Active energy ray-curable resin composition, cured film and film

Abstract

To provide a novel active energy ray-curable resin composition that can give a cured film having high antistatic properties, a good appearance and high moist-heat resistance.SOLUTION: An active energy ray-curable resin composition contains a carboxyl group-containing methacrylate (A) and an ion conductive compound (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable resin composition, a cured film, and a cured layer. [Background technology]

[0002] As coating agents for various substrates, for example, coating agents used for the front panels of various display devices such as liquid crystal displays, plasma displays, and organic EL displays (hereinafter collectively referred to as flat panel displays), compositions containing as a main component a compound having a (meth)acryloyl group in the molecule (so-called active energy ray-curable resin), such as pentaerythritol poly(meth)acrylate or urethane (meth)acrylate, are known. These compositions are characterized by high productivity because they can be instantaneously cured by irradiation with ultraviolet rays or electron beams to form a cured film on the surface of various substrates.

[0003] When the active energy ray-curable resin composition is used for flat panel displays, the resulting cured film must have not only high transparency but also good antistatic properties to prevent problems caused by static electricity during assembly and operation of the display and to realize high-definition images. To date, methods for imparting antistatic properties to the cured film have been proposed, such as using a conductive filler, a π-conjugated conductive polymer, and an ionic conductive compound in the active energy ray-curable resin (Patent Documents 1 and 2).

[0004] Patent Document 1 proposes an active energy ray-curable resin composition containing a conductive filler (zinc antimonate fine particles). However, in order to impart a sufficient antistatic effect to a cured film obtained from the composition, a large amount of conductive filler must be used, which can reduce the transparency and hardness of the cured film. In addition, active energy ray-curable resin compositions containing π-conjugated conductive polymers such as poly(thiophene) and poly(aniline) are generally strongly colored, which makes it difficult to color the cured film.

[0005] On the other hand, when an ion-conductive compound is used in an active energy ray-curable resin, the above-mentioned coloring problem is said to hardly occur. For example, Patent Document 2 proposes an active energy ray-curable resin composition containing a polymer containing a quaternary ammonium salt structure, and describes that a cured film having excellent antistatic properties and transparency can be obtained. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-051116 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-31297 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the inventors have found that active energy ray-curable resin compositions containing ion-conductive compounds sometimes produce cured films with uneven surfaces, resulting in poor appearance. Furthermore, under high-temperature and high-humidity conditions, the cured films sometimes bleed out, resulting in reduced transparency (haze) and poor appearance, resulting in poor moist heat resistance.

[0008] An object of the present invention is to provide a novel active energy ray-curable resin composition that can give a cured film that is excellent in antistatic properties, appearance, and moist heat resistance. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by a composition containing an ion-conductive compound and a carboxyl group-containing (meth)acrylate, and have thus completed the present invention.

[0010] Specifically, the present inventors have found that a composition combining an ionically conductive compound with a carboxyl group-containing (meth)acrylate suppresses precipitation of the ionically conductive compound from the surface of the cured film, resulting in a cured film with excellent appearance. They have also found that such a cured film also suppresses bleed-out of the ionically conductive compound and the like in a high-temperature, high-humidity environment. Furthermore, the present inventors have found that the above composition can form a cured film with excellent antistatic properties. That is, the present invention relates to the following active energy ray-curable resin composition, cured film, and film.

[0011] 1. An active energy ray-curable resin composition comprising a carboxyl group-containing (meth)acrylate (A) and an ion-conductive compound (B).

[0012] 2. The active energy ray-curable resin composition according to item 1, wherein the acid value of component (A) is 10 mgKOH / g or more.

[0013] 3. The active energy ray-curable resin composition according to item 1 or 2, wherein component (B) comprises at least one selected from the group consisting of an ionic polymer, an alkali metal salt, and an ionic liquid.

[0014] 4. The active energy ray-curable resin composition according to any one of items 1 to 3, wherein the component (B) is a polymer (B1) having a quaternary ammonium salt structure.

[0015] 5. (B1) component is a structural unit (b1) derived from a vinyl monomer having a quaternary ammonium salt structure; a ring-opening polyaddition product of a hydroxyl group-containing vinyl monomer and a lactone, a structural unit (b2) derived from a vinyl monomer having a weight-average molecular weight of 1,000 to 10,000; and a structural unit (b3) derived from a vinyl monomer containing an alkyl ester group having 1 to 18 carbon atoms; 5. The active energy ray-curable resin composition according to item 4, wherein the polymer comprises:

[0016] 6. The active energy ray-curable resin composition according to any one of items 1 to 5, further comprising a poly(meth)acrylate (C) having no carboxyl group in the molecule.

[0017] 7. The active energy ray-curable resin composition according to item 6, wherein component (C) is a urethane poly(meth)acrylate.

[0018] 8. A cured film made of the active energy ray-curable resin composition according to any one of items 1 to 7 above.

[0019] 9. A film comprising the cured film according to item 8 above. [Effects of the Invention]

[0020] The active energy ray-curable resin composition of the present invention provides a cured film obtained therefrom with excellent appearance and excellent moist heat resistance because bleeding out under high temperature and high humidity conditions is suppressed. Furthermore, the cured film obtained from the active energy ray-curable resin composition has excellent antistatic properties.

[0021] The active energy ray-curable resin composition can be used favorably as a coating agent for the front panel of various flat panel displays, since it gives a cured film that is excellent in antistatic properties, appearance, and moist heat resistance.

[0022] The film of the present invention is excellent in antistatic properties, appearance and moist heat resistance, and is therefore suitable for use in flat panel displays such as liquid crystal displays, plasma displays and organic EL displays. DETAILED DESCRIPTION OF THE INVENTION

[0023] [Active energy ray-curable resin composition] The active energy ray-curable resin composition of the present invention contains a carboxyl group-containing (meth)acrylate (A) (hereinafter referred to as component (A)) and an ion-conductive compound (B) (hereinafter referred to as component (B)).

[0024] In this specification, "(meth)acrylic" means "at least one selected from the group consisting of acrylic and methacrylic." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate," and "(meth)acryloyl group" means "at least one selected from the group consisting of acryloyl group and methacryloyl group."

[0025] <Carboxyl group-containing (meth)acrylate (A)> Component (A) is not particularly limited as long as it is a compound having at least one carboxyl group and at least one (meth)acryloyl group in the molecule, and various known compounds can be used. Component (A) can be used alone or in combination of two or more types.

[0026] Examples of the component (A) include a carboxyl group-containing mono(meth)acrylate (A1) (hereinafter referred to as the component (A1)) and a carboxyl group-containing poly(meth)acrylate (A2) (hereinafter referred to as the component (A2)).

[0027] (Carboxyl group-containing mono(meth)acrylate (A1)) The component (A1) is not particularly limited as long as it is a compound having at least one carboxyl group and one (meth)acryloyl group in the molecule, and various known compounds can be used. The component (A1) can be used alone or in combination of two or more.

[0028] Examples of the component (A1) include (meth)acrylic acid, (meth)acrylic acid dimer, carboxylethyl (meth)acrylate, carboxylpentyl (meth)acrylate, carboxypolycaprolactone mono(meth)acrylate, a reaction product of a hydroxyl group-containing mono(meth)acrylate with an acid anhydride, a carboxyl group-containing urethane mono(meth)acrylate, a carboxyl group-containing polyester mono(meth)acrylate, a carboxyl group-containing epoxy mono(meth)acrylate, and a carboxyl group-containing polyether mono(meth)acrylate.

[0029] (Reaction product of hydroxyl group-containing mono(meth)acrylate and acid anhydride) Examples of hydroxyl group-containing mono(meth)acrylates include hydroxyl group-containing linear alkyl(meth)acrylates, hydroxyl group-containing branched alkyl(meth)acrylates, hydroxyl group-containing cycloalkyl(meth)acrylates, hydroxyl group-containing aryl(meth)acrylates, polyalkylene glycol mono(meth)acrylates, glycerin mono(meth)acrylates, ethylene oxide-modified glycerin mono(meth)acrylates, propylene oxide-modified glycerin mono(meth)acrylates, trimethylolpropane mono(meth)acrylates, and caprolactone adducts of these mono(meth)acrylates.

[0030] Examples of the hydroxyl group-containing linear alkyl(meth)acrylate include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.

[0031] Examples of the hydroxyl group-containing branched alkyl(meth)acrylate include 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 3-hydroxybutyl(meth)acrylate.

[0032] Examples of the hydroxyl group-containing cycloalkyl(meth)acrylate include 1,4-cyclohexanedimethanol mono(meth)acrylate, etc. Examples of the hydroxyl group-containing aryl(meth)acrylate include 1,4-benzenedimethanol mono(meth)acrylate, etc.

[0033] Examples of the polyalkylene glycol mono(meth)acrylate include (meth)acrylates having an oxyalkylene chain such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate; (meth)acrylates having an oxyalkylene chain with a block structure such as polyethylene glycol-polypropylene glycol mono(meth)acrylate and polyoxybutylene-polyoxypropylene mono(meth)acrylate; and (meth)acrylates having an oxyalkylene chain with a random structure such as poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate.

[0034] Examples of the acid anhydride include succinic anhydride, 1-dodecenylsuccinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride, which have one acid anhydride group in the same molecule. and compounds having two acid anhydride groups in the same molecule, such as pyromellitic anhydride, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, diphenyl ether tetracarboxylic anhydride, and trimellitic anhydride-ethylene glycol ester (commercially available products include, for example, Rikacid TMEG-100, manufactured by New Japan Chemical Co., Ltd.).

[0035] Examples of the reaction product of the above-mentioned hydroxyl group-containing mono(meth)acrylate with an acid anhydride include 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxyethyl tetrahydrophthalic acid, 4-hydroxybutyl(meth)acrylate succinic acid adduct, 1,4-cyclohexanedimethanol mono(meth)acrylate succinic acid adduct, 1,4-benzenedimethanol mono(meth)acrylate succinic acid adduct, and polyalkylene glycol mono(meth)acrylate succinic acid adduct.

[0036] (Carboxyl group-containing urethane mono(meth)acrylate) Examples of the carboxyl group-containing urethane mono(meth)acrylate include a reaction product of an unreacted hydroxyl group in an addition reaction product (urethane mono(meth)acrylate) of the hydroxyl group-containing mono(meth)acrylate, a polyol, and a polyisocyanate with the acid anhydride; or an addition reaction product of the hydroxyl group-containing mono(meth)acrylate, a carboxyl group-containing polyol, and a polyisocyanate.

[0037] The polyol may be any known compound having at least two hydroxyl groups in the molecule, and may be used alone or in combination of two or more thereof.

[0038] Examples of the polyol include aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, and (meth)acrylic polyols.

[0039] Examples of the aliphatic polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1,6 Examples of the alcohols include aliphatic alcohols containing two hydroxyl groups such as 1,4-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, and 2-methyl-1,8-octanediol; sugar alcohols such as xylitol and sorbitol; and aliphatic alcohols containing three or more hydroxyl groups such as glycerin, trimethylolpropane, and trimethylolethane.

[0040] Examples of the alicyclic polyol include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecane dimethanol.

[0041] Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols.

[0042] Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid or an anhydride thereof; a ring-opening polymer of a cyclic ester (lactone); and a reaction product of three components: a polyhydric alcohol, a polycarboxylic acid or an anhydride thereof, and a cyclic ester.

[0043] Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

[0044] Examples of the polycarboxylic acid or anhydride thereof include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid, or anhydrides thereof.

[0045] Examples of the cyclic ester include propiolactone, butyrolactone, valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0046] Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol with phosgene; and a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).

[0047] Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the polyester polyols, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0048] The polycarbonate polyol may be any compound having a carbonate bond in the molecule and a hydroxyl group at the end, and may have an ester bond in addition to the carbonate bond.

[0049] The polyolefin polyols include, for example, those having a homopolymer or copolymer of ethylene, propylene, butene, or the like as a saturated hydrocarbon skeleton and having hydroxyl groups at the molecular terminals.

[0050] The polybutadiene polyol may be, for example, a polybutadiene polyol having a butadiene copolymer as a hydrocarbon skeleton and hydroxyl groups at its molecular terminals. The polybutadiene polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the polybutadiene polyol structure have been hydrogenated.

[0051] Examples of the (meth)acrylic polyol include those having at least two hydroxyl groups in the molecule of a (meth)acrylic acid ester polymer or copolymer. Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate.

[0052] Examples of the carboxyl group-containing polyol include ring-opening addition polymers of dihydroxycarboxylic acids and the cyclic esters. Examples of the dihydroxycarboxylic acids include dimethylolbutanoic acid, dimethylolpropionic acid, and dioxyadipic acid.

[0053] The polyisocyanate may be any known compound having at least two isocyanate groups in the molecule, and may be used alone or in combination of two or more kinds.

[0054] Examples of the polyisocyanate include linear aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, biuret forms, isocyanurate forms, allophanate forms, and adduct forms of these diisocyanates, as well as complexes obtained by reacting two or more selected from the group consisting of biuret forms, isocyanurate forms, allophanate forms, and adduct forms.

[0055] Examples of the linear aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0056] Examples of the branched aliphatic diisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0057] Examples of the alicyclic diisocyanate include hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and bicyclodecylene diisocyanate.

[0058] Examples of the aromatic diisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and 1,5-naphthylene diisocyanate.

[0059] The biuret compound of the diisocyanate is The following structural formula: [ka] [where n b is an integer equal to or greater than 1, and R bA ~R bE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, or an aromatic diisocyanate residue, and R bα ~R bβ are each independently an isocyanate group or [ka] (n b1 is an integer greater than or equal to 0, and R b1 ~R b5 is R bA ~R bE is similar to R b '~R b '' each independently represent an isocyanate group or R bα ~R bβ It is a group of its own. R b4 ~R b5 , R b '' may be different groups for each structural unit. bD ~R bE , R bβ may have different groups for each structural unit.

[0060] Specific examples of the biuret derivatives of the diisocyanates include Duranate 24A-100, Duranate 22A-75P, and Duranate 21S-75E (all manufactured by Asahi Kasei Corporation), and Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate) (all manufactured by Sumika Covestro Urethane Co., Ltd.).

[0061] The isocyanurate of the diisocyanate is The following structural formula: [ka] [where n i is an integer greater than or equal to 0, and RiA ~R iE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, or an aromatic diisocyanate residue, and R iα ~R iβ are each independently an isocyanate group or [ka] (n i1 is an integer greater than or equal to 0, and R i1 ~R i5 is R iA ~R iE is similar to R i '~R i '' each independently represent an isocyanate group or R iα ~R iβ It is a group of its own. R i4 ~R i5 , R i '' may be different groups for each structural unit. iD ~R iE , R iβ may have different groups for each structural unit.

[0062] Specific examples of the isocyanurate derivatives of the diisocyanates include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate MHG-80B (all manufactured by Asahi Kasei Corporation), Coronate HXR and Coronate HX (all isocyanurate derivatives of hexamethylene diisocyanate) (all manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate derivatives of hydrogenated xylylene diisocyanate) (all manufactured by Mitsui Chemicals, Inc.), and VESTANAT T1890 / 100 (isocyanurate derivatives of isophorone diisocyanate) (all manufactured by Evonik Japan Co., Ltd.).

[0063] The allophanate of the diisocyanate is The following structural formula: [ka] [where n a is an integer greater than or equal to 0, and R aA is an alkyl group, an aryl group, a polyether group, a polyester group, or a polycarbonate group, and R aB ~R aG are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, or an aromatic diisocyanate residue, and R aα ~R aγ are each independently an isocyanate group or [ka] (n a1 is an integer greater than or equal to 0, and R a1 ~R a6 is R aB ~R aG is similar to R a '~R a ''' each independently represent an isocyanate group or R aα ~R aγ It is a group of its own. R a1 ~R a4 , R a '~R a '' may be different groups for each structural unit. aB ~R aE , R aα ~R aβ may have different groups for each structural unit.

[0064] Specific examples of the allophanate derivatives of the diisocyanates include Coronate 2793 (manufactured by Tosoh Corporation) and Takenate D-178N (manufactured by Mitsui Chemicals, Inc.).

[0065] The adduct of the diisocyanate is The following structural formula: [ka] [where n ad is an integer greater than or equal to 0, and RadA ~R adE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, or an aromatic diisocyanate residue, and R ad1 ~R ad2 are each independently [ka] (In the formula, n ad’ is an integer greater than or equal to 0, and R ad’ ~R ad’’ is R adA ~R adE is similar to R ad’’’ is R ad1 ~R ad2 Its own base, R ad’ ~R ad’’’ may have different groups for each structural unit. and R adD ~R adE , R ad2 may be different groups for each structural unit.] an adduct of trimethylolpropane and diisocyanate represented by The following structural formula [ka] [where n ad1 is an integer greater than or equal to 0, and R adα ~R adε are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, or an aromatic diisocyanate residue, and R adA ~R adB are each independently [ka] (In the formula, n ad1’ is an integer greater than or equal to 0, and R adδ’ ~R adε’ is R adα ~R adε is similar to R adB’ is R adA ~RadB Its own base, R adδ’ ~R adε’ , R adB’ may have different groups for each structural unit. R adδ ~R adε , R adB may be different groups for each structural unit.] Examples of suitable glycerin compounds include adducts of glycerin and diisocyanate represented by the following formula:

[0066] Specific examples of the adducts of the diisocyanates include Duranate P301-75E (both manufactured by Asahi Kasei Corporation), Takenate D-110N, Takenate D-160N (both manufactured by Mitsui Chemicals, Inc.), Coronate L, Coronate HL (both manufactured by Tosoh Corporation), and the like.

[0067] In the above formulas, the term "linear aliphatic diisocyanate residue, branched aliphatic diisocyanate residue, alicyclic diisocyanate residue, and aromatic diisocyanate residue" refers to the remaining groups of the linear aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, excluding the isocyanate group.

[0068] (Carboxyl group-containing polyester mono(meth)acrylate) The carboxyl group-containing polyester mono(meth)acrylate may be, for example, a reaction product of an unreacted hydroxyl group in a dehydration condensation product (polyester mono(meth)acrylate) of one molecule of polyester polyol and one molecule of (meth)acrylic acid with the acid anhydride. The polyester polyol may, for example, be the polyester polyol.

[0069] (Carboxyl group-containing epoxy mono(meth)acrylate) The carboxyl group-containing epoxy mono(meth)acrylate may be, for example, a reaction product of a hydroxyl group in an addition reaction product (epoxy mono(meth)acrylate) of a terminal epoxy group of one molecule of an epoxy resin with one molecule of (meth)acrylic acid, and the acid anhydride. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

[0070] Examples of the aromatic epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A type novolac type epoxy resins, naphthalenediol type epoxy resins, phenol dicyclopentadiene novolac type epoxy resins, and hydrides thereof.

[0071] Examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers of polyethylene glycol and polypropylene glycol; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol, and alkylene oxide adducts thereof; polyglycidyl ethers of polyhydric alcohols such as di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin, and alkylene oxide adducts thereof, and di-, tri-, or tetraglycidyl ethers of pentaerythritol and alkylene oxide adducts thereof; di- or polyglycidyl ethers of hydrogenated bisphenol A and alkylene oxide adducts thereof; tetrahydrophthalic acid diglycidyl ether; and hydroquinone diglycidyl ether.

[0072] (Carboxyl group-containing polyether mono(meth)acrylate) Examples of the carboxyl group-containing polyether mono(meth)acrylate include a dehydration condensation product of one molecule of polyether polyol and one molecule of (meth)acrylic acid (a reaction product of an unreacted hydroxyl group in the polyether mono(meth)acrylate with an acid anhydride). Examples of the polyether polyol include the above-mentioned polyether polyols.

[0073] (Carboxyl group-containing poly(meth)acrylate (A2)) The component (A2) is not particularly limited as long as it is a compound having at least one carboxyl group and at least two (meth)acryloyl groups in the molecule, and various known compounds can be used. The component (A2) can be used alone or in combination of two or more.

[0074] Examples of component (A2) include dimethylolpropionic acid di(meth)acrylate, 2,2'-bis(hydroxymethyl)butyric acid di(meth)acrylate, a reaction product of a hydroxyl group-containing poly(meth)acrylate with an acid anhydride, a carboxyl group-containing urethane poly(meth)acrylate, a carboxyl group-containing polyester poly(meth)acrylate, a carboxyl group-containing epoxy poly(meth)acrylate, a carboxyl group-containing polyether poly(meth)acrylate, and a carboxyl group-containing polyacryl poly(meth)acrylate.

[0075] (Reaction product of hydroxyl group-containing poly(meth)acrylate with acid anhydride) Examples of hydroxyl group-containing poly(meth)acrylates include hydroxyl group-containing glycerin poly(meth)acrylate, hydroxyl group-containing polyglycerin poly(meth)acrylate, hydroxyl group-containing pentaerythritol poly(meth)acrylate, hydroxyl group-containing polypentaerythritol poly(meth)acrylate, hydroxyl group-containing trimethylolpropane poly(meth)acrylate, and hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate.

[0076] Examples of the hydroxyl group-containing glycerin poly(meth)acrylate include glycerin di(meth)acrylate, ethylene oxide-modified glycerin di(meth)acrylate, propylene oxide-modified glycerin di(meth)acrylate, and a mixture of at least two selected from the group consisting of glycerin mono(meth)acrylate, glycerin di(meth)acrylate, and glycerin tri(meth)acrylate.

[0077] Examples of the hydroxyl group-containing polyglycerol poly(meth)acrylate include diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, triglycerol di(meth)acrylate, triglycerol tri(meth)acrylate, and triglycerol tetra(meth)acrylate.

[0078] Examples of the hydroxyl group-containing pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol di(meth)acrylate, propylene oxide-modified pentaerythritol di(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified pentaerythritol tri(meth)acrylate, and a mixture of at least two selected from the group consisting of pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0079] Examples of the hydroxyl group-containing polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and mixtures of at least two selected from these (meth)acrylates, as well as mixtures of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0080] Examples of the hydroxyl group-containing trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate, ethylene oxide-modified trimethylolpropane di(meth)acrylate, and propylene oxide-modified trimethylolpropane di(meth)acrylate.

[0081] Examples of the hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropane di(meth)acrylate and ditrimethylolpropane tri(meth)acrylate.

[0082] Examples of the reaction product of the hydroxyl group-containing poly(meth)acrylate with an acid anhydride include trimethylolpropane di(meth)acrylate succinic acid adduct, pentaerythritol di(meth)acrylate succinic acid adduct, pentaerythritol tri(meth)acrylate succinic acid adduct, dipentaerythritol tetra(meth)acrylate succinic acid adduct, dipentaerythritol penta(meth)acrylate succinic acid adduct, trimethylolpropane di(meth)acrylate phthalic acid adduct, pentaerythritol di(meth)acrylate phthalic acid adduct, pentaerythritol tri(meth)acrylate phthalic acid adduct, dipentaerythritol tetra(meth)acrylate phthalic acid adduct, and dipentaerythritol penta(meth)acrylate phthalic acid adduct.

[0083] (Carboxyl group-containing urethane poly(meth)acrylate) Examples of the carboxyl group-containing urethane poly(meth)acrylate include a reaction product of an unreacted hydroxyl group in an addition reaction product (urethane poly(meth)acrylate) of the hydroxyl group-containing poly(meth)acrylate having at least two hydroxyl groups in the molecule with a polyisocyanate, and the acid anhydride; or a reaction product of an unreacted hydroxyl group in an addition reaction product (urethane poly(meth)acrylate) of the hydroxyl group-containing poly(meth)acrylate with a polyol and a polyisocyanate, and the acid anhydride.

[0084] The polyol may be any known compound having at least two hydroxyl groups in the molecule, and may be used alone or in combination of two or more thereof.

[0085] Examples of the polyol include the polyols described above.

[0086] The polyisocyanate may be any known compound having at least two isocyanate groups in the molecule, and may be used alone or in combination of two or more kinds.

[0087] Examples of the polyisocyanate include the polyisocyanates described above.

[0088] (Carboxyl group-containing polyester poly(meth)acrylate) The carboxyl group-containing polyester poly(meth)acrylate may be, for example, a reaction product of an unreacted hydroxyl group in a dehydration condensation product (polyester poly(meth)acrylate) of one molecule of polyester polyol and at least two molecules of (meth)acrylic acid with the acid anhydride. The polyester polyol may, for example, be the polyester polyol.

[0089] (Carboxyl group-containing epoxy poly(meth)acrylate) The carboxyl group-containing epoxy poly(meth)acrylate may be, for example, a reaction product of a hydroxyl group in an addition reaction product (epoxy poly(meth)acrylate) of a terminal epoxy group of one molecule of an epoxy resin with at least two molecules of (meth)acrylic acid and the acid anhydride. Examples of the epoxy resin include the aromatic epoxy resins and aliphatic epoxy resins.

[0090] (Carboxyl group-containing polyether poly(meth)acrylate) Examples of the carboxyl group-containing polyether poly(meth)acrylate include a dehydration condensation product of one molecule of polyether polyol and at least two molecules of (meth)acrylic acid (a reaction product of an unreacted hydroxyl group in the polyether poly(meth)acrylate and the acid anhydride). Examples of the polyether polyol include the polyether polyols mentioned above.

[0091] (Carboxyl group-containing polyacrylic poly(meth)acrylate) Examples of the carboxyl group-containing polyacrylic poly(meth)acrylate include a reaction product of a hydroxyl group in an addition reaction product of a homopolymer of an epoxy group-containing mono(meth)acrylate or a copolymer of an epoxy group-containing mono(meth)acrylate and another monomer with (meth)acrylic acid and the acid anhydride.

[0092] Examples of the epoxy group-containing mono(meth)acrylate include glycidyl(meth)acrylate, β-methylglycidyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, and vinylcyclohexene monoxide (i.e., 1,2-epoxy-4-vinylcyclohexane).

[0093] The carboxyl group-containing polyacrylic poly(meth)acrylate may also be, for example, a ring-opening addition reaction product of a part of the carboxyl groups in a homopolymer of (meth)acrylic acid or a copolymer of (meth)acrylic acid and another monomer with the epoxy group-containing mono(meth)acrylate. Commercially available products of such ring-opening addition reaction products include "Cyclomer P(ACA)Z251" manufactured by Daicel Corporation.

[0094] Component (A) is preferably component (A2) in view of the excellent appearance and moist heat resistance of the cured film. Component (A2) is more preferably a compound having at least three (meth)acryloyl groups in the molecule in view of the excellent appearance and moist heat resistance of the cured film. Component (A2) is particularly preferably a reaction product of a hydroxyl group-containing poly(meth)acrylate with an acid anhydride, a carboxyl group-containing polyacrylpoly(meth)acrylate, in view of the excellent appearance and moist heat resistance of the cured film.

[0095] (Physical properties of carboxyl group-containing (meth)acrylate (A)) The physical properties of component (A) are not particularly limited. The acid value of component (A) is preferably 10 mgKOH / g or more from the viewpoint of excellent appearance and moist heat resistance of the cured film, and from the same viewpoint, it is more preferably about 10 to 200 mgKOH / g, and particularly preferably about 20 to 150 mgKOH / g. In this specification, the acid value is a value measured according to JIS K 0070.

[0096] The weight average molecular weight (Mw) of component (A) is preferably about 400 to 30,000 in order to provide a cured film with excellent wet heat resistance. The weight average molecular weight of component (A) refers to a polyethylene oxide equivalent value measured by gel permeation chromatography, but the measurement method is not particularly limited, and various known means can be used, and commercially available measuring machines can also be used.

[0097] The content of the component (A) in the active energy ray-curable resin composition is not particularly limited, but in terms of excellent moist heat resistance and appearance, it is preferably about 10 to 90 parts by mass, converted into solid content, per 100 parts by mass of the active energy ray-curable resin composition.

[0098] <Ion-conductive compound (B)> The component (B) is not particularly limited as long as it is an ionically conductive compound that exhibits conductivity through the movement of ions, and various known compounds can be used. The component (B) can be used alone or in combination of two or more.

[0099] Examples of the component (B) include cationic conductive compounds, anionic conductive compounds, nonionic conductive compounds, amphoteric conductive compounds, ionic polymers, and ionic liquids.

[0100] Examples of the cationic conductive compound include quaternary ammonium salts and pyridinium salts. Examples of the quaternary ammonium salts include alkyltrimethylammonium halides, dialkyldimethylammonium halides, (poly)oxyalkylenetrialkylammonium halides, acyloylamidopropyltrimethylammonium methosulfate, and alkylbenzylmethylammonium halides. Examples of the pyridinium salts include alkylpyridinium halides.

[0101] Examples of the anionic conductive compound include alkali metal salts and alkaline earth metal salts. Examples of the alkali metal in the alkali metal salt include lithium, sodium, and potassium. Examples of the alkaline earth metal in the alkaline earth metal salt include magnesium and calcium.

[0102] Examples of the alkali metal salt include alkali metal salts of inorganic acids, alkali metal salts of alkylsulfonic acids, alkali metal salts of alkylbenzenesulfonic acids, alkali metal salts of alkyl sulfates, alkali metal salts of alkylethoxy sulfates, alkali metal salts of alkyl phosphates, alkali metal salts of fluorosulfonic acids, alkali metal salts of bis(fluorosulfonyl)imides, alkali metal salts of tris(fluorosulfonyl)methides, alkali metal salts of fluoroalkylsulfonic acids, alkali metal salts of bis(fluoroalkylsulfonyl)imides, and alkali metal salts of tris(fluoroalkylsulfonyl)methides.

[0103] Examples of alkali metal salts of inorganic acids include LiCl, LiBr, LiI, LiBF4, LiPF6, LiSCN, LiClO4, NaCl, NaBr, NaI, NaBF4, NaPF6, NaSCN, NaClO4, KCl, KBr, KI, KBF4, KPF6, KSCN, and KClO4.

[0104] Furthermore, as the alkali metal salt (lithium salt) in which the alkali metal is lithium, a mixture containing the lithium salt and (meth)acrylate, polyalkylene glycol, adipate, or the nonionic conductive compound can also be used. Examples of commercially available products of such mixtures include the "Sankonol" series manufactured by Sanko Chemical Industry Co., Ltd.

[0105] Examples of the nonionic conductive compound include fatty acid alkanolamides, di(2-hydroxyethyl)alkylamines, polyoxyethylene alkylamines, fatty acid glycerin esters, polyoxyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxysorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol, polyoxyethylene diamines, copolymers of polyether, polyester and polyamide, and methoxypolyethylene glycol (meth)acrylate.

[0106] Examples of the amphoteric ion type conductive compound include sulfobetaine, alkylbetaine, alkylimidazolium betaine, carbobetaine graft copolymer, and alkylalanine.

[0107] Examples of the ionic polymer include polymers having ion-conductive groups of the cationic type (quaternary ammonium salts, etc.), amphoteric type (betaine compounds, etc.), anionic type (sulfonates, etc.), or nonionic type (glycerin, etc.). Examples of the ionic polymer include homopolymers of vinyl monomers having the above-mentioned various ion-conductive groups, and copolymers of the vinyl monomers with other monomers.

[0108] The ionic liquid refers to a molten salt (ionic compound) that is liquid at room temperature (25° C.).

[0109] The ionic liquid is composed of a cation component and an anion component, and the cation component and anion component are not particularly limited, but those used in general ionic liquids can be used. Note that the ionic liquid also includes the cationic conductive compounds that are liquid at room temperature (25°C).

[0110] Examples of the cation component include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a 1,3-dimethylimidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, a phosphonium cation, and a sulfide cation.

[0111] The anion component may be, for example, Cl - , Br - , AlCl4 - , Al2Cl7 - , BF4 - , PF6 - , ClO4 - , NO3 - , CH3COO - , CF3COO - , CH3SO3 - , CH3SO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , AsF6 - , SbF6 - , NbF6 - , TaF6 - , F(HF) n- , (CN)2N - , C4F9SO3 - , (C2F5SO2)2N - , C3F7COO - , (CF3SO2)(CF3CO)N - , (C n F2n+1 SO2)2N - (where n is an integer from 1 to 10), CF2(C m F 2m SO2)2N - (where m is an integer from 1 to 10), - O3S(CF2) l SO3 - (wherein l is an integer from 1 to 10), (C p F 2p+1 SO2)(C q F 2q+1 SO2)N - , (where p and q are integers from 1 to 10), (FSO2)2N - etc.

[0112] In view of the excellent antistatic properties of the cured film, the component (B) preferably contains at least one selected from the group consisting of an ionic polymer, an alkali metal salt, and an ionic liquid. The ionic polymer is more preferably a polymer (B1) having a quaternary ammonium salt structure (hereinafter referred to as component (B1)) in view of the excellent antistatic properties of the cured film. The alkali metal salt is more preferably an alkali metal salt of bis(fluoroalkylsulfonyl)imide in view of the excellent antistatic properties of the cured film, and from the same viewpoint, an alkali metal salt of bis(trifluoromethanesulfonyl)imide is particularly preferable. The ionic liquid is preferably a tetraalkylammonium salt derivative or an imidazolium salt derivative in view of the excellent antistatic properties of the cured film, and from the same viewpoint, a tetraalkylammonium salt derivative of bis(trifluoromethanesulfonyl)imide or an imidazolium salt derivative of 1,3-dimethylimidazolium methyl sulfate is more preferable.

[0113] (Polymer (B1) having a quaternary ammonium salt structure) As the component (B1), any known polymer having a quaternary ammonium salt structure can be used without any particular restrictions.

[0114] From the viewpoints of the transparency and antistatic properties of the cured film, the component (B1) is preferably a polymer containing a structural unit (b1) derived from a vinyl monomer containing a quaternary ammonium salt structure (hereafter referred to as structural unit (b1)), a structural unit (b2) derived from a vinyl monomer which is a ring-opening polyaddition product of a hydroxyl group-containing vinyl monomer and a lactone and has a weight-average molecular weight of 1,000 to 10,000 (hereafter referred to as structural unit (b2)), and a structural unit (b3) derived from a vinyl monomer which contains an alkyl ester group having 1 to 18 carbon atoms (hereafter referred to as structural unit (b3)).

[0115] The structural unit (b1) is a structural unit contained in a polymer chain when a polymer is produced using a vinyl monomer (b1') (hereinafter referred to as component (b1')) containing a quaternary ammonium salt structure. The component (b1') can be used alone or in combination of two or more types.

[0116] The component (b1') can be any known vinyl monomer having a quaternary ammonium salt structure in the molecule, without any particular limitation. [CH2=C(R 1 )-C(=O)-ABN + (R 2 )(R 3 )(R 4 )] n X n- (In the formula, R 1 is H or CH3, R 2 ~R 4 represents an alkyl group having about 1 to 3 carbon atoms, A represents O or NH, B represents an alkylene group having about 1 to 3 carbon atoms, and X n- represents a counter anion species, and n represents an integer of 1 or more). n- is Cl - , SO4 2- , SO3 2- , C2H5SO4 - , Br - In terms of antistatic effect, Cl -Examples of commercially available products of the component (b1') include "Light Ester DQ-100" manufactured by Kyoeisha Chemical Co., Ltd. and "DMAEA-Q" manufactured by Kohjin Co., Ltd.

[0117] Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

[0118] The content of the structural unit (b1) in the component (B1) is not particularly limited, but in terms of providing a cured film with excellent transparency and antistatic properties, it is preferably about 30 to 60% by mass relative to 100% by mass of the component (B1).

[0119] The structural unit (b2) is a ring-opening polyaddition product of a hydroxyl group-containing vinyl monomer and a lactone, and is a structural unit contained in a polymer chain when a polymer is produced using a vinyl monomer (b2') (hereinafter referred to as component (b2')) having a weight-average molecular weight of 1,000 to 10,000. One type of component (b2') can be used alone, or two or more types can be used in combination.

[0120] Component (b2') is produced by a ring-opening polyaddition reaction using a hydroxyl group-containing vinyl monomer and a lactone by a known method. The hydroxyl group-containing vinyl monomer can be used alone or in combination of two or more types, and the lactone can be used alone or in combination of two or more types.

[0121] The hydroxyl group-containing vinyl monomer may be any known monomer without any particular limitation. Specific examples include hydroxyl group-containing (meth)acrylic compounds and hydroxyl group-containing vinyl ethers. Among these, hydroxyl group-containing (meth)acrylic compounds are preferred from the viewpoint of radical copolymerizability.

[0122] Examples of the hydroxyl group-containing (meth)acrylic compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acrylamide.

[0123] Examples of the hydroxyl group-containing vinyl ether include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and hydroxydiethylene glycol vinyl ether.

[0124] The lactone may be any known lactone without any particular limitation. Specific examples include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone. Among these, one selected from the group consisting of ε-caprolactone and δ-valerolactone is preferred, particularly in terms of reactivity in ring-opening polymerization.

[0125] The weight-average molecular weight (Mw) of component (b2') is 1,000 to 10,000. If the weight-average molecular weight is less than 1,000, the antistatic properties and moist heat resistance of the cured film tend to decrease. If the weight-average molecular weight exceeds 10,000, synthesis of component (b2') becomes difficult. The weight-average molecular weight is preferably about 1,000 to 5,000, as this provides the cured film with excellent transparency, antistatic properties, scratch resistance, and moist heat resistance, and facilitates synthesis. In this specification, the weight-average molecular weight of component (b2') refers to the polystyrene-equivalent value measured by gel permeation chromatography, but the measurement method is not particularly limited, and various known methods can be used, and commercially available measuring instruments can also be used.

[0126] The content of the structural unit (b2) in the component (B1) is not particularly limited, but in order to provide a cured film with excellent transparency and scratch resistance, it is preferably about 25 to 55% by mass relative to 100% by mass of the component (B1).

[0127] Component (b2') can be obtained by various known methods. Specific examples include a method of subjecting the lactone to a ring-opening polyaddition reaction using the hydroxyl group-containing vinyl monomer as an initiator. Furthermore, the weight-average molecular weight can be adjusted by appropriately selecting the ratio of the two components charged during the reaction, the reaction temperature, and the type and amount of catalyst.

[0128] A catalyst may be used in the reaction. Examples of the catalyst include mineral acids such as sulfuric acid and phosphoric acid; alkali metals such as lithium, sodium, and potassium; alkyl metal compounds such as n-butyllithium and t-butyllithium; metal alkoxides such as titanium tetrabutoxide; and tin compounds such as dibutyltin dilaurate, dibutyltin dioctolate, dibutyltin mercaptide, and tin octoate. The amount of catalyst used is not particularly limited, but is preferably about 0.01 to 10% by mass relative to 100% by mass of the total of the hydroxyl group-containing vinyl monomer and lactone.

[0129] The structural unit (b3) is a structural unit that is contained in a polymer chain when a polymer is produced using a vinyl monomer (b3') (hereinafter referred to as component (b3')) that contains an alkyl ester group having 1 to 18 carbon atoms. The component (b3') can be used alone, or two or more types can be used in combination.

[0130] The component (b3') can be any known vinyl monomer having an alkyl ester group of 1 to 18 carbon atoms, and is not particularly limited thereto. In this specification, the term "alkyl ester group of 1 to 18 carbon atoms" refers to an ester group represented by -C(=O)-OR, where R is an alkyl group of 1 to 18 carbon atoms.

[0131] Examples of the alkyl ester group having 1 to 18 carbon atoms include a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group, a hexyl ester group, a heptyl ester group, an octyl ester group, a nonyl ester group, a decyl ester group, an undecyl ester group, a lauryl ester group, a tridecyl ester group, a myristyl ester group, a pentadecyl ester group, a palmityl ester group, a heptadecyl ester group, a stearyl ester group, an isopropyl ester group, an isobutyl ester group, and a sec-butyl ester group. Examples of the alkyl ester group include a tert-butyl ester group, a 1-methylbutyl ester group, a 2-methylbutyl ester group, a 3-methylbutyl ester group, a 1-ethylpropyl ester group, a 1,1-dimethylpropyl ester group, a 1,2-dimethylpropyl ester group, a 2,2-dimethylpropyl ester group, an isopentyl ester group, an isododecyl ester group, an isotridecyl ester group, an isomyristyl ester group, an isopentadecyl ester group, an isohexadecyl ester group, an isoheptadecyl ester group, and an isostearyl ester group.

[0132] Examples of the component (b3') include the above mono(meth)acrylates containing an alkyl ester group having 1 to 18 carbon atoms.

[0133] Examples of the mono(meth)acrylate containing an alkyl ester group having 1 to 18 carbon atoms 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, decyl(meth)acrylate, undecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, myristyl(meth)acrylate, pentadecyl(meth)acrylate, palmitic acid(meth)acrylate, and the like. butyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, methylbutyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl (meth)acrylate, isomyristyl (meth)acrylate, isopentadecyl (meth)acrylate, isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, and isostearyl (meth)acrylate.

[0134] By including the structural unit (b3) in the component (B1), a cured film containing the component (B1) exhibits excellent antistatic properties over time. For the same reasons, the component (b3') is particularly preferably one selected from the group consisting of tert-butyl (meth)acrylate and isobutyl (meth)acrylate.

[0135] There are no particular limitations on the content of the structural unit (b3) in the component (B1), but in order to achieve excellent transparency and scratch resistance in the cured film, it is preferably about 5 to 30% by mass relative to 100% by mass of the component (B1).

[0136] The component (B1) may further contain a structural unit (b4) (hereinafter also referred to as structural unit (b4)) other than the above structural units (b1) to (b3). The structural unit (b4) is a structural unit that is contained in the polymer chain when a polymer is produced using a monomer (b4') (hereinafter referred to as component (b4')) other than the above monomers (b1') to (b3'). Two or more types of component (b4') can be used in combination.

[0137] Examples of the component (b4') include mono(meth)acrylates and vinyl monomers containing an aromatic ring structure that do not fall under the category of the component (b3').

[0138] Examples of mono(meth)acrylates that do not fall under the category of component (b3') include mono(meth)acrylates containing an alkyl ester group having 19 or more carbon atoms.

[0139] Examples of the mono(meth)acrylate containing an alkyl ester group having 19 or more carbon atoms include nonadecyl(meth)acrylate, eicosyl(meth)acrylate, heneicosyl(meth)acrylate, docosyl(meth)acrylate, tricosyl(meth)acrylate, tetracosyl(meth)acrylate, pentacosyl(meth)acrylate, hexacosyl(meth)acrylate, heptacosyl(meth)acrylate, and octacosyl(meth)acrylate.

[0140] Examples of the aromatic ring structure-containing vinyl monomer include styrene, α-methylstyrene, and 4-methylstyrene.

[0141] There are no particular limitations on the content of the structural unit (b4) in the component (B1), but from the viewpoint of providing a cured film with excellent antistatic properties, moist heat resistance, and transparency, it is preferably about 0 to 20% by mass relative to 100% by mass of the component (B1).

[0142] The content ratio of the structural units (b1) to (b3) in component (B1) is not particularly limited, but in consideration of the antistatic properties and transparency of the cured film, it is preferably approximately 35-45:35-45:5-15 (mass ratio), in that order. Furthermore, when component (B1) contains structural unit (b4), the content ratio of the structural units (b1) to (b4) in component (B1) is also not particularly limited, but for the same reasons it is preferably approximately 35-45:35-45:5-15:0-15 (mass ratio), in that order.

[0143] (Physical Properties and Production Method of Polymer (B1) Having a Quaternary Ammonium Salt Structure) The physical properties of component (B1) are not particularly limited. The weight-average molecular weight (Mw) of component (B1) is preferably 300,000 or less, and more preferably approximately 150,000 to 300,000. When the weight-average molecular weight is 150,000 or more, bleed-out of the antistatic agent from the cured film is further suppressed, resulting in superior moist heat resistance of the cured film. The weight-average molecular weight of component (B1) refers to the polyethylene oxide equivalent value measured by gel permeation chromatography, but the measurement method is not particularly limited, and various known methods can be used, including commercially available measuring devices.

[0144] Component (B1) can be obtained by radical copolymerization of components (b1'), (b2'), (b3'), and, if necessary, component (b4') using any of the known methods (bulk polymerization, solution polymerization, emulsion polymerization, etc.). The reaction temperature is typically about 40 to 160°C, and the reaction time is about 2 to 12 hours.

[0145] When synthesizing the component (B1), various known radical polymerization initiators may be used. Examples of such radical polymerization initiators include azo-based polymerization initiators and peroxide-based polymerization initiators. The radical polymerization initiators may be used alone or in combination of two or more.

[0146] Examples of the azo-based polymerization initiator include azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylbutyronitrile) (e.g., Nippon Hydrazine Kogyo Co., Ltd., trade name "ABN-E"), and 2,2-azobis(2,4-dimethylvaleronitrile) (e.g., Nippon Hydrazine Kogyo Co., Ltd., trade name "ABN-V").

[0147] The azo-based polymerization initiator also includes, for example, a polyazo compound having a polyoxyethylene structure. Examples of the polyazo compound include those represented by the general formula (2):

[0148] [ka]

[0149] (wherein m1 represents an integer of 3 to 50, and n1 represents an integer of 3 to 200), and / or a polyazo compound having a structure represented by general formula (3):

[0150] [ka]

[0151] (wherein m2 is an integer of 3 to 50, and n2 is an integer of 3 to 200), and the like.

[0152] Commercially available polyazo compounds having the structure represented by the general formula (3) include, for example, the VPE series manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., such as "VPE-0201" (the number average molecular weight of the polyoxyethylene structural portion is approximately 2,000, n2 = approximately 45, m2 = approximately 10), "VPE-0401" (the number average molecular weight of the polyoxyethylene structural portion is approximately 4,000, n2 = approximately 90, m2 = approximately 7), and "VPE-0601" (the number average molecular weight of the polyoxyethylene structural portion is approximately 6,000, n2 = approximately 135, m2 = approximately 5).

[0153] Examples of the peroxide-based polymerization initiator include inorganic peroxides and organic peroxides. Examples of inorganic peroxides include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of organic peroxides include benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctoate, tert-butyl peroxybenzoate, lauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, and didodecanoyl peroxide (e.g., NOF Corporation, trade name "Perloyl (registered trademark) L").

[0154] The amount of the radical polymerization initiator used is not particularly limited, but is usually about 0.01 to 30% by mass relative to the total mass of components (b1') to (b3') and component (b4').

[0155] Furthermore, when synthesizing component (B1), a chain transfer agent such as lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, or bromotrichloromethane may be used. There are no particular restrictions on the amount used, but it is usually about 0.01 to 10% by mass based on the total mass of components (b1') to (b3') and component (b4').

[0156] For solution polymerization, organic solvents that can be used include glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; alcohols such as methanol, ethanol, and n-propanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; acetates such as ethyl acetate and butyl acetate; and chloroform and dimethylformamide. Among these, glycol ethers are preferred in terms of their ability to dissolve components (b1') to (b3') and component (b4'). For emulsion polymerization, various known anionic, nonionic, and cationic surfactants can be used.

[0157] The content of the component (B) in the active energy ray-curable resin composition is not particularly limited, but in terms of excellent antistatic properties, it is preferably about 1 to 20 parts by mass, converted into solid content, per 100 parts by mass of the active energy ray-curable resin composition.

[0158] <Poly(meth)acrylate (C) not having a carboxyl group in the molecule> The active energy ray-curable resin composition of the present invention may further contain a poly(meth)acrylate (C) (hereinafter referred to as component (C)) that does not have a carboxyl group in the molecule. The component (C) is not particularly limited as long as it is a compound that does not have a carboxyl group in the molecule and has at least two (meth)acryloyl groups in the molecule. The component (C) may be used alone or in combination of two or more types. Note that the component (C) does not include the component (A).

[0159] Examples of component (C) include the above-mentioned hydroxyl group-containing poly(meth)acrylate, di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, urethane poly(meth)acrylate, polyester poly(meth)acrylate, epoxy poly(meth)acrylate, polyether poly(meth)acrylate, and polyacryl poly(meth)acrylate.

[0160] Examples of the di(meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, and hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate.

[0161] (urethane poly(meth)acrylate) Examples of the urethane poly(meth)acrylate include a reaction product of a hydroxyl group-containing (meth)acrylate with the above polyisocyanate, and a reaction product of a hydroxyl group-containing (meth)acrylate with the above polyol and the above polyisocyanate.

[0162] Examples of the hydroxyl group-containing (meth)acrylate in the urethane poly(meth)acrylate include the hydroxyl group-containing mono(meth)acrylate and the hydroxyl group-containing poly(meth)acrylate.

[0163] The hydroxyl group-containing (meth)acrylate is preferably a hydroxyl group-containing (meth)acrylate having at least three (meth)acryloyl groups in the molecule, more preferably a hydroxyl group-containing (meth)acrylate having one hydroxyl group and at least three (meth)acryloyl groups in the molecule, from the viewpoint of excellent curability and scratch resistance of the cured film. The hydroxyl group-containing (meth)acrylate is preferably the hydroxyl group-containing pentaerythritol poly(meth)acrylate or the hydroxyl group-containing polypentaerythritol poly(meth)acrylate, from the viewpoint of excellent curability and scratch resistance of the cured film.

[0164] The polyisocyanate in the urethane poly(meth)acrylate is preferably a polyisocyanate having at least three isocyanate groups in the molecule, in order to provide a cured film with excellent scratch resistance. Preferred polyisocyanates having at least three isocyanate groups in the molecule include the biuret, isocyanurate, allophanate, and adduct.

[0165] In the urethane poly(meth)acrylate, the molar ratio (NCO:OH) of the isocyanate groups contained in the polyisocyanate to the hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate and the hydroxyl groups contained in the polyol is not particularly limited, but is preferably 1:1 to 10, and more preferably about 1:1 to 8, in order to obtain an excellent balance between the flexibility and scratch resistance of the cured film.

[0166] The method for producing the urethane poly(meth)acrylate is not particularly limited as long as it is a method of reacting the hydroxyl group-containing (meth)acrylate, the polyisocyanate, and, if necessary, the polyol, and various known production methods can be exemplified. Specific examples include a method of reacting the hydroxyl group-containing (meth)acrylate, the polyisocyanate, and, if necessary, the polyol in the presence of a catalyst at an appropriate reaction temperature (e.g., 60 to 90°C). The order in which the hydroxyl group-containing (meth)acrylate, the polyisocyanate, and the polyol are reacted is not particularly limited, and examples include a method of mixing and reacting them in any order, and a method of mixing and reacting all the components at once.

[0167] Examples of the catalyst include organic tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, organic acid tin catalysts such as tin octoate, organic titanium catalysts such as titanium ethylacetoacetate, organic zirconium catalysts such as zirconium tetraacetylacetonate, organic iron catalysts such as iron acetylacetonate, etc. The catalysts may be used alone or in combination of two or more.

[0168] (Polyester poly(meth)acrylate) Examples of the polyester poly(meth)acrylate include a dehydration condensate of the polyester polyol and (meth)acrylic acid.

[0169] (epoxy poly(meth)acrylate) Examples of the epoxy poly(meth)acrylate include compounds obtained by an addition reaction between the terminal epoxy groups of the epoxy resins and (meth)acrylic acid.

[0170] (Polyether poly(meth)acrylate) Examples of the polyether poly(meth)acrylate include a dehydration condensate of the polyether polyol and (meth)acrylic acid.

[0171] (Polyacrylic poly(meth)acrylate) Examples of the polyacrylpoly(meth)acrylate include a reaction product of an acrylic copolymer obtained by polymerizing the epoxy group-containing mono(meth)acrylate and, if necessary, a mono(meth)acrylate, with (meth)acrylic acid.

[0172] The component (C) is preferably a urethane poly(meth)acrylate, as this provides excellent antistatic properties in the cured film.

[0173] (Physical properties of poly(meth)acrylate (C) having no carboxyl group in the molecule) The physical properties of component (C) are not particularly limited. The number of (meth)acryloyl groups in the molecule of component (C) is preferably at least 3, as this provides a cured film with excellent scratch resistance.

[0174] The weight-average molecular weight (Mw) of component (C) is preferably about 500 to 100,000, in order to provide a cured film with excellent antistatic properties, scratch resistance, and moist heat resistance. The weight-average molecular weight of component (C) refers to a polystyrene-equivalent value measured by gel permeation chromatography, but the measurement method is not particularly limited, and various known means can be used, and commercially available measuring machines can also be used.

[0175] The content of the component (C) in the active energy ray-curable resin composition is not particularly limited, but in terms of providing a cured film with excellent antistatic properties, scratch resistance, and moist heat resistance, it is preferably about 0 to 85 parts by mass, calculated as solid content, per 100 parts by mass of the active energy ray-curable resin composition.

[0176] (reactive diluent) The active energy ray-curable resin composition of the present invention may contain a reactive diluent. The reactive diluent is a compound other than components (A) and (C) that has an active energy ray-reactive functional group such as a carbon-carbon unsaturated bond. One reactive diluent may be used alone, or two or more reactive diluents may be used in combination. The use of a reactive diluent in combination further improves the compatibility between components (A) and (B). As a result, the transparency of the active energy ray-curable resin composition is improved, and a cured film that is particularly excellent in antistatic properties, transparency, hardness, scratch resistance, etc. is obtained.

[0177] Examples of the reactive diluent include the components (b1') to (b3'), the mono(meth)acrylate containing an alkyl ester group having 19 or more carbon atoms, the aromatic ring structure-containing vinyl monomer, and ethyl carbitol acrylate.

[0178] When a reactive diluent is used in the above-mentioned active energy ray-curable resin composition, the total content of component (A), component (C), and reactive diluent in the composition is preferably about 80 to 97 mass % relative to 100 mass % of the composition.

[0179] In the active energy ray-curable resin composition, the content ratio of the components (A) and (C) to the reactive diluent is not particularly limited, but typically, when the total of the components (A), (C), and reactive diluent is taken as 100% by mass, the total amount of the components (A) and (C) is about 20 to 100% by mass, and the reactive diluent is about 0 to 80% by mass. However, considering the transparency of the resulting active energy ray-curable resin composition and the antistatic properties, transparency, hardness, and scratch resistance of the cured film, it is preferable that the total amount of the components (A) and (C) is about 50 to 95% by mass, and the reactive diluent is about 5 to 50% by mass.

[0180] (Photopolymerization initiator) The active energy ray-curable resin composition may contain a photopolymerization initiator. Two or more photopolymerization initiators may be used in combination. Examples of photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 4-methylbenzophenone. Note that a photopolymerization initiator is used when UV curing is performed, but is not necessarily required when electron beam curing is performed.

[0181] The content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited. From the viewpoint of the progress of the reaction of the (meth)acryloyl group, the content of the photopolymerization initiator is preferably about 0.5 to 15 parts by mass, calculated as solid content, per 100 parts by mass of the composition.

[0182] (solvent) The active energy ray-curable resin composition may contain a solvent in consideration of coating workability, etc. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol, acetylacetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. The dilution solvent may be used alone or in combination of two or more. In consideration of the surface smoothness of the cured film obtained from the composition, the solvent is preferably at least one selected from the group consisting of glycol ethers, alcohols, and ketones.

[0183] The content of the solvent in the active energy ray-curable resin composition is not particularly limited. When the composition contains a solvent, the content of the solvent is preferably in a range such that the solid content of the composition is about 1 to 60 wt % from the viewpoint of coatability.

[0184] (additives) The active energy ray-curable resin composition may contain, as necessary, an additive other than the solvent, reactive diluent, or photopolymerization initiator, as long as the effect of the present invention is not impaired. The additives may be used alone or in combination of two or more. Examples of the additives include antistatic agents other than component (B), antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifogging agents, hydrophilizing agents, antifouling agents, pigments, metal oxide fine particle dispersions, and organic fine particle dispersions.

[0185] The content of the additive in the active energy ray-curable resin composition is not particularly limited, but the content of the additive is preferably about 0 to 60 parts by mass, calculated as solid content, per 100 parts by mass of the composition.

[0186] [Cured film] The cured film of the present invention can be obtained from the active energy ray-curable resin composition. Specifically, for example, the composition can be applied to various substrate films in an amount of 0.05 to 30 g / m after drying. 2 Approximately, preferably 0.1 to 20 g / m 2 The composition is then applied to a thickness of about 1000 nm, dried, and then cured by irradiation with active energy rays such as ultraviolet rays, electron beams, or radioactive rays.

[0187] Examples of active energy rays used in the curing reaction include ultraviolet rays and electron beams. As a light source for ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. The light intensity, light source arrangement, transport speed, etc. can be adjusted as needed. For example, when using a high-pressure mercury lamp, curing is preferably carried out at a transport speed of about 5 to 50 m / min using one lamp with a lamp output of about 80 to 160 W / cm. On the other hand, when using electron beams, curing is preferably carried out at a transport speed of about 5 to 50 m / min using an electron beam accelerator with an acceleration voltage of about 10 to 300 kV.

[0188] [film] The film of the present invention includes the cured film described above. The film is an article having the cured film and various substrate films as constituent elements.

[0189] Examples of the substrate film include plastic films, and various known films can be used. Examples of the plastic film include polycarbonate films, polyester films, polyolefin films, polystyrene films, epoxy resin films, melamine resin films, triacetyl cellulose films, ABS resin films, AS resin films, acrylic resin films, and alicyclic polyolefin resin films. From the viewpoints of transparency and adhesion to the cured film, the plastic film is preferably one film selected from the group consisting of polycarbonate films, triacetyl cellulose films, acrylic resin films, and alicyclic polyolefin resin films. The average thickness of the substrate film is not particularly limited, but is usually about 20 to 1,000 μm, preferably 20 to 200 μm.

[0190] The film can be produced by various known methods. Examples of the method for producing the film include a method in which the active energy ray-curable resin composition is applied to at least one side of the substrate film, dried as necessary, and then irradiated with the active energy rays. Alternatively, a laminated film can be produced by applying the resin composition of the present invention to the uncoated side of the obtained substrate film, laminating another substrate film thereon, and then irradiating with the active energy rays.

[0191] Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

[0192] The amount of coating is not particularly limited, but the amount after drying is preferably 0.1 to 30 g / m 2 The preferred range is 1 to 20 g / m 2 The cured film formed on the substrate film usually has an average thickness of about 0.05 to 30 μm, and preferably about 0.1 to 20 μm. [Example]

[0193] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In the examples, "%" and "parts" mean "% by mass" and "parts by mass" unless otherwise specified.

[0194] The weight average molecular weights of the components (B1-1) and (B1-2) are actual values ​​measured under the following conditions using a commercially available molecular weight measuring device.

[0195] Molecular weight analyzer: Product name "HLC-8220GPC", 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 solution Flow rate: 0.5mL / min Sample concentration: 0.5g / L Standard material: Polyethylene oxide (TSKgel Standard Polyethylene Oxide SE-Kit, manufactured by Tosoh Corporation)

[0196] The weight average molecular weights of the components (b2-1), (C1), and (C2) are actual values ​​measured under the following conditions using a commercially available molecular weight measuring device.

[0197] Molecular weight analyzer: Product name "HLC-8220GPC", manufactured by Tosoh Corporation Columns: Product names "TSKGel G1000H" and "TSKGel G2000H", manufactured by Tosoh Corporation Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min, Sample concentration: 0.5g / L Standard material: Polystyrene (Standard polystyrene kit PStQuickA, B, C manufactured by Tosoh Corporation)

[0198] (Synthesis of component (b2)) Synthesis Example 1 130 parts of hydroxyethyl methacrylate, 1,140 parts of ε-caprolactone, and 1.3 parts of tin octoate were added to a reaction vessel equipped with a stirrer and a cooling tube, and the mixture was heated to 150°C. After maintaining the temperature for 6 hours, the mixture was cooled to obtain a ring-opening polyaddition product of a hydroxyl group-containing vinyl monomer and lactone having a weight-average molecular weight of 2,760 (hereinafter referred to as component (b2-1)).

[0199] <Synthesis of component (B1)> Manufacturing Example 1 In a reaction vessel similar to that used in Synthesis Example 1, 100 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) (hereinafter referred to as component (b1-1)), 60 parts of component (b2-1), 40 parts of tert-butyl methacrylate (t-BMA) (hereinafter referred to as component (b3-1)), and 800 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were added and heated to 80°C. Next, 8 parts of 2,2-azobis(2-methylbutyronitrile) (hereinafter referred to as ABN-E) and 32 parts of PGM were added to initiate the polymerization reaction. The mixture was then kept at 80°C for 3 hours, then at 113°C for 2 hours, after which it was cooled to obtain a solution of quaternary ammonium salt structure-containing polymer (B1-1) (20% nonvolatile content). The weight-average molecular weight of the resulting polymer was 220,000.

[0200] Manufacturing Example 2 In a reaction vessel similar to that used in Synthesis Example 1, 94 parts of component (b2-1), 24 parts of component (b3-1), 22 parts of a polyazo compound having a polyoxyethylene structure (manufactured by Wako Pure Chemical Industries, Ltd., trade name "VPE-0201"; a compound represented by the general formula (3) above; hereinafter referred to as VPE-0201), and 508 parts of PGM were added and heated to 80°C. Next, 100 parts of component (b1-1) and 455 parts of PGM were added and the mixture was kept at 80°C for 1 hour. Subsequently, 5 parts of VPE-0201 and 15 parts of PGM were added and the mixture was kept at 80°C for 1 hour. The mixture was then kept at 113°C for 2 hours, after which it was cooled to obtain a solution of a quaternary ammonium salt structure-containing polymer (B1-2) (non-volatile content: 20%). The weight-average molecular weight of the resulting polymer was approximately 210,000.

[0201] <Synthesis of Component (C) (Urethane Poly(meth)acrylate)> Manufacturing Example 3 A reaction vessel equipped with a stirrer, a condenser, a dropping funnel, and a nitrogen inlet tube was charged with 70 parts of isophorone diisocyanate (trade name "Vencorex IPDI" manufactured by Vencorex France), 0.03 parts of tin octoate, and 177 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Viscoat #300" manufactured by Osaka Organic Chemical Industry Ltd.), and the temperature inside the system was raised to approximately 80°C over approximately 1 hour. The reaction system was then maintained at this temperature for 1 hour and then cooled to obtain a mixture of urethane poly(meth)acrylate and unreacted monomers with a solids content of 100% by mass (urethane poly(meth)acrylate (C1), hereinafter referred to as component (C1)). The component (C1) was a mixture containing a urethane poly(meth)acrylate having nine (meth)acryloyl groups in the molecule, and the weight-average molecular weight of the urethane poly(meth)acrylate was 2,000.

[0202] Manufacturing Example 4 A reaction vessel equipped with a stirrer, a condenser, a dropping funnel, and a nitrogen inlet tube was charged with 70 parts of a biuret-modified hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation under the trade name "Duranate 24A-100"), 0.03 parts of tin octoate, and 177 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. under the trade name "NK Ester A-9550W"), and the temperature inside the system was raised to approximately 80°C over approximately 1 hour. The reaction system was then maintained at this temperature for 1 hour and then cooled to obtain a mixture of urethane poly(meth)acrylate and unreacted monomers with a solids content of 100% by mass (urethane poly(meth)acrylate (C2), hereinafter referred to as component (C2)). The component (C2) was a mixture containing a urethane poly(meth)acrylate having nine (meth)acryloyl groups in the molecule, and the weight-average molecular weight of the urethane poly(meth)acrylate was 44,000.

[0203] (Production of PEDOT / PSS dispersion) Comparative Manufacturing Example 1 100 g of PEDOT / PSS aqueous dispersion (Agfa-Gevaert Japan, product name "Orgacon ICP1010," 1.2% solids) was sprayed using a spray dryer (Yamato Scientific, product name "GA-32") at a spray pressure of 0.6 MPa and a drying temperature (inlet) of 150°C to obtain 0.9 g of a blue solid. Next, 95 g of ethanol was placed in a beaker, and 1.6 g of an amine alkylene oxide adduct (Lion Akzo, product name "Esomin C / 25") was added. 0.9 g of the blue solid was then added. The mixture was then treated at 18,000 rpm for 10 minutes using an emulsifier / disperser (M Technique, product name "Clearmix"), followed by 10 minutes of ultrasonic treatment at 400 W using an ultrasonic disperser (Ginsen, product name 19.6 kHz) to obtain a PEDOT / PSS dispersion (hereafter referred to as "component (B')").

[0204] <Preparation of active energy ray-curable resin composition> Example 1 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared by blending 12 parts of solution of component (B1-1), 88 parts of a reaction product of dipentaerythritol pentaacrylate and succinic anhydride (acid value 23 mgKOH / g, manufactured by Toagosei Co., Ltd., trade name "Aronix M-520") (hereinafter referred to as component (A2-1)), and 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV, trade name "Omnirad184") (hereinafter referred to as Omni184) in solids ratios, and diluting with methyl ethyl ketone (hereinafter referred to as MEK).

[0205] Example 2 A solution of 5 parts of the component (B1-1), 60 parts of the component (A2-1), 35 parts of the component (C1), and 5 parts of Omni184 was blended in a solids ratio and diluted with MEK to prepare an active energy ray-curable resin composition with a non-volatile content of 50%.

[0206] Example 3 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared in the same manner as in Example 2, except that in Example 2, 5 parts of a pentaerythritol triacrylate solution containing 20% ​​lithium bis(trifluoromethanesulfonyl)imide (manufactured by Sanko Chemical Industry Co., Ltd., product name "Sankonol PETA-20R") (hereinafter referred to as "component (B2)") was used instead of component (B1-1).

[0207] Example 4 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared by blending 10 parts of tri-n-butylmethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by 3M Japan Limited, trade name "FC-4400") (hereinafter referred to as "component (B3)"), 55 parts of component (A2-1), 35 parts of component (C1), and 5 parts of Omni184 in a solids content ratio, and diluting with MEK.

[0208] Example 5 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared in the same manner as in Example 2, except that in Example 2, 60 parts of a ring-opening addition reaction product of a copolymer of (meth)acrylic acid and a (meth)acrylic acid ester with 3,4-epoxycyclohexylmethyl (meth)acrylate (acid value 66 mgKOH / g, manufactured by Daicel Corporation, trade name "Cyclomer P(ACA)Z251") (hereinafter referred to as "component (A2-2)") was used instead of the component (A2-1).

[0209] Example 6 A mixture of 5 parts of the solution of component (B1-2), 10 parts of a reaction product of pentaerythritol triacrylate and succinic anhydride (acid value 97 mgKOH / g, manufactured by Toagosei Co., Ltd., trade name "Aronix M-510") (hereinafter referred to as component (A2-3)), 30 parts of component (C2), 30 parts of a hydroxyl group-containing polypentaerythritol polyacrylate (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 10 mgKOH / g, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "A-DPH") (hereinafter referred to as component (C3)), and 10 parts of ethyl carbitol acrylate (manufactured by Osaka Organic Chemical Industry Ltd., trade name "A-DPH") was used. 25 parts of Viscoat #190 (trade name) and 5 parts of Omni184 were mixed in a solid content ratio and diluted with MEK to prepare an active energy ray-curable resin composition with a nonvolatile content of 50%.

[0210] Example 7 An active energy ray-curable resin composition with a nonvolatile content of 50% was prepared by blending 7 parts of a solution of component (B1-1), 10 parts of acrylic acid (acid value 775 mgKOH / g) (hereinafter referred to as component (A1-1)), 33 parts of component (C1), 50 parts of a hydroxyl group-containing pentaerythritol polyacrylate (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value 125 mgKOH / g, manufactured by Osaka Organic Chemical Industry Ltd. under the trade name "Viscoat #300") (hereinafter referred to as component (C4)), and 5 parts of Omni184 in a solids ratio, and diluting with MEK.

[0211] Comparative Example 1 Five parts of the solution-like component (B1-1), 35 parts of the component (C1), 60 parts of the component (C4), and 5 parts of Omni184 were blended in a solids ratio, and the mixture was diluted with MEK to prepare an active energy ray-curable resin composition with a non-volatile content of 50%.

[0212] Comparative Example 2 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared in the same manner as in Comparative Example 1, except that in Comparative Example 1, 60 parts of a hydroxyl group-containing polypentaerythritol polyacrylate (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 90 mgKOH / g, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-9570W") (hereinafter referred to as "component (C5)") was used instead of the component (C4).

[0213] Comparative Example 3 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared by blending 30 parts of the component (A2-3), 40 parts of the component (C1), 30 parts of the component (C5), and 5 parts of Omni184 in a solids content ratio and diluting with MEK.

[0214] Comparative Example 4 An active energy ray-curable resin composition with a non-volatile content of 50% was prepared by blending 30 parts of the component (A2-1), 1 part of the PEDOT / PSS dispersion of Comparative Production Example 1, 39 parts of the component (C1), 30 parts of the component (C5), and 5 parts of Omni184 in a solids content ratio, and diluting with MEK.

[0215] [Table 1]

[0216] The blending amounts in Table 1 are values ​​in parts by mass converted into solid content. The annotations in Table 1 are as follows: *The cured film turned blue.

[0217] <Film Preparation> The active energy ray-curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were applied to a 100 μm-thick PET film (manufactured by Toray Industries, Inc., trade name "Lumirror 100U483") using a #15 bar coater so that the thickness of the cured film would be 5 μm, and the film was dried at 80°C for 1 minute to produce a film. The resulting film was then cured using an ultraviolet curing device (manufactured by Multiply Corporation, trade name "UBT-080-7A / BM") using a high-pressure mercury lamp at 600 mJ / cm. 2 ) was used to obtain a film with a cured coating. The evaluation results of the prepared film are shown in Table 1.

[0218] (Surface resistance test) The surface resistance (Ω / □) of the film immediately after production was measured using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Analytech Corporation, trade name "Hiresta MCP-HT-450") in accordance with JIS K 6911 at an applied voltage of 500V.

[0219] (Heat and humidity resistance test) The film was left standing for 24 hours in an environment at a temperature of 80° C. and a humidity of 95% Rh, and then the presence or absence of surface deposits on the film surface was visually confirmed. No surface deposits... Surface deposits present...×

[0220] (Appearance test) The appearance of the cured film in the above film was visually observed and evaluated according to the following criteria. A: A transparent and smooth cured film was obtained. ×: The cured film was cloudy or colored, or irregularities were observed on the cured film.

Claims

1. An active energy ray-curable resin composition comprising a carboxyl group-containing (meth)acrylate (A) and an ion-conductive compound (B), The active energy ray-curable resin composition contains 1 to 20 parts by mass of the component (B) relative to 100 parts by mass of the active energy ray-curable resin composition, the component (B) is a polymer (B1) having a quaternary ammonium salt structure, The polymer (B1) having a quaternary ammonium salt structure is a structural unit (b1) derived from a vinyl monomer having a quaternary ammonium salt structure; a ring-opening polyaddition product of a hydroxyl group-containing vinyl monomer and a lactone, a structural unit (b2) derived from a vinyl monomer having a weight average molecular weight of 1,000 to 10,000; and a structural unit (b3) derived from a vinyl monomer containing an alkyl ester group having 1 to 18 carbon atoms; An active energy ray-curable resin composition comprising a polymer comprising:

2. 2. The active energy ray-curable resin composition according to claim 1, wherein the acid value of the component (A) is 10 mgKOH / g or more.

3. 3. The active energy ray-curable resin composition according to claim 1, further comprising a poly(meth)acrylate (C) having no carboxyl group in the molecule.

4. 4. The active energy ray-curable resin composition according to claim 3, wherein the component (C) is a urethane poly(meth)acrylate.

5. A cured film comprising the active energy ray-curable resin composition according to any one of claims 1 to 4.

6. A film comprising the cured film of claim 5 .

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