unit (1)) The quaternary ammonium salt-containing monomer may be used alone or in combination of two or more.

[0020] Examples of the quaternary ammonium salt-containing monomer include (meth)acrylates represented by the following formula. [CH2=C(R 1 )-C(=O)-A-B-N + (R 2 )(R 3 )(R 4 )] n ·X n－ (Where R 1 Represents H or CH3. 2 ~R 4 Each independently represents a C1-4 alkyl group. A represents O or NH. B represents a C1-3 alkylene group.－ represents an anion. n represents an integer greater than 1. )

[0021] Examples of the C1-4 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0022] Examples of the C1-3 alkylene group include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

[0023] X n－ For example, halogen ions and sulfur-containing ions are mentioned.

[0024] Examples of the halogen ion include a fluoride ion, a chloride ion, a bromide ion, and an iodine ion.

[0025] Sulfur-containing ions include sulfate ions, sulfite ions, C2H5SO4 － , R S1 -(OR S2 ) s -OSO3 － Etc. R S1 represents an alkyl group or an aryl group. S2 represents an alkylene group. s represents an integer greater than 1.

[0026] R S1 Preferably, an alkyl group is used, and more preferably, a C1-4 alkyl group is used. S2 Preferably, a C2-3 alkylene group is used.

[0027] In one embodiment, X n－ Preferred are chloride ion, R S1 -(OR S2 ) s -OSO3 － .

[0028] Examples of n include 1 and 2. In one embodiment, preferably n is 1.

[0029] Examples of the quaternary ammonium salt-containing monomer (excluding anions) include trimethyl-2-(meth)acryloyloxyethylammonium and (3-(meth)acryloylaminopropyl)trimethylammonium.

[0030] Examples of commercially available products (monomers containing quaternary ammonium salts) include "Light Ester DQ-100" manufactured by Kyoeisha Chemical Co., Ltd., "DMAEA-Q" manufactured by Kojin Co., Ltd., and "Amino Ion RE3000MF" manufactured by Nippon Emulsifier Co., Ltd.

[0031] The mass % content (structural unit (1) / total polymer structural units) includes, for example, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, etc. In one embodiment, the content is preferably 25 mass % to 70 mass %, more preferably 35 mass % to 60 mass %.

[0032] The mole % content (structural unit (1) / total structural units of the polymer) includes 84 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 21 mol%, 20 mol%, 15 mol%, 14 mol%, etc. In one embodiment, the content is preferably 14 mol% to 84 mol%, more preferably 21 mol% to 80 mol%.

[0033] (Structural unit (2)) The compound α may be used alone or in combination of two or more.

[0034] Compound α is represented by the following formula. A-B-(C) n -D (A represents a (meth)acryloyloxy group. B represents a single bond or an alkylene group. C represents -O-C(=O)CH2CH2CH2CH2CH2- or an oxyalkylene group. D represents a hydroxyl group, an alkoxy group or an alkyl group. n represents an integer greater than 1.)

[0035] Examples of the compound α include a lactone ring-opening adduct (C: -O-C(=O)CH2CH2CH2CH2CH2-), a polyalkylene-containing substance (C: oxyalkylene), and the like.

[0036] In compound α, examples of the alkyl group include C1-4 alkyl and the like.

[0037] In compound α, examples of the alkoxy group include C1-18 alkoxy groups.

[0038] Examples of the C1-18 alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-octyloxy, 2-ethylhexyloxy, n-decyloxy, 2-ethyloctyloxy, n-lauryloxy, and n-stearyloxy.

[0039] <Lactone Ring-Opening Adduct> A lactone ring-opening adduct can be produced by using a hydroxyl group-containing vinyl monomer and a lactone and subjecting them to ring-opening addition.

[0040] The hydroxyl group-containing vinyl monomer may be used alone or in combination of two or more. Examples of the hydroxyl group-containing vinyl monomer include hydroxyl group-containing (meth)acrylates and hydroxyl group-containing vinyl monomers.

[0041] Examples of the hydroxyl group-containing (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acrylamide.

[0042] Examples of the hydroxyl group-containing vinyl ether include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and hydroxydiethylene glycol vinyl ether.

[0043] Lactones may be used alone or in combination of two or more. Examples of lactones include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0044] Examples of the weight average molecular weight (lactone ring-opening adduct) include 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3999, 3000, 2000, and 1000. In one embodiment, the weight average molecular weight is preferably 1000 to 10000, more preferably 1000 or more and less than 4000.

[0045] The weight average molecular weight (lactone ring-opening adduct) can be measured under the following conditions. Measuring machine: Product name: "HLC-8220GPC", manufactured by Tosoh Corporation Column: Product name "TSKgel SuperHZ-M", manufactured by Tosoh Corporation Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Sample concentration: 0.5% Standard material: Polystyrene (Standard polystyrene set PStQuick A, B, C manufactured by Tosoh Corporation)

[0046] In the ring-opening addition polymerization process, a catalyst may be optionally used. Examples of the catalyst include inorganic acids, alkali metals, alkyl metal compounds, metal alkoxides, and tin compounds.

[0047] Examples of the inorganic acid include sulfuric acid and phosphoric acid.

[0048] Examples of the alkali metal include lithium, sodium, and potassium.

[0049] Examples of the alkyl metal compound include n-butyl lithium, sec-butyl lithium, tert-butyl lithium and the like.

[0050] Examples of the metal alkoxide include tetrabutoxytitanium and the like.

[0051] Examples of the tin compound include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin mercaptide, and tin octoate.

[0052] In one embodiment, the amount used in parts by mass (catalyst / hydroxyl-containing vinyl monomer and lactone) is preferably 0.01 parts by mass to 10 parts by mass.

[0053] <Polyalkylene-containing substances> Examples of the polyalkylene group-containing substance include hydroxypolyalkylene glycol mono(meth)acrylate and alkoxypolyalkylene glycol mono(meth)acrylate.

[0054] Examples of the hydroxypolyalkylene glycol mono(meth)acrylate include hydroxypolyethylene glycol mono(meth)acrylate and hydroxypolypropylene glycol mono(meth)acrylate.

[0055] Examples of the alkoxypolyalkylene glycol mono(meth)acrylate include methoxypolyalkylene glycol mono(meth)acrylate, ethoxypolyalkylene glycol mono(meth)acrylate, propoxypolyalkylene glycol mono(meth)acrylate, butoxypolyalkylene glycol mono(meth)acrylate, alkoxypolyethylene glycol mono(meth)acrylate, alkoxypolypropylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol mono(meth)acrylate, ethoxypolypropylene glycol mono(meth)acrylate, propoxypolyethylene glycol mono(meth)acrylate, propoxypolypropylene glycol mono(meth)acrylate, butoxypolyethylene glycol mono(meth)acrylate, and butoxypolypropylene glycol mono(meth)acrylate.

[0056] Examples of commercially available products (polyalkylene-containing products) include Brunmer PME-100, PME-200, PME-400, PME-1000, PME-4000, 50POEP-800B, PLE-200, PLE-1300, PSE-1300 (all manufactured by NOF Corporation), Light Esther BC, 130MA, 041MA (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

[0057] The mass % content (structural unit (2) / total polymer structural units) includes, for example, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, etc. In one embodiment, the content is preferably 25 mass % to 60 mass %, more preferably 30 mass % to 55 mass %.

[0058] The mole % content (structural unit (2) / total structural units of the polymer) includes, for example, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 2 mol%, 1 mol%, 0.5 mol%, etc. In one embodiment, the content is preferably 0.5 mol% to 50 mol%, more preferably 1 mol% to 40 mol%.

[0059] (Structural unit (3)) The (meth)acrylic acid alkyl esters may be used alone or in combination of two or more.

[0060] Examples of the alkyl (meth)acrylate include linear alkyl (meth)acrylate, branched alkyl (meth)acrylate, and cycloalkyl (meth)acrylate.

[0061] Examples of the linear alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, and n-hexyl (meth)acrylate.

[0062] Examples of the branched alkyl (meth)acrylate include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 1-methylbutyl (meth)acrylate, 2-methylbutyl (meth)acrylate, 3-methylbutyl (meth)acrylate, 1-ethylpropyl (meth)acrylate, 1,1-dimethylpropyl (meth)acrylate, 1,2-dimethylpropyl (meth)acrylate, and 2,2-dimethylpropyl (meth)acrylate.

[0063] Examples of the cycloalkyl (meth)acrylate include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0064] In one embodiment, as the alkyl (meth)acrylate, preferably, a branched alkyl (meth)acrylate is used, and more preferably, a C3-5 branched alkyl (meth)acrylate is used.

[0065] Examples of the mass % content (structural unit (3) / total polymer structural units) include 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, etc. In one embodiment, the content is preferably 5 to 50 mass %.

[0066] The mole % content (structural unit (3) / total structural units of the polymer) includes, for example, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, etc. In one embodiment, the content is preferably 10 mol% to 80 mol%.

[0067] (Structural unit (4): other structural units) The polymer may optionally contain structural unit (4). "Structural unit (4)" refers to "structural unit derived from other monomers". "Other monomers" refers to monomers other than quaternary ammonium salt-containing monomers, compound α, and (meth) alkyl acrylate. Other monomers may be used alone or in combination of two or more.

[0068] Examples of other monomers include vinyl monomers containing an aromatic ring structure.

[0069] Examples of the aromatic ring structure-containing vinyl monomer include styrene, α-methylstyrene, and 4-methylstyrene.

[0070] Examples of the mass % content (structural unit (4) / total structural units of the polymer) include less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, and 0 mass %.

[0071] Examples of the mol% content (structural unit (4) / total structural units of the polymer) include less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, and 0 mol%.

[0072] Examples of the mass % content (structural unit (4) / any of the structural units (1) to (3)) include less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, and 0 mass %.

[0073] Examples of the mol% content (structural unit (4) / any of the structural units (1) to (3)) include less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, and 0 mol%.

[0074] <Physical properties (polymer)> Examples of the weight average molecular weight (polymer) (Mw) include 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, and 180,000. In one embodiment, the weight average molecular weight is preferably 180,000 to 500,000.

[0075] Examples of the number average molecular weight (polymer) (Mn) include 200,000, 175,000, 150,000, 125,000, 100,000, and 50,000. In one embodiment, the number average molecular weight is preferably 50,000 to 200,000.

[0076] Examples of the molecular weight distribution (polymer) (Mw / Mn) include 5.0, 4.9, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.9, and 1.8. In one embodiment, the molecular weight distribution is preferably 1.8 to 5.0.

[0077] The weight average molecular weight and number average molecular weight (polymer) can be measured under the following conditions. Measuring machine: Product name "HLC-8320GPC", manufactured by Tosoh Corporation Column: Product name "TSKgel G6000PW XL -CP", "TSKgel G3000PW XL -CP", manufactured by Tosoh Corporation Developing solvent: 0.1M NaNO3 and 0.1M acetic acid aqueous solution Flow rate: 0.5mL / min Sample concentration: 0.5g / L Standard substance: Polyethylene oxide (TSKgel Standard Polyethylene Oxide SE - Complete set, manufactured by Tosoh Corporation)

[0078] <Production method (polymer)> Examples of the production method (polymer) include radical polymerization.

[0079] The radical polymerization initiator may be used alone or in combination of two or more. Examples of the radical polymerization initiator include inorganic peroxides, organic peroxides, and azo compounds.

[0080] Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, potassium persulfate, and the like.

[0081] Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, and lauroyl peroxide.

[0082] Examples of the azo compound include 2,2'-azobisisobutyronitrile and dimethyl 2,2'-azobisisobutyrate.

[0083] The amount used (radical polymerization initiator / total monomer components) is preferably about 0.01 parts by mass to 10 parts by mass.

[0084] When producing a polymer, a chain transfer agent may be used optionally. The chain transfer agent may be used alone or in combination of two or more. Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer.

[0085] The usage-amount (chain transfer agent / total monomer components) is preferably about 0 to 10 parts by mass.

[0086] In the case of solution polymerization, examples of the reaction solvent include the following organic solvents.

[0087] The reaction time is preferably 2 hours to 12 hours.

[0088] The polymerization temperature is preferably 70 to 130°C.

[0089] Examples of the mass % content (quaternary ammonium salt-containing polymer / active energy ray-curable resin composition non-volatile component) include 20 mass %, 19 mass %, 17 mass %, 15 mass %, 13 mass %, 11 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 3 mass %, etc. In one embodiment, the content is preferably 3 mass % to 20 mass %.

[0090] <Phosphate ester> In one embodiment, the composition may optionally include a phosphoric acid ester. The phosphoric acid ester may be used alone or in combination of two or more.

[0091] In one embodiment, the phosphate ester is represented by the following formula. (R P ) m -P(=O)(OX) 3－m (wherein, m represents 1, 2 or 3. X represents a hydrogen atom, a metal atom or an ammonium ion. R P represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a polyalkylenealkyl group. )

[0092] Examples of the substituent include a (meth)acryloyloxy group and an alkoxy group.

[0093] Examples of the metal atom include an alkali metal atom and an alkaline earth metal atom.

[0094] Examples of the phosphoric acid monoester include (meth)acryloyloxyalkyl phosphate and (poly)alkyleneoxyalkyl phosphate.

[0095] Examples of the (meth)acryloxyalkyl phosphate include (meth)acryloxyethyl phosphate, (meth)acryloxypropyl phosphate, and (meth)acryloxybutyl phosphate.

[0096] Examples of the (poly)alkyleneoxyalkyl phosphate include ethyleneoxybutyl phosphate and decyl (ethyleneoxydecyl) phosphate.

[0097] Examples of commercially available products (phosphate esters) include Light Esther P-1M and P-2M (Kyoeisha Chemical Co., Ltd.), MP-4 and MP-8 (manufactured by Daihachi Chemical Co., Ltd.), and the like.

[0098] The acid value (phosphate ester) includes, for example, 600 mgKOH / g, 590 mgKOH / g, 580 mgKOH / g, 570 mgKOH / g, 560 mgKOH / g, 550 mgKOH / g, 540 mgKOH / g, 530 mgKOH / g, 520 mgKOH / g, 510 mgKOH / g, 500 mgKOH / g, 490 mgKOH / g, 480 mgKOH / g, 470 mgKOH / g, 460 mgKOH / g, 450 mgKOH / g, 440 mgKOH / g, 430 mgKOH / g, 420 mgKOH / g, 410 mgKOH / g, 400 mgKOH / g, etc. In one embodiment, the acid value preferably includes 400 mgKOH / g to 600 mgKOH / g.

[0099] The mass % content (non-volatile components of the phosphate ester / active energy ray-curable resin composition) includes, for example, 12 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 3 mass %, 1 mass %, 0.9 mass %, 0.5 mass %, 0.3 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 12 mass %, more preferably 0.3 mass % to 12 mass %.

[0100] The non-volatile component mass ratio (phosphate ester / quaternary ammonium salt-containing polymer) is, for example, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0, etc. In one embodiment, the non-volatile component mass ratio (phosphate ester / quaternary ammonium salt-containing polymer) is preferably 0 to 0.7, more preferably 0.1 to 0.7, and even more preferably 0.1 to 0.6. The reason for further preference is, for example, HAZE improvement.

[0101] <Salt: Salt containing a polyalkylene structure> In one embodiment, the composition may optionally include a salt. The salt may be used alone or in combination of two or more.

[0102] "Salt" refers to a compound composed only of anions and cations.

[0103] (Anion) The anion contains a polyoxyalkylene structure.

[0104] A "polyoxyalkylene structure" refers to two or more oxyalkylene structures (-O-C n H 2n -)Continuous structure.

[0105] Examples of the polyoxyalkylene structure include a polyoxyethylene structure and a polyoxypropylene structure.

[0106] In one embodiment, the number of polyoxyalkylene modifications is preferably 2-25, more preferably 5-20.

[0107] Examples of the anion include a polyoxyalkylene structure-containing sulfate ion and a polyoxyalkylene structure-containing phosphate ion.

[0108] In one embodiment, the anion is represented by the following formula. R a1 -(OR a2 ) n -OXO3 － (R a1 represents an alkyl group (for example, a C1-6 alkyl group) or a group containing an unsaturated group. a2 represents an alkylene group (e.g., ethylene group, propylene group). n represents an integer greater than 2. X represents S or P.)

[0109] Examples of the unsaturated group-containing group include the following groups. [Chemistry 1] (R b1 represents an alkyl group. Y represents a single bond or an oxygen atom. R b2 ~R b4 Each independently represents a hydrogen atom or a methyl group. ) [Chemistry 2] (R c1 ~R c3 R each independently represents a hydrogen atom or a methyl group. c4 ~R c7 Each independently represents a hydrogen atom or [Chemistry 3] . )

[0110] (cation) Cations include ammonium ions (NH4 + ), monomers containing quaternary ammonium salts, metal ions, etc.

[0111] Examples of the quaternary ammonium salt-containing monomer include the above-mentioned monomers.

[0112] Examples of the metal ions include alkali metal ions.

[0113] Examples of the alkali metal ion include lithium ion, sodium ion, potassium ion, and the like.

[0114] Examples of salts (anions-cations) include alkyl polyethylene sulfate ion-ammonium ion, alkyl polyethylene sulfate ion-trimethyl-2-(meth)acryloyloxyethylammonium, alkyl polyethylene sulfate ion-(3-(meth)acryloylaminopropyl)trimethylammonium, alkyl polyethylene sulfate ion-sodium ion, alkyl polyethylene phosphate ion-ammonium ion, alkyl polyethylene phosphate ion-trimethyl-2-(meth)acryloyloxyethylammonium, alkyl polyethylene phosphate ion-(3-(meth)acryloylaminopropyl)trimethylammonium, alkyl polyethylene phosphate ion-sodium ion, [Chemistry 4] (In the formula, n1 to n5 each independently represent an integer greater than 2 (e.g., 2 to 25, 5 to 20, etc.) wait.

[0115] Examples of commercially available products (sulfates containing a polyoxyalkylene structure) include AMINOIONE RE3000MF (manufactured by Nippon Emulsifier Co., Ltd.), ADEKA SOAP SR-10 and SR-20 (manufactured by ADEKA Corporation), and Aqualon KH-05, KH-10, AR-10 and AR-20 (manufactured by Dai-ichi Kogyo Co., Ltd.).

[0116] Examples of commercially available products (polyoxyalkylene structure-containing phosphates) include Diesparon PW-36 (manufactured by Kusumoto Chemicals Co., Ltd.).

[0117] The mass % content (non-volatile component of the salt / active energy ray-curable resin composition) includes, for example, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 2 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 50 mass %, more preferably 1 mass % to 50 mass %.

[0118] The content (salt / quaternary ammonium salt-containing polymer) in parts by mass includes, for example, 1667 parts by mass, 1500 parts by mass, 1000 parts by mass, 500 parts by mass, 200 parts by mass, 100 parts by mass, 75 parts by mass, 50 parts by mass, 25 parts by mass, 20 parts by mass, 15 parts by mass, 10 parts by mass, 5 parts by mass, 0 parts by mass, etc. In one embodiment, the content is preferably 0 parts by mass to 1667 parts by mass, more preferably 5 parts by mass to 1667 parts by mass, further preferably 5 parts by mass to 75 parts by mass, and particularly preferably 5 parts by mass to 50 parts by mass. Further preferred reasons and particularly preferred reasons include, for example, improvement of HAZE, etc.

[0119] <Poly (meth)acrylate> In one embodiment, the composition may optionally include a multi-(meth)acrylate. The multi-(meth)acrylate may be used alone or in combination of two or more.

[0120] “Multi (meth)acrylate” refers to a compound having two or more (meth)acryloyl groups.

[0121] Examples of the poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate and urethane poly(meth)acrylate.

[0122] ((Poly)pentaerythritol poly(meth)acrylate) Examples of the (poly)pentaerythritol poly(meth)acrylate include pentaerythritol poly(meth)acrylate and polypentaerythritol poly(meth)acrylate.

[0123] Examples of the pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0124] Examples of the polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate and tripentaerythritol octa(meth)acrylate.

[0125] (Urethane poly(meth)acrylate) Examples of the urethane poly(meth)acrylate include a reaction product of a compound group consisting of a hydroxyl group-containing poly(meth)acrylate and a polyisocyanate.

[0126] <Hydryl-containing poly(meth)acrylate> Examples of the hydroxyl group-containing poly(meth)acrylate include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and (poly)glycerol poly(meth)acrylate.

[0127] The polyisocyanate may be used alone or in combination of two or more.

[0128] <Polyisocyanate> “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0129] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret forms, isocyanurate forms, allophanate forms, and adduct forms thereof.

[0130] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate and decamethylene diisocyanate.

[0131] Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0132] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0133] Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0134] Examples of the bridged alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0135] Examples of the condensed-ring alicyclic polyisocyanate include bicyclodecylene diisocyanate and the like.

[0136] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed-ring aromatic polyisocyanate.

[0137] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethyl-m-xylylene diisocyanate.

[0138] Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate and the like.

[0139] In one embodiment, the urethane poly(meth)acrylate preferably includes a urethane poly(meth)acrylate having a (poly)pentaerythritol poly(meth)acrylate as a structural unit.

[0140] The mass % content (non-volatile component of the multi-(meth)acrylate / active energy ray-curable resin composition) includes, for example, 97 mass %, 95 mass %, 90 mass %, 85 mass %, 80 mass %, 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 97 mass %.

[0141] <Photopolymerization initiator> In one embodiment, the active energy ray-curable composition may optionally include a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0142] Examples of the photopolymerization initiator include an α-hydroxydimethylacetophenone group-containing photopolymerization initiator, α-hydroxyphenylcycloalkyl ketone, α-aminophenylalkyl ketone, benzyl dimethyl ketal, unsubstituted or substituted phenylalkyl ketone, unsubstituted or substituted benzil, unsubstituted or substituted benzophenone, acylphosphine oxide, substituted thioxanthone, and oxime ester.

[0143] Examples of the α-hydroxydimethylacetophenone group-containing photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one.

[0144] Examples of the α-hydroxyphenylcycloalkyl ketone include 1-hydroxycyclohexyl phenyl ketone and the like.

[0145] Examples of α-aminoalkylphenone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one and the like.

[0146] Examples of benzyl dimethyl ketal include 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0147] Examples of the unsubstituted or substituted alkyl phenone include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4′-morpholinobutylphenone, 2-methyl-4′-(methylthio)-2-morpholinopropiophenone, 2-isonitrosopropiophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one.

[0148] Examples of the unsubstituted or substituted benzil include benzil and anisil (p-anisil).

[0149] Examples of the unsubstituted or substituted benzophenone include benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and methyl 2-benzoylbenzoate.

[0150] Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0151] Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0152] Examples of oxime esters include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)] (1,2-oktandione, 1-[4-(fenilthio)-, 2-(o-benziloxime)]) (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one); Ethyl ketone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(ortho Acetyl oxime)(エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-, 1-(O-アセチルオキシム)) (i.e. 1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylene)amino)oxy)ethane-1-one, etc.

[0153] When electron beam curing is performed, no photopolymerization initiator is required.

[0154] The mass % content (photopolymerization initiator / active energy ray-curable resin composition non-volatile component) includes, for example, 15 mass %, 13 mass %, 11 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 3 mass %, 1 mass %, etc. In one embodiment, the content is preferably 0 mass % to 15 mass %, more preferably 1 mass % to 15 mass %.

[0155] <Leveling agent> In one embodiment, the active energy ray-curable composition may optionally include a leveling agent. The leveling agent may be used alone or in combination of two or more.

[0156] Examples of the leveling agent include silicone leveling agents and fluorine leveling agents.

[0157] Examples of the mass % content (leveling agent / active energy ray-curable resin composition non-volatile component) include 10 mass %, 9 mass %, 7 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass %, 0 mass %, etc. In one embodiment, the content is preferably 0 mass % to 10 mass %.

[0158] <Organic solvents> In one embodiment, the active energy ray-curable composition may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0159] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, alkyl halide solvents, and amide solvents.

[0160] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0161] Examples of the aromatic solvent include toluene and xylene.

[0162] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, and butanol.

[0163] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0164] Examples of the glycol ether solvent 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-tert-butyl ether.

[0165] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0166] Examples of the petroleum-based solvent include Solbecso #100 (manufactured by Exxon Corporation) and Solbecso #150 (manufactured by Exxon Corporation).

[0167] Examples of the halogenated alkyl solvent include chloroform and the like.

[0168] Examples of the amide solvent include dimethylformamide.

[0169] The content (organic solvent / active energy ray-curable resin composition non-volatile component) in parts by mass is, for example, 1900 parts by mass, 1750 parts by mass, 1500 parts by mass, 1250 parts by mass, 1000 parts by mass, 500 parts by mass, 100 parts by mass, 75 parts by mass, 50 parts by mass, 25 parts by mass, 10 parts by mass, 0 parts by mass, etc. In one embodiment, the content is preferably 0 parts by mass to 1900 parts by mass, more preferably 10 parts by mass to 1000 parts by mass.

[0170] <Additives> The active energy ray-curable resin composition may optionally contain agents (additives) other than the “quaternary ammonium salt-containing polymer, phosphoric acid ester, (poly) (meth)acrylate, photopolymerization initiator, leveling agent, and organic solvent”.

[0171] Examples of the additives include antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface conditioners, antifouling agents, pigments, metal oxide fine particle dispersions, and organic fine particle dispersions.

[0172] In one embodiment, the mass % content (additive / active energy ray-curable resin composition) is, for example, less than 10 mass %, less than 5 mass %, less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, or 0 mass %.

[0173] In one embodiment, the content by mass (additive / a quaternary ammonium salt-containing polymer, phosphate, (poly) (meth) acrylate, photopolymerization initiator, organic solvent) is, for example, less than 5 mass %, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part, etc.

[0174] The active energy ray-curable resin composition can be produced by dispersing and mixing a quaternary ammonium salt-containing polymer and a phosphoric acid ester and, if necessary, a (poly) (meth) acrylate, a photopolymerization initiator, a leveling agent, an organic solvent, and additives.

[0175] Examples of the dispersing and mixing means include an emulsifying disperser and an ultrasonic dispersing device.

[0176] The acid value (active energy ray-curable resin composition) includes, for example, 600 mgKOH / g, 590 mgKOH / g, 580 mgKOH / g, 570 mgKOH / g, 560 mgKOH / g, 550 mgKOH / g, 540 mgKOH / g, 530 mgKOH / g, 520 mgKOH / g, 510 mgKOH / g, 500 mgKOH / g, 490 mgKOH / g, 480 mgKOH / g. In one embodiment, the acid value is preferably 0 to 600 mgKOH / g, more preferably 400 to 600 mgKOH / g.

[0177] The acid value can be measured under the following conditions. The following conditions are based on JIS K-0070. Reagent A: 0.5 mol / dm 3 Potassium hydroxide ethanol solution Reagent B: Neutralize with reagent A using phenolphthalein indicator just before using toluene ethanol solution (volume ratio: toluene / ethanol = 1 / 1) (1) Measure 1 g of sample without any inorganic acid and place it in a 300 mL Erlenmeyer flask. (2) Add 100 mL of reagent B and a few drops of phenolphthalein indicator to the conical flask and shake thoroughly until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating (warming) in a water bath. (3) The sample solution at room temperature is titrated with reagent A. The neutralization endpoint is determined when the light red color of the phenolphthalein indicator persists for 30 seconds. (4) The acid value was calculated based on the following formula. Acid value = (28.05 × A × f) / SA: Titration amount of reagent A (mL) f: coefficient of reagent A S: Sample collection volume (g) (5) If the color of the reagent is dark, add 20 mL of saturated saline solution to (2). In (3), the neutralization endpoint is considered when the color of the saline solution layer does not disappear within 30 seconds.

[0178] When the composition contains phosphoric acid ester, the transmittance of the cured product of the composition is also good. In addition, a highly polar resin (urethane (meth) acrylate, etc.) can be used for the composition containing phosphoric acid ester.

[0179] When the composition contains a salt, the surface properties of the cured product of the composition are also good, and the liquid compatibility of the composition is also good. In addition, a low-polarity solvent (methyl isobutyl ketone, etc.) can be used for the composition containing a salt.

[0180] Examples of the usage form (active energy ray-curable composition) include an antistatic agent and a coating agent.

[0181] [cured material] The present disclosure relates to a cured product of the active energy ray-curable resin composition.

[0182] Examples of curing conditions include the following conditions.

[0183] [Laminate] The present disclosure relates to a laminate comprising the cured product.

[0184] The laminate is manufactured by various known methods. In one embodiment, the method for manufacturing the laminate includes: a step of applying the composition to at least one side of a substrate (coating step); and a step of irradiating active energy rays to form a cured layer (active energy ray curing step).

[0185] Examples of the substrate include polycarbonate films, acrylic films (polymethyl methacrylate films, etc.), polystyrene films, polyester films, polyolefin films, epoxy resin films, melamine resin films, triacetyl cellulose films, ABS films, AS films, norbornene-based resin films, cyclic olefin films, and polyvinyl alcohol films.

[0186] In one embodiment, the thickness (substrate) is preferably 10 μm to 2000 μm.

[0187] In one embodiment, the thickness (cured material layer) is preferably 0.1 μm to 20 μm.

[0188] (Coating process) Examples of the coating method include rod coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coater coating, offset printing, flexographic printing, and screen printing.

[0189] (Active Energy Ray Irradiation Process) Examples of active energy rays include ultraviolet rays and electron beams.

[0190] Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp.

[0191] When a high pressure mercury lamp is used, the following conditions are preferably mentioned as curing conditions. Lamp output: 25W / cm2~160W / cm2 UV illumination: 10mW / cm 2 ~800mW / cm 2 Accumulated light intensity: 25mJ / cm 2 ~2000mJ / cm 2 Conveying speed: 1m / min~50m / min

[0192] When an electron beam is used, the following conditions are preferably mentioned as curing conditions. Accelerating voltage: 10kV~300kV Conveying speed: 5m / min~50m / min [Example]

[0193] The present invention is specifically described below by way of examples and comparative examples. However, the above description and the following examples are not intended to limit the purpose of the present invention. The present invention is limited only to the claims. Unless otherwise specified, the values ​​of parts, % and the like are by mass.

[0194] Synthesis example 1 130 parts of hydroxyethyl methacrylate, 1140 parts of ε-caprolactone and 1.3 parts of tin octoate were added to a reaction apparatus equipped with a stirring device and a cooling tube, and the temperature was raised to 150° C., kept warm for 6 hours, and then cooled to obtain a ring-opening adduct of a hydroxyl-containing vinyl monomer and lactone having a weight average molecular weight of 2750.

[0195] The weight average molecular weight of the ring-opening adduct is a value measured under the following conditions using a commercially available molecular weight meter (main product name "HLC-8220GPC", manufactured by Tosoh Corporation; column product name "TSKgel SuperHZ-M", manufactured by Tosoh Corporation). Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Sample concentration: 0.5% Standard material: Polystyrene (Standard polystyrene set PStQuick A, B, C manufactured by Tosoh Corporation)

[0196] Preparation Example 1: Polymer containing quaternary ammonium salt In the same reaction apparatus as in Synthesis Example 1, 100 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) (hereinafter referred to as component (a1-1)), 80 parts of component (a2-1), 20 parts of tert-butyl methacrylate (t-BMA) (hereinafter referred to as component (a3-1)) and 800 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were added, and the temperature was raised to 80° C. Then, 8 parts of 2,2'-azobis(methylbutyronitrile) (hereinafter referred to as AMBN) and 32 parts of PGM were added to start a polymerization reaction, and the mixture was kept at 85° C. for 6 hours and then cooled to obtain a solution of a polymer containing a quaternary ammonium salt (non-volatile content 20%).

[0197] Production Example 2 A quaternary ammonium salt-containing polymer solution (non-volatile content 20%) was obtained by the same operation as in Production Example 1 except that the component (a2-1) was replaced with Brenma 50POEP-800B (manufactured by NOF Corporation).

[0198] Example 1-1 Active energy ray-curable resin composition 5 parts of the polymer of Production Example 1, 2-methacryloyloxyethyl phosphate Ester (trade name "Lite Ester P-1M" manufactured by Kyoeisha Chemical Co., Ltd.), 0.5 parts, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-9550W"), 89.5 parts, and 5 parts of a photopolymerization initiator (manufactured by IGM Resins, trade name "Omnirad 184") were mixed in a non-volatile component ratio, and 50.0 parts of methyl ethyl ketone and 50.0 parts of PGM as organic solvents were further added to prepare an active energy ray-curable resin composition.

[0199] Unless otherwise specified, the following examples were performed in the same manner as in Example 1-1 except for changes as shown in the table.

[0200]

Table 1

[0201] <Explanation of Abbreviations> P-1M: 2-Methacryloyloxyethyl phosphate (2-Methacryloyl phosphate (2-Methyloxyethyl phosphate) (trade name "Lactol P-1M" manufactured by Kyeisha Chemical Co., Ltd.)) P-2M: Bis(2-methacryloyloxyethyl) phosphate (2-Methacryloyl ester) (trade name "Radical P-2M" manufactured by Kyoeisha Chemical Co., Ltd.) 9550W: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "NK Ester A-9550W" A-TMM-3: Pentaerythritol triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-TMM-3" V#802: Tripentaerythritol poly(meth)acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., product name "Biscot #802" UA: Urethane acrylate (reaction product of isophorone diisocyanate and pentaerythritol triacrylate)

[0202] Acid value The acid value was measured under the following conditions. Reagent A: 0.5 mol / dm 3 Potassium hydroxide ethanol solution Reagent B: A toluene-ethanol solution (volume ratio: toluene / ethanol = 1 / 1) was neutralized with reagent A using a phenolphthalein indicator just before use. (1) Measure 1 g of sample without any inorganic acid and place it in a 300 mL Erlenmeyer flask. (2) Add 100 mL of reagent B and a few drops of phenolphthalein indicator to the conical flask and shake thoroughly until the sample is completely dissolved. (3) The sample solution at room temperature is titrated with reagent A. The neutralization endpoint is determined when the light red color of the phenolphthalein indicator persists for 30 seconds. (4) The acid value was calculated based on the following formula. Acid value = (28.05 × A × f) / SA: Titration amount of reagent A (mL) f: coefficient of reagent A S: Sample collection volume (g)

[0203] Laminate Manufacturing Each active energy ray-curable resin composition was applied to a triacetyl cellulose film (FTTD60UL manufactured by Fujifilm Co., Ltd., film thickness: 60 μm) using a #11 bar coater to a cured layer thickness of 5 μm, and dried at 80°C for 1 minute. Next, an ultraviolet curing device (product name "UBT-080-7A / BM", manufactured by Multiplicity Co., Ltd., high pressure mercury lamp 600 mJ / cm 2 ) thereby obtaining a laminate containing a cured product.

[0204] Surface resistance The surface resistance of the laminate immediately after production was measured using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Corporation, product name: "HIRESTA MCP-HT-450") at an applied voltage of 500 V in accordance with JIS K 6911. "OVER" means exceeding the measurement range. In addition, in Comparative Examples 1 to 3, precipitates were generated in the active energy ray-curable resin composition. Therefore, Comparative Examples 1 to 3 could not be evaluated.

[0205] Evaluation Example Transmittance The total light transmittance of the laminate was measured using a haze meter (product name "HZ-V3", manufactured by SUGA Testing Instruments Co., Ltd.) in accordance with JIS K 7361-1 (1997). When the transmittance is low, the coating film becomes turbid or colored.

[0206] Evaluation example HAZE The HAZE of the laminate was measured using a haze meter (product name: "HZ-V3", manufactured by SUGA Test Instruments Co., Ltd.) in accordance with JIS K 7361-1 (1997).

[0207]

Table 2

[0208] Example 2-1 Active energy ray-curable resin composition 25 parts of the polymer of Production Example 1 and 1 part of a salt (Aminion RE3000MF, manufactured by Nippon Emulsifier Co., Ltd.) were heated at 60°C for 1 hour and mixed with a shaker to obtain a polymer composition. Then, 5 parts of a photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins BV), the above polymer composition, 70.5 parts of propylene glycol monomethyl ether, and 215.5 parts of methyl isobutyl ketone were mixed with an oscillator. Next, 125 parts of poly(meth)acrylate A and 1.5 parts of a leveling agent (Factory 602A) were added and mixed with a shaker to prepare an active energy ray-curable resin composition.

[0209] Unless otherwise specified, the following examples were performed in the same manner as in Example 2-1 except for changes as shown in the table.

[0210] Laminate Manufacturing The active energy ray-curable resin composition was applied to a polyethylene terephthalate film (Lumira 100 manufactured by Toray Industries, Ltd., film thickness: 100 μm) using a #11 bar coater to a cured layer thickness of 5 μm, and dried at 80°C for 1 minute. Next, an ultraviolet curing device (product name "UBT-080-7A / BM", manufactured by MULTIPLY, high pressure mercury lamp 200 mJ / cm 2 ) thereby obtaining a laminate containing a cured product.

[0211] Liquid compatibility Evaluation was performed according to the following criteria: For the samples in which the liquid compatibility was rated as ×, no other evaluation was performed. ○···Completely dissolved. ×···Partially dissolved or not dissolved.

[0212] Surface resistance The surface resistance of the laminate immediately after production was measured using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Corporation, product name: "HIRESTA MCP-HT-450") at an applied voltage of 500 V in accordance with JIS K 6911.

[0213]

Table 3

[0214] The salt / quaternary ammonium salt-containing polymer ratio was calculated based on the following formula. The ratio of salt / quaternary ammonium salt-containing polymer = [(A×a) / (B×b)]×100 A: Salt ratio a: non-volatile components of salt B: Proportion of polymer containing quaternary ammonium salt b: Non-volatile components of polymers containing quaternary ammonium salts

[0215] <Explanation of Abbreviations> Production Example 1: Non-volatile matter 20% 1SX-1055F: quaternary ammonium salt-containing polymer, non-volatile content 40%, manufactured by Daisei Fine Chemicals Co., Ltd. RE3000MF: Amino-ion RE3000MF (sulfate containing polyoxyalkylene structure, non-volatile content 50%, manufactured by Nippon Emulsifier Co., Ltd.) SR-20: ADEKA SOAP SR-20 (sulfate containing a polyoxyalkylene structure, non-volatile content 100%, manufactured by ADEKA Co., Ltd.) KH-10: Aqualon KH-10 (sulfate containing a polyoxyalkylene structure, non-volatile content 100%, manufactured by Daiichi Industry Co., Ltd.) PW-36: Disparon PW-36 (phosphate containing a polyoxyalkylene structure, non-volatile content 50%, manufactured by Kusumoto Chemicals Co., Ltd.) Fatty acid amaranth S: stearic acid amide (amaranic acid amaranth), 100% non-volatile content, manufactured by Kao Micron Co., Ltd. P-1M: Light Ester P-1M, 2-methacryloyloxyethyl phosphate, non-volatile content 100%, manufactured by Kyoeisha Chemical Co., Ltd. Poly(meth)acrylate A: reaction product of the biuret form of hexamethylene diisocyanate and pentaerythritol triacrylate (urethane acrylate), non-volatile matter 80% Poly(meth)acrylate B: Reaction product of urethane ester of hexamethylene diisocyanate and pentaerythritol triacrylate (urethane acrylate), non-volatile content 80% Poly(meth)acrylate C: Product name "SC-2152", reaction product of urethane form of hexamethylene diisocyanate and dipentaerythritol pentaacrylate (urethane acrylate), manufactured by MIWON, non-volatile content 100% Omnirad2959, manufactured by IGM Resins BV, non-volatile content 100% FT602A: FT602A is a fluorine-based leveling agent having a free radical polymerizable group and a branched fluorinated aliphatic hydrocarbon group (branched fluorinated aliphatic carbonized hydrogen group), manufactured by Neos Co., Ltd. MIBK: Methyl isobutyl ketone PGME: Propylene glycol monomethyl ether

[0216] Evaluation of the example Evaluation was performed according to the following criteria. ○···Transparent and without bumps. ×···Transparent but with uneven surfaces, or opaque.

[0217] Evaluation example HAZE The HAZE of the laminate was measured using a haze meter (product name: "HZ-V3", manufactured by SUGA Test Instruments Co., Ltd.) in accordance with JIS K 7361-1 (1997).

[0218]

Table 4

Claims

1. An active energy ray-curable resin composition, The active energy ray-curable resin composition comprises: a polymer containing a quaternary ammonium salt and a phosphate ester and / or salt, The anion of the salt comprises a polyoxyalkylene structure, When the active energy ray-curable resin composition contains a phosphoric acid ester, the acid value of the active energy ray-curable resin composition is 400 mgKOH / g to 600 mgKOH / g. 2 . The active energy ray-curable resin composition according to claim 1 , comprising urethane poly(meth)acrylate. 3 . A cured product of the active energy ray-curable resin composition according to claim 1 . A laminate comprising the cured product according to claim 3.

Images