1. An active energy ray-curable resin composition comprising:

a polymer (A) having a quaternary ammonium salt structure;

a polyfunctional (meth) acrylate (B) having a weight-average molecular weight (Mw) of 10,000 to 50,000, with the exception of the component (C); and

a hydroxyl group-containing (meth) acrylate (C) having a hydroxyl value of 50mgKOH/g to 200 mgKOH/g.

2. The active energy ray-curable resin composition according to claim 1, wherein the component (A) is a polymer comprising the following structural units:

structural units derived from a vinyl monomer having a quaternary ammonium salt structure (a 1);

structural units (a2) derived from a vinyl monomer which is a ring-opening addition polymer of a hydroxyl group-containing vinyl monomer and a lactone and has a weight average molecular weight of 1,000 to 10,000; and

a structural unit (a3) derived from a vinyl monomer having an alkyl ester group having 1 to 18 carbon atoms.

3. The active energy ray-curable resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the component (B) is 15,000 to 50,000.

4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the component (B) is a urethane (meth) acrylate.

5. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the hydroxyl value of the component (C) is from 90mgKOH/g to 150 mgKOH/g.

6. The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the component (C) is a hydroxyl group-containing (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule.

7. A cured film formed from the active energy ray-curable resin composition according to any one of claims 1 to 6.

8. A film comprising the cured film of claim 7.

Background

As a coating agent for various substrates, for example, a composition containing, as a main component, a compound having a plurality of (meth) acryloyl groups in a molecule (so-called active energy ray curable resin) such as pentaerythritol poly (meth) acrylate or ditrimethylolpropane poly (meth) acrylate has been known as a hard coating agent used for 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). The composition is instantly cured by irradiation with ultraviolet rays or electron beams, and therefore, has high productivity, and forms a cured film having excellent hardness and scratch resistance on the surface of various substrates.

However, when the active energy ray-curable resin composition is used for flat panel displays, the cured film thereof is required to have high transparency, and good antistatic properties are required to prevent troubles caused by static electricity during display assembly and operation and to realize high-definition images.

As a method for imparting antistatic properties to a cured film, 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, it is necessary to use a large amount of a conductive filler, and in such a case, transparency, hardness, and the like of the cured film may be adversely affected. As a method for imparting antistatic properties, an active energy ray curable resin composition containing an organic substance (pi-conjugated conductive polymer) such as poly (thiophene) or poly (aniline) may be used, but since these are generally strongly colored, there is still a problem in coloring of the cured film.

On the other hand, even in the case of a conductive polymer, if a polymer having a quaternary ammonium salt structure is used, the above-mentioned problem concerning coloring does not occur. Patent document 2 proposes an active energy ray-curable resin composition containing a polymer having a quaternary ammonium salt structure, and describes that a cured film having excellent antistatic properties and transparency can be obtained.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 9-051116

Patent document 2: japanese laid-open patent publication No. 2012-31297

Disclosure of Invention

Technical problem to be solved by the invention

However, the present inventors have found, after investigation, that the active energy ray-curable resin composition in patent document 2 may bleed out (ブリードアウト) from the obtained cured film under a high-temperature and high-humidity environment, and that the cured film may have a reduced transparency (haze) and a poor appearance, and that the cured film has a problem in terms of moisture and heat resistance.

The present invention addresses the problem of providing a novel active energy ray-curable resin composition that can provide a cured film having excellent antistatic properties and moist heat resistance.

Means for solving the problems

As a result of intensive studies by the present inventors, it was found that the above problems can be solved by a composition comprising a polymer having a quaternary ammonium salt structure, a polyfunctional (meth) acrylate having a specific weight average molecular weight, and a hydroxyl group-containing (meth) acrylate having a specific hydroxyl value (aquo-acid group value), and the present invention was completed.

Specifically, the present inventors have found that bleeding in a high-temperature and high-humidity environment is suppressed in a cured film obtained from a composition in which a polymer having a quaternary ammonium salt structure is combined with a polyfunctional (meth) acrylate having a high weight average molecular weight and a hydroxyl group-containing (meth) acrylate having a high hydroxyl value. The present inventors have also found that the above composition can form a cured film excellent in antistatic properties and scratch resistance. Namely, the present invention relates to the following active energy ray-curable resin composition, cured film and film.

1. An active energy ray-curable resin composition comprising:

a polymer (A) having a quaternary ammonium salt structure;

a polyfunctional (meth) acrylate (B) having a weight-average molecular weight (Mw) of 10,000 to 50,000 (excluding the component (C)); and

a hydroxyl group-containing (meth) acrylate (C) having a hydroxyl value of 50mgKOH/g to 200 mgKOH/g.

2. The active energy ray-curable resin composition according to the above item 1, wherein the component (A) is a polymer comprising the following structural units:

structural units derived from a vinyl monomer having a quaternary ammonium salt structure (a 1);

structural units derived from a vinyl monomer having a hydroxyl group-containing vinyl monomer and a lactone, the structural units being an open-ring addition polymer (a2) having an open-ring and a lactone, and having a weight-average molecular weight of 1,000 to 10,000; and

a structural unit (a3) derived from a vinyl monomer having an alkyl ester group having 1 to 18 carbon atoms.

3. The active energy ray-curable resin composition according to the above 1 or 2, wherein the weight average molecular weight (Mw) of the component (B) is 15,000 to 50,000.

4. The active energy ray-curable resin composition according to any one of the above items 1 to 3, wherein the component (B) is a urethane (meth) acrylate.

5. The active energy ray-curable resin composition according to any one of the above items 1 to 4, wherein the hydroxyl value of the component (C) is from 90mgKOH/g to 150 mgKOH/g.

6. The active energy ray-curable resin composition according to any one of the above items 1 to 5, wherein the component (C) is a hydroxyl group-containing poly (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule.

7. A cured film comprising the active energy ray-curable resin composition according to any one of the above items 1 to 6.

8. A film comprising the cured film as described in the above item 7.

Advantageous effects

The active energy ray-curable resin composition of the present invention can provide a cured film excellent in moist heat resistance since bleeding under a high-temperature and high-humidity environment is suppressed in the cured film obtained therefrom. Further, a cured film obtained from the active energy ray-curable resin composition is excellent in antistatic properties and also has excellent scratch resistance due to high hardness.

The active energy ray-curable resin composition can be suitably used as a coating agent for front panels of various flat panel displays because it can give a cured film excellent in antistatic properties, moist heat resistance and scratch resistance.

The film of the present invention is excellent in antistatic properties, moist heat resistance and scratch resistance, and therefore, is suitable for flat panel display applications such as liquid crystal displays, plasma displays and organic EL displays.

Detailed Description

[ active energy ray-curable resin composition ]

The active energy ray-curable resin composition of the present invention comprises: a polymer (a) having a quaternary ammonium salt structure (hereinafter referred to as component (a)); a polyfunctional (meth) acrylate (B) having a weight-average molecular weight (Mw) of 10,000 to 50,000 (excluding the component (C)) (hereinafter referred to as the component (B)); and a hydroxyl group-containing (meth) acrylate (C) (hereinafter referred to as component (C)) having a hydroxyl value of 50mgKOH/g to 200 mgKOH/g.

In the present specification, "(meth) acrylic acid" ("(メタ) アクリル") means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Likewise, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate", and "(meth) acryl" means "at least one selected from the group consisting of acryl and methacryl".

< Polymer (A) having Quaternary ammonium salt Structure >

(A) As the component (c), any known one may be used without particular limitation as long as it is a polymer having a quaternary ammonium salt structure. When the component (a) is a monomer having a quaternary ammonium salt structure and a carbon-carbon unsaturated double bond, the antistatic property and the moist heat resistance of the cured film are not sufficient, which is not preferable.

(A) Examples of the component (A) include polymers containing the following structural units: a structural unit (a1) derived from a vinyl monomer having a quaternary ammonium salt structure (hereinafter referred to as structural unit (a 1)); a structural unit (a2) (hereinafter referred to as structural unit (a2)) derived from a vinyl monomer which is a ring-opening addition polymer of a hydroxyl group-containing vinyl monomer and a lactone and has a weight average molecular weight of 1,000 to 10,000; a structural unit (a3) (hereinafter referred to as a structural unit (a3)) derived from a vinyl monomer having an alkyl ester group having 1 to 18 carbon atoms.

The structural unit (a1) is a structural unit contained in a polymer chain when a polymer is produced using a vinyl monomer (a1 ') having a quaternary ammonium salt structure (hereinafter referred to as (a 1') component). The component (a 1') may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The component (a 1') is not particularly limited and various known vinyl monomers having a quaternary ammonium salt structure in the molecule can be used. Specifically, for example, a (meth) acrylate compound represented by the following general formula (1):

[CH₂＝C(R¹)-C(＝O)-A-B-N⁺(R²)(R³)(R⁴)]_n·X^n-

(in the formula, R¹Represents H or CH₃，R²～R⁴Represents 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, and n represents an integer of 1 or more). Further, X^n-Mention of Cl^-、SO₄ ^2-、SO₃ ^2-、C₂H₅SO₄ ^-、Br^-Etc., Cl is preferable from the viewpoint of antistatic effect^-. Further, commercially available products of component (a 1') include, for example, "LIGHT ESTER (ライトエステル) DQ-100" manufactured by Kyoeisha chemical Co., Ltd, "DMAEA-Q" manufactured by Kyoeisha Co., Ltd.

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. 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.

(A) The content of the structural unit (a1) in the component (a) is not particularly limited, but is preferably about 30 to 60 mass% with respect to 100 mass% of the component (a) from the viewpoint of excellent transparency and antistatic property of the cured film.

The structural unit (a2) is a structural unit contained in a polymer chain in the production of a polymer using a vinyl monomer (a2 ') having a weight average molecular weight of 1,000 to 10,000 (hereinafter referred to as (a 2') component) which is a ring-opening addition polymer of a hydroxyl group-containing vinyl monomer and a lactone. The component (a 2') may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The component (a 2') is produced by ring-opening addition polymerization using a hydroxyl group-containing vinyl monomer and a lactone by a known method. The hydroxyl-containing vinyl monomers can be used singly in 1 type, or in combination in 2 or more types; similarly, 1 kind of lactone may be used alone, or 2 or more kinds may be used in combination.

The hydroxyl group-containing vinyl monomer may be any of various known monomers without particular limitation. Specifically, for example, a hydroxyl group-containing (meth) acrylic compound, a hydroxyl group-containing vinyl ether, and the like are mentioned. Among them, from the viewpoint of radical copolymerizability, a hydroxyl group-containing (meth) acrylic compound is preferable.

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

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

The lactone may be any of various known ones without particular limitation. Specific examples thereof include β -propiolactone, γ -butyrolactone, δ -valerolactone, β -methyl- δ -valerolactone, and ∈ -caprolactone. Among them, from the viewpoint of reactivity of ring-opening polymerization, 1 kind selected from the group consisting of epsilon-caprolactone and delta-valerolactone is preferable.

The component (a 2') has a weight average molecular weight (Mw) of 1,000 to 10,000. When the weight average molecular weight is less than 1,000, the antistatic property and the moist heat resistance of the cured film tend to be lowered. When the weight average molecular weight exceeds 10,000, the synthesis of the component (a 2') becomes difficult. The weight average molecular weight is preferably about 1,000 to 5,000 from the viewpoint of excellent transparency, antistatic property, scratch resistance and moist heat resistance of the cured film and easy synthesis. In the present specification, the weight average molecular weight of the component (a 2') is a polystyrene equivalent value in gel permeation chromatography, but the measurement method is not particularly limited, and various known methods may be used or a commercially available measuring instrument may be used.

(A) The content of the structural unit (a2) in the component (a) is not particularly limited, but is preferably about 25 to 55 mass% with respect to 100 mass% of the component (a) from the viewpoint of excellent transparency and scratch resistance of the cured film.

The component (a 2') can be obtained by various known methods. Specifically, for example, a method of ring-opening addition polymerization of the lactone using the hydroxyl group-containing vinyl monomer as an initiator is exemplified. The weight average molecular weight can be adjusted by appropriately selecting the charging ratio of the catalyst and the catalyst, the reaction temperature, and the type and amount of the catalyst during the reaction.

In carrying out the above reaction, a catalyst may be used. Examples of the catalyst include inorganic 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 alkoxide compounds such as titanium tetrabutoxide; and tin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin mercaptide (ジブチルスズメルカプチド), and tin octylate. The amount of the catalyst used is not particularly limited, but is preferably about 0.01 to 10% by mass based on 100% by mass of the total of the hydroxyl group-containing vinyl monomer and the lactone.

The structural unit (a3) is a structural unit contained in a polymer chain in the production of a polymer using a vinyl monomer (a3 ') having an alkyl ester group having 1 to 18 carbon atoms (hereinafter referred to as component (a 3'). The component (a 3') may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In addition, the component (a 3') preferably does not have an alicyclic structure from the viewpoint of satisfactory compatibility (compatibility) between the component (a) and the component (B) and the component (C) and the reactive diluent described later, and in this case, the structural unit (a3) does not have an alicyclic structure.

The component (a 3') is not particularly limited and various known vinyl monomers can be used as long as they have an alkyl ester group having 1 to 18 carbon atoms. In the present specification, the term "alkyl ester group having 1 to 18 carbon atoms" refers to an ester group represented by — C (═ O) -O — R, wherein R is an alkyl group having 1 to 18 carbon atoms.

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 dodecyl ester group, a tridecyl ester group, a tetradecyl ester group, a pentadecyl ester group, a hexadecyl ester group, a heptadecyl ester group, an octadecyl ester group, an isopropyl ester group, an isobutyl ester group, a sec-butyl ester group, 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, a1, 1-dimethylpropyl ester group, a1, 2-dimethylpropyl ester group, a2, 2-dimethylpropyl ester group, an isopentyl ester group, an isododecyl ester group, an isotridecyl ester group, an isotetradecyl ester group, an ester group, a heptadecyl ester group, an octadecyl ester group, an isopropyl ester group, a methyl ester group, a, An isopentadecanyl ester group, an isohexadecyl ester group, an isoheptadecyl ester group, and an isooctadecyl ester group.

The component (a 3') includes, for example, the above-mentioned mono (meth) acrylate having an alkyl ester group having 1 to 18 carbon atoms.

Examples of the mono (meth) acrylate containing the 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, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, and the like, Isoamyl (meth) acrylate, methylbutyl (meth) acrylate, isododecyl (meth) acrylate, isotridecyl (meth) acrylate, isotetradecyl (meth) acrylate, isotentadecyl (meth) acrylate, isocetyl (meth) acrylate, isoheptadecyl (meth) acrylate, and isostearyl (meth) acrylate.

By containing the structural unit (a3) in the component (a), the cured film containing the component (a) has good antistatic properties over time. For the same reason, the component (a 3') is particularly preferably 1 selected from the group consisting of t-butyl (meth) acrylate and isobutyl (meth) acrylate.

(A) The content of the structural unit (a3) in the component (a) is not particularly limited, but is preferably about 5 to 30% by mass based on 100% by mass of the component (a) from the viewpoint of excellent transparency and scratch resistance of the cured film.

(A) Component (b) may further contain a structural unit (a4) (hereinafter also referred to as a structural unit (a4)) other than the structural units (a1) to (a 3). The structural unit (a4) is a structural unit contained in a polymer chain in the production of a polymer using a monomer (a4 ') other than the above-mentioned monomer (a 1') to monomer (a3 ') (hereinafter, also referred to as a (a 4') component). The component (a 4') may be used in combination of 2 or more.

Examples of the component (a 4') include mono (meth) acrylates and aromatic ring structure-containing vinyl monomers which do not correspond to the component (a 3).

Examples of the mono (meth) acrylate not corresponding to the component (a3) include mono (meth) acrylates containing an alkyl ester group having 19 or more carbon atoms.

Examples of the mono (meth) acrylate having 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, ditetradecyl (meth) acrylate, pentacosyl (meth) acrylate, hexacosyl (meth) acrylate, heptacosyl (meth) acrylate, and dioctadecyl (meth) acrylate.

Examples of the vinyl monomer having an aromatic ring structure include styrene, α -methylstyrene and 4-methylstyrene.

(A) The content of the structural unit (a4) in the component (a) is not particularly limited, but is preferably about 0 to 20% by mass based on 100% by mass of the component (a) from the viewpoint of excellent antistatic properties, moist heat resistance and transparency of the cured film.

(A) The content ratio of the structural units (a1) to (a3) in the component (a) is not particularly limited, but is preferably (35 to 45): 5 to 15) (mass ratio) in order from the viewpoints of compatibility of the component (a) with the component (B) and the component (C) with a reactive diluent, which will be described later, and antistatic properties and transparency of the cured film. When the component (A) contains the structural unit (a4), the content ratio of the structural unit (a1) to the structural unit (a4) in the component (A) is not particularly limited, and for the same reason, it is preferably (35 to 45), (5 to 15), (0 to 15) (mass ratio) or so.

< physical Properties of Polymer (A) having Quaternary ammonium salt Structure and production method >

(A) The physical properties of the components are not particularly limited. (A) The weight average molecular weight (Mw) of the component (B) is preferably 300,000 or less, more preferably about 150,000 to 300,000. When the weight average molecular weight is 150,000 or more, bleeding of the antistatic agent from the cured film is further suppressed, and thus the moisture-heat resistance of the cured film becomes more excellent. When the weight average molecular weight is 300,000 or less, the compatibility of the component (a) with the component (B), the component (C) and a reactive diluent described later becomes more excellent, and thus the transparency of the cured film becomes more excellent. The weight average molecular weight of the component (a) is a polyethylene oxide equivalent in gel permeation chromatography, but the measurement method is not particularly limited, and various known methods can be used, or a commercially available measuring instrument can be used.

(A) The component (c) can be obtained by radical copolymerization of the above-mentioned component (a1 '), (a 2'), (a3 ') and, if necessary, (a 4') by various known methods (bulk polymerization, solution polymerization, emulsion polymerization, etc.). The reaction temperature is usually about 40 ℃ to 160 ℃ and the reaction time is about 2 hours to 12 hours.

In synthesizing the component (a), various known radical polymerization initiators can be used. Examples of such a radical polymerization initiator include an azo polymerization initiator, a peroxide polymerization initiator, and the like. The radical polymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the azo polymerization initiator include Azobisisobutyronitrile (AIBN), 2-azobis (2-methylbutyronitrile) [ for example, manufactured by NIPPHIAZO INDUSTRY (ヒドラジン, Inc. , Inc.; product name "ABN-E"), and 2, 2-azobis (2, 4-dimethylvaleronitrile) [ for example, manufactured by NIPPHIAZO INDUSTRY, product name "ABN-V", and the like ].

Examples of the peroxide-based polymerization initiator include inorganic peroxides and organic peroxides. Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the organic peroxide include benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide (ジクミルパーオキサイド), t-butyl hydroperoxide, cumene hydroperoxide (クメンハイドロパーオキサイド), t-butyl peroctoate, t-butyl peroxobenzoate, lauroyl peroxide, t-butyl peroxy-2-ethylhexanoate (tert- ブチルパーオキシ -2- エチルヘキサノエート), and dilauroyl peroxide [ for example, manufactured by Nichigan corporation, product name "PEROYL (パーロイル, registered trademark) L", etc. ].

The amount of the radical polymerization initiator used is not particularly limited, but is usually about 0.01 to 30% by mass based on the total mass of the components (a1 ') to (a3 ') and (a4 ').

In the synthesis of component (A), a chain transfer agent such as lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, or the like may be used. The amount of the chain transfer agent to be used is not particularly limited, but is usually about 0.01 to 10% by mass based on the total mass of the components (a1 ') to (a3 ') and (a4 ').

In the case of solution polymerization, 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; chloroform, dimethylformamide and the like. Among them, glycol ethers are preferable from the viewpoint of the dissolving power of the components (a1 ') to (a3 ') and (a4 '). In addition, in the case of emulsion polymerization, various known anionic, nonionic, and cationic surfactants can be used.

The content of the component (a) in the active energy ray-curable resin composition is not particularly limited, and is preferably about 5 to 20 parts by mass in terms of solid content with respect to 100 parts by mass of the active energy ray-curable resin composition, from the viewpoint of excellent antistatic properties.

< polyfunctional (meth) acrylate (B) >

(B) The component (C) is not particularly limited as long as it is a compound having a weight average molecular weight (Mw) of 10,000 to 50,000 and at least 2 (meth) acryloyl groups in the molecule. The component (B) does not include the component (C) described later. In the present specification, the weight average molecular weight of the component (B) is a polystyrene equivalent value in gel permeation chromatography, but the measurement method is not particularly limited, and various known methods may be used, or a commercially available measuring instrument may be used.

Conventionally, in order to obtain a cured film having antistatic properties while suppressing bleeding from the cured film, it is preferable to use a low-molecular-weight polyfunctional (meth) acrylate or a hydroxyl group-containing (meth) acrylate having a low hydroxyl value, and to use a low-molecular-weight polyfunctional (meth) acrylate or a hydroxyl group-containing (meth) acrylate having a high hydroxyl value in a small amount, in an active energy ray-curable resin composition containing a compound having a quaternary ammonium salt structure. However, the present inventors have conducted extensive studies and found that the use of a component (B) having a high molecular weight and a component (C) having a high hydroxyl value in combination in a composition containing a component (a) suppresses bleeding from a cured film in a high-temperature and high-humidity environment, and that the cured film is excellent in antistatic properties and scratch resistance.

(B) When the weight average molecular weight of the component (a) is 10,000 or more, the above-mentioned bleeding is suppressed, and the cured film is excellent in moist heat resistance. When the weight average molecular weight is 50,000 or less, the cured film has excellent transparency because the component (B) has excellent compatibility with other components.

The weight average molecular weight (Mw) of the component (B) is preferably 15,000 or more, and more preferably 30,000 or more, from the viewpoint of excellent wet heat resistance of the cured film. The weight average molecular weight (Mw) of the component (B) is preferably about 15,000 to 50,000, more preferably 30,000 to 50,000, from the viewpoint of excellent moisture and heat resistance of the cured film.

(B) The component (B) includes, for example, an oligomer having at least 2 (meth) acryloyl groups in the molecule. (B) Examples of the component (A) include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyacrylic (meth) acrylate, and polyvinyl (meth) acrylate. (B) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(urethane (meth) acrylate)

Examples of the urethane (meth) acrylate include a reaction product of a hydroxyl group-containing (meth) acrylate and a polyisocyanate; hydroxyl group-containing (meth) acrylates, reactants of polyols and polyisocyanates, and the like.

The hydroxyl group-containing (meth) acrylate is not particularly limited, and various known compounds can be used as long as the compound has at least 1 hydroxyl group and at least 1 (meth) acryloyl group in the molecule. The hydroxyl group-containing (meth) acrylate may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The hydroxyl group-containing (meth) acrylate may be the same as the component (C) described later.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxyl group-containing glycerol (meth) acrylate, hydroxyl group-containing polyglycerol poly (meth) acrylate, hydroxyl group-containing pentaerythritol poly (meth) acrylate, hydroxyl group-containing polypentaerythritol poly (meth) acrylate, hydroxyl group-containing trimethylolpropane poly (meth) acrylate, hydroxyl group-containing mono (meth) acrylate, and the like.

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

Examples of the above-mentioned hydroxyl group-containing polyglycerol poly (meth) acrylate include diglycerol di (meth) acrylate, diglycerol tri (meth) acrylate, triglycerol di (meth) acrylate, triglycerol tri (meth) acrylate, triglycerol tetra (meth) acrylate, and the like.

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, and 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, and the like.

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 kinds selected from these (meth) acrylates; mixtures of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and the like.

Examples of the above-mentioned hydroxyl group-containing trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate, ethylene oxide-modified trimethylolpropane di (meth) acrylate, propylene oxide-modified trimethylolpropane di (meth) acrylate and the like.

Examples of the above-mentioned hydroxyl group-containing polytrimethylolpropane poly (meth) acrylate include ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate and the like.

Examples of the hydroxyl group-containing mono (meth) acrylate include hydroxyl group-containing linear alkyl (meth) acrylates, hydroxyl group-containing branched alkyl (meth) acrylates, hydroxyl group-containing cycloalkyl (meth) acrylates, polyalkylene glycol mono (meth) acrylates, and caprolactone adducts of these mono (meth) acrylates.

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

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

Examples of the above-mentioned cycloalkyl (meth) acrylate containing a hydroxyl group include hydroxycyclohexyl (meth) acrylate and the like.

The polyalkylene glycol mono (meth) acrylate includes (meth) acrylates having an oxyalkylene chain (オキシアルキレン lock), 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 of a random structure such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate.

The hydroxyl group-containing (meth) acrylate is preferably a hydroxyl group-containing (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule, and more preferably a hydroxyl group-containing (meth) acrylate having 1 hydroxyl group and at least 3 (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 multi (meth) acrylate or the hydroxyl group-containing polypentaerythritol multi (meth) acrylate, from the viewpoint of excellent curability and scratch resistance of the cured film.

The polyisocyanate is not particularly limited, and any known polyisocyanate may be used as long as it has at least 2 isocyanate groups in the molecule. The polyisocyanate may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

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 (アダクト form); and a complex obtained by reacting two or more selected from the group consisting of a biuret form, an isocyanurate form, an allophanate form and an adduct form.

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.

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

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.

Examples of the aromatic diisocyanate include dialkyl diphenylmethane diisocyanates such as 4, 4' -diphenyldimethylmethane diisocyanate; tetraalkyldiphenylmethane diisocyanates such as 4, 4' -diphenyltetramethylmethane diisocyanate; 4,4 '-diphenylmethane diisocyanate, 4' -dibenzyl diisocyanate, 1, 3-phenylene diisocyanate (1, 3- フェニレンジイソシアネート), 1, 4-phenylene diisocyanate, toluene diisocyanate (トリレンジイソシアネート), xylylene diisocyanate (キシリレンジイソシアネート), m-tetramethylxylylene diisocyanate (m- テ ト ラ メ チ ル キシリレンジイソシアネート), 1, 5-naphthalene diisocyanate (1, 5- ナフチレンジイソシアネート) and the like.

The biuret form of the diisocyanate includes compounds represented by the following structural formula:

[ solution 1]

{ formula (II) wherein n^bIs an integer of 1 or more; r^bA～R^bEEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; r^bα～R^bβEach independently is an isocyanate group or

[ solution 2]

(n^b1Is an integer of 0 or more; r^b1～R^b5And R^bA～R^bEThe same; r^b’～R^bEach independently isIsocyanate group or R^bα～R^bβA group of itself. For each structural unit, R^b4～R^b5、R^bThe "groups may also be different. )

For each structural unit, R^bD～R^bE、R^bβThe groups of (a) may also be different. }.

Specifically, examples of the biuret form of the diisocyanate include Duranate (デュラネ - ト)24A-100 and Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei corporation, supra); desmodur (デスモジュール) N3200A (biuret form of hexamethylene diisocyanate) (manufactured by Sumitomo バイエルウレタン, Inc.) and the like.

The isocyanurate form of the diisocyanate includes a compound represented by the following structural formula:

[ solution 3]

{ formula (II) wherein nⁱIs an integer of 0 or more; r^iA～R^iEEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; r^iα～R^iβEach independently is an isocyanate group or

[ solution 4]

(nⁱ¹Is an integer of 0 or more; rⁱ¹～Rⁱ⁵And R^iA～R^iEThe same; rⁱ’～Rⁱ"are each independently an isocyanate group or R^iα～R^iβA group of itself. For each structural unit, Rⁱ⁴～Rⁱ⁵、RⁱThe "groups may also be different. )

For each structural unit, R^iD～R^iE、R^iβThe groups of (a) may also be different. }.

Specifically, the isocyanurate form of the diisocyanate includes Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate MHG-80B (manufactured by Asahi Kasei corporation); coronate (コロネート) HXR, Coronate HX (above in the form of the isocyanurate of hexamethylene diisocyanate) (above manufactured by imperial ソー strain); takenate (タケネート) D-127N (isocyanurate form of hydrogenated xylylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.); VESTANAT T1890/100 (isocyanurate form of isophorone diisocyanate) (manufactured by Evonik Japan (エボニック. ジャパン, Inc.) and the like.

The allophanate form of the diisocyanate includes a compound represented by the following structural formula:

[ solution 5]

{ formula (II) wherein n^aIs an integer of 0 or more; r^aAIs an alkyl group, an aryl group, a polyether group, a polyester group or a polycarbonate group; r^aB～R^aGEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; r^aα～R^aγEach independently is an isocyanate group or

[ solution 6]

(n^a1Is an integer of 0 or more; r^a1～R^a6And R^aB～R^aGThe same; r^a’～R^a"' are each independently an isocyanate group or R^aα～R^aγA group of itself. For each structural unit, R^a1～R^a4、R^a’～R^aThe "groups may also be different. )

For each structural unit, R^aB～R^aE、R^aα～R^aβThe groups of (a) may also be different. }.

Specifically, examples of the allophanate form of the diisocyanate include Coronate 2793 (manufactured by Egyptian ソー Co., Ltd.), Takenate D-178N (manufactured by Mitsui chemical Co., Ltd.), and the like.

The above adduct form of the above diisocyanate is exemplified by an adduct form of trimethylolpropane and diisocyanate represented by the following structural formula:

[ solution 7]

{ formula (II) wherein n^adIs an integer of 0 or more; r^adA～R^adEEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; r^ad1～R^ad2Each independently is

[ solution 8]

(in the formula, n^ad’Is an integer of 0 or more; r^ad’～R^adAnd R^adA～R^adEThe same; r^ad”^’Is R^ad1～R^ad2A group of itself; for each structural unit, R^ad’～R^ad”^’The groups of (a) may also be different. ) For each structural unit, R^adD～R^adE、R^ad2The groups of (a) may also be different. };

an adduct form of glycerol and a diisocyanate represented by the following structural formula:

[ solution 9]

{ formula (II) wherein n^ad1Is an integer of 0 or more; r^adα～R^adεEach independently is any one of a straight-chain aliphatic diisocyanate residue, a branched-chain aliphatic diisocyanate residue, an alicyclic diisocyanate residue and an aromatic diisocyanate residue; r^adA～R^adBEach independently is

[ solution 10]

(in the formula, n^ad1’Is an integer of 0 or more; r^adδ’～R^adε’And R^adα～R^adεThe same; r^adB’Is R^adA～R^adBA group of itself; for each structural unit, R^adδ’～R^adε’、R^adB’The groups of (a) may also be different. ) For each structural unit, R^adδ～R^adε、R^adBThe groups of (a) may also be different. And so on.

Specifically, the adduct form of the diisocyanate is Duranate P301-75E (manufactured by Asahi Kasei corporation, supra); takenate D-110N and Takenate D-160N (manufactured by Mitsui Chemicals, Inc.); coronate L and Coronate HL (manufactured by imperial ソー, imperial arts).

In the above formulae, the expression "straight-chain aliphatic diisocyanate residue, branched-chain aliphatic diisocyanate residue, alicyclic diisocyanate residue and aromatic diisocyanate residue" means the remaining groups of the straight-chain aliphatic diisocyanate, the branched-chain aliphatic diisocyanate, the alicyclic diisocyanate and the aromatic diisocyanate except the isocyanate group.

The polyisocyanate is preferably a polyisocyanate having at least 3 isocyanate groups in the molecule, from the viewpoint of excellent scratch resistance of the cured film. The polyisocyanate having at least 3 isocyanate groups in the molecule is preferably the biuret form, the isocyanurate form, the allophanate form, or the adduct form.

The polyol is not particularly limited, and various known compounds can be used as long as the polyol has at least 2 hydroxyl groups in the molecule. The above polyols may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

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

Examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2-diethyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-tetramethylene glycol, aliphatic alcohols having 2 hydroxyl groups such as 1, 3-tetramethylene glycol, 2-methyl-1, 3-trimethylene glycol, 1, 5-pentamethylene glycol, 1, 6-hexamethylene glycol, 3-methyl-1, 5-pentamethylene glycol, 2, 4-diethyl-1, 5-pentamethylene glycol, pentaerythritol diacrylate, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, etc.; sugar alcohols such as xylitol and sorbitol; and aliphatic alcohols having 3 or more hydroxyl groups such as glycerin, trimethylolpropane and trimethylolethane.

Examples of the alicyclic polyhydric alcohol include cyclohexanediols such as 1, 4-cyclohexanediol and cyclohexyldimethanol; hydrogenated bisphenols such as hydrogenated bisphenol a; tricyclodecanedimethanol and the like.

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

Examples of the polyester-based polyol include polycondensates of a polyol and a polycarboxylic acid or an anhydride thereof; ring-opening polymers of cyclic esters (lactones); and a reaction product of three components of a polyhydric alcohol, a polybasic carboxylic acid or an acid anhydride thereof, and a cyclic ester thereof.

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

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; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, p-phenylenedicarboxylic acid (パラフェニレンジカルボン acid) and trimellitic acid (トリメリット acid), and anhydrides thereof.

Examples of the cyclic ester include propiolactone, β -methyl- δ -valerolactone, and ∈ -caprolactone.

Examples of the polycarbonate-series polyol include a reaction product of a polyol and phosgene; ring-opening polymers of cyclic carbonates (alkylene carbonates, etc.), and the like.

Examples of the polyol include the polyols exemplified in the polyester polyols; examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

The polycarbonate polyol may have an ester bond together with a carbonate bond, as long as it is a compound having a carbonate bond in the molecule and a hydroxyl group at the end.

Examples of the polyolefin-based polyol include compounds having a homopolymer or copolymer of ethylene, propylene, butene, or the like as a saturated hydrocarbon skeleton and having a hydroxyl group at a molecular terminal thereof.

Examples of the polybutadiene polyol include compounds having a copolymer of butadiene as a hydrocarbon skeleton and having a hydroxyl group at a molecular terminal thereof. The polybutadiene-based polyol may also be a hydrogenated polybutadiene polyol in which all or a part of the ethylenically unsaturated groups contained in the structure thereof has been hydrogenated.

Examples of the (meth) acrylic polyol include compounds having at least 2 hydroxyl groups in the molecule of a polymer or copolymer of a (meth) acrylate ester. Examples of the (meth) acrylic acid ester include alkyl (meth) acrylates 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.

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

The method for producing the urethane (meth) acrylate is not particularly limited as long as it is a method of reacting the hydroxyl group-containing (meth) acrylate, the polyisocyanate, and the polyol as needed, and various known production methods are exemplified. Specifically, for example, a method of reacting a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and a polyol as needed in the presence of a catalyst at an appropriate reaction temperature (for example, 60 to 90 ℃ C.). The order of reacting the hydroxyl group-containing (meth) acrylate, the polyisocyanate and the polyol is not particularly limited, and examples thereof include a method of optionally mixing and reacting each of the components, a method of mixing all the components together and reacting the components, and the like.

Examples of the catalyst include organotin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; organic acid tin catalysts such as tin octylate; organic titanium catalysts such as titanium ethylacetoacetate; organic zirconium catalysts such as zirconium tetraacetylacetonate; organic iron catalysts such as iron acetylacetonate, and the like. The catalyst can be used alone in 1, also can be combined with more than 2.

(polyester (meth) acrylate)

Examples of the polyester (meth) acrylate include dehydration condensates of polyester polyols and (meth) acrylic acid. Examples of the polyester polyol include the polyester polyols described above.

(epoxy (meth) acrylate)

Examples of the epoxy (meth) acrylate include compounds obtained by an addition reaction between a terminal epoxy group of an epoxy resin and (meth) acrylic acid. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

Examples of the aromatic epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin, phenol novolac type epoxy resin (フェノールノボラック type エポキシ colophony), cresol novolac type epoxy resin (クレゾールノボラック type エポキシ colophony), bisphenol a novolac type epoxy resin, naphthalene diol type epoxy resin, phenol dicyclopentadiene novolac type epoxy resin, and hydrogenated products thereof.

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; diglycidyl ethers or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerol and alkylene oxide adducts thereof; and polyglycidyl ethers of polyhydric alcohols such as diglycidyl ether, triglycidyl ether, and tetraglycidyl ether of pentaerythritol and alkylene oxide adducts thereof; diglycidyl ethers or polyglycidyl ethers of hydrogenated bisphenol a and alkylene oxide adducts thereof; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.

(polyether (meth) acrylate)

Examples of the polyether (meth) acrylate include dehydration condensates of polyether polyol and (meth) acrylic acid; examples of the polyether polyol include the above polyether polyols. Examples of the polyether (meth) acrylate include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.

(polyacrylic acid (meth) acrylate)

Examples of the polyacrylic acid (meth) acrylate include homopolymers of epoxy group-containing mono (meth) acrylates and reaction products of copolymers of epoxy group-containing mono (meth) acrylates with other monomers and (meth) acrylic acid.

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 (ビニルシクロヘキセンモノオキサイド) (i.e., 1, 2-epoxy-4-vinylcyclohexane).

(polyvinyl (meth) acrylate)

Examples of the polyvinyl (meth) acrylate include vinyl polymers of vinyl-containing (meth) acrylates, vinyl copolymers of vinyl-containing (meth) acrylates with other monomers, and the like.

Examples of the vinyl group-containing (meth) acrylate include vinyl ether group-containing (meth) acrylates and the like. Examples of the vinyl ether group-containing (meth) acrylate include 2-vinyloxyethyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexyl methyl (meth) acrylate, p-vinyloxymethylphenyl methyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- [2- (2-vinyloxyethoxy) ethoxy ] ethyl (meth) acrylate, and mixtures thereof, 2- (2-vinyloxypropyloxy) propyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) isopropyl (meth) acrylate, polyethylene glycol monovinyl ether (meth) acrylate, polypropylene glycol monovinyl ether (meth) acrylate, and the like.

The component (B) is preferably urethane (meth) acrylate from the viewpoint of excellent antistatic properties and moist heat resistance of the cured film.

(physical Properties of polyfunctional (meth) acrylate (B))

(B) Physical properties other than the weight average molecular weight of the component are not particularly limited. The component (B) is preferably a compound having at least 3 (meth) acryloyl groups in the molecule, from the viewpoint of excellent scratch resistance of the cured film.

The content of the component (B) in the active energy ray-curable resin composition is not particularly limited, and is preferably about 20 to 60 parts by mass in terms of solid content with respect to 100 parts by mass of the active energy ray-curable resin composition, from the viewpoint of excellent scratch resistance of the cured film.

< hydroxyl group-containing (meth) acrylate (C) >

(C) As the component (B), any known compound can be used without particular limitation as long as it has a hydroxyl value (JIS K0070; the same applies to the hydroxyl value hereinafter) of 50mgKOH/g to 200mgKOH/g and has at least 1 hydroxyl group and at least 1 (meth) acryloyl group in the molecule. (C) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(C) When the hydroxyl value of the component (B) is 50mgKOH/g or more, the above-mentioned bleeding is suppressed, and the cured film is excellent in moist heat resistance. When the hydroxyl value is 200mgKOH/g or less, the cured film is excellent in antistatic properties and moist heat resistance.

The hydroxyl value of the component (C) is preferably 70mgKOH/g or more, more preferably 90mgKOH/g or more, from the viewpoint of excellent wet heat resistance of the cured film. The hydroxyl value of component (C) is preferably 170mgKOH/g or less, more preferably 150mgKOH/g or less, from the viewpoint of excellent antistatic properties and moist heat resistance of the cured film. The hydroxyl value of component (C) is preferably about 70mgKOH/g to 170mgKOH/g, more preferably about 90mgKOH/g to 150mgKOH/g, from the viewpoint of excellent antistatic properties and moist heat resistance of the cured film.

(C) Examples of the component (B) include compounds having a hydroxyl value of 50 to 200mgKOH/g in the hydroxyl group-containing (meth) acrylate in the urethane (meth) acrylate.

The component (C) is preferably a hydroxyl group-containing polypentaerythritol poly (meth) acrylate or a hydroxyl group-containing pentaerythritol poly (meth) acrylate from the viewpoint of excellent antistatic properties, scratch resistance and moist heat resistance of the cured film; from the same viewpoint, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate are more preferable.

< physical Properties of hydroxyl group-containing (meth) acrylate (C) >

(C) Physical properties other than the hydroxyl value of the component are not particularly limited. The number of (meth) acryloyl groups in the molecule in the component (C) is preferably at least 3 from the viewpoint of excellent scratch resistance of the cured film.

The content of the component (C) in the active energy ray-curable resin composition is not particularly limited, and is preferably about 10 to 75 parts by mass in terms of solid content with respect to 100 parts by mass of the active energy ray-curable resin composition, from the viewpoint of excellent antistatic properties, scratch resistance and wet heat resistance of the cured film.

(reactive diluent)

The active energy ray-curable resin composition may contain a reactive diluent. The reactive diluent is a compound having an active energy ray-reactive functional group such as a carbon-carbon unsaturated bond other than the components (B) and (C). The reactive diluent may be used alone in 1 kind, or may be used in combination of 2 or more kinds. By using a reactive diluent in combination, the compatibility between the component (A) and the component (B) becomes better. As a result, the transparency of the active energy ray-curable resin composition is improved, and a cured film particularly excellent in antistatic property, transparency, hardness, scratch resistance, and the like can be obtained.

Examples of the reactive diluent include di (meth) acrylate, the components (a1 ') to (a 3'), the mono (meth) acrylate having an alkyl ester group having 19 or more carbon atoms, the vinyl monomer having an aromatic ring structure, and ethyl carbitol acrylate. In particular, di (meth) acrylates are preferred from the viewpoint of compatibility and cured film properties (hardness, scratch resistance, etc.).

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 type di (meth) acrylate, propylene oxide-modified bisphenol a type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, and mixtures thereof, Phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid (ヒドロキシピバリン acid) -modified neopentyl glycol di (meth) acrylate, and the like.

When a reactive diluent is used in the active energy ray-curable resin composition, the total content of the component (B), the component (C) and the reactive diluent in the composition is preferably about 80 to 97% by mass based on 100% by mass of the composition.

The content ratio of the components (B) and (C) and the reactive diluent in the active energy ray-curable resin composition is not particularly limited, but generally, when the total of the components (B), (C) and the reactive diluent is 100% by mass, the total amount of the components (B) and (C) is about 20% by mass to 100% by mass, and the reactive diluent is about 0% by mass to 80% by mass. However, in view of transparency of the obtained active energy ray-curable resin composition and antistatic properties, transparency, hardness, scratch resistance and the like of the cured film, it is preferable that the total amount of the component (B) and the component (C) is about 50 to 95% by mass and the reactive diluent is about 5 to 50% by mass.

(photopolymerization initiator)

The active energy ray-curable resin composition may contain a photopolymerization initiator. The photopolymerization initiator may be used in combination of 2 or more. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl ketone, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-cyclohexyl-phenyl 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-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like. The photopolymerization initiator is used when ultraviolet curing is performed, but is not necessarily required when electron beam curing is performed.

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 in terms of solid content with respect to 100 parts by mass of the composition.

(solvent)

The active energy ray-curable resin composition may contain a solvent in consideration of coating workability and the like. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 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 diluent solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In view 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 the above glycol ethers, alcohols, and ketones.

The content of the solvent in the active energy ray-curable resin composition is not particularly limited. When a solvent is contained in the composition, the content of the solvent is preferably in a range such that the solid content concentration of the composition is about 1 to 60% by weight from the viewpoint of coatability.

(additives)

The active energy ray-curable resin composition may contain, as an additive, a reagent other than any one of the solvent, the reactive diluent, and the photopolymerization initiator, if necessary, as long as the effects of the present invention are not impaired. The additive may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Examples of the additives include antistatic agents other than the component (A), antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface control agents, antifogging agents, hydrophilizing agents, antifouling agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.

The content of the additive in the active energy ray-curable resin composition is not particularly limited. The content of the additive is preferably about 0 to 60 parts by mass in terms of solid content with respect to 100 parts by mass of the composition.

[ cured film ]

The cured film of the present invention is obtained from the active energy ray-curable resin composition. Specifically, for example, the composition is applied to various substrate films so that the mass after drying is 0.05g/m²～30g/m²About 0.1g/m is preferable²～20g/m²And left and right sides, and then, the cured product is obtained by irradiating the cured product with active energy rays such as ultraviolet rays, electron beams, and radioactive rays.

Examples of the active energy ray used for the curing reaction include ultraviolet rays and electron beams. As the light source of the ultraviolet ray, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. The amount of light, the arrangement of light sources, the transport speed, and the like may be adjusted as needed, and for example, in the case of using a high-pressure mercury lamp, it is preferable to cure the lamp at a transport speed of about 5 to 50 m/min with respect to one lamp having a lamp output of about 80 to 160W/cm. On the other hand, in the case of an electron beam, it is preferable to cure the resin at a transport speed of about 5 m/min to 50 m/min using an electron beam accelerator having an acceleration voltage of about 10kV to 300 kV.

[ film ]

The film of the present invention contains the above cured film. The film is a product comprising the cured film and various base films.

Examples of the substrate film include plastic films, and various known substrates can be used. Examples of the plastic film include a polycarbonate film, a polyester film, a polyolefin film, a polystyrene film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS resin film, an AS resin film, an acrylic resin film, and an alicyclic polyolefin resin film. From the viewpoint of transparency and adhesion to a cured film, the plastic film is preferably 1 film selected from the group consisting of a polycarbonate film, a triacetyl cellulose film, an acrylic resin film, and an alicyclic polyolefin resin film. The average thickness of the base film is not particularly limited, but is usually about 20 to 1000. mu.m, preferably 20 to 200. mu.m.

The above-mentioned film can be produced by various known methods. The following methods are exemplified as the film production method: the active energy ray-curable resin composition is applied to at least one surface of the substrate film, dried as necessary, and then irradiated with the active energy ray. The laminate film (the body frame フィルム) may be produced by applying the resin composition of the present invention to the non-coated side of the resulting substrate film, bonding another substrate film thereto, and then irradiating the laminate film with an active energy ray.

Examples of the coating method include bar coater coating, wire bar coating (ワイヤーバー coating), meyer bar coating (メイヤーバー coating), air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

The coating amount is not particularly limited, and the mass after drying is preferably 0.1g/m²～30g/m²About 1g/m is more preferable²～20g/m². The average thickness of the cured film formed on the substrate film is usually about 0.05 μm to 30 μm, and preferably about 0.1 μm to 20 μm.

Examples

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Further, in the examples, "%" and "parts" mean "% by mass" and "parts by mass" unless otherwise specified.

(A) The weight average molecular weight of the component (d) is an actual value measured under the following conditions by a commercially available molecular weight measuring instrument.

Molecular weight analyzer: manufactured by DONG ソー, product name "HLC-8220 GPC

Column: the product name "TSKGel G6000PW_XL-CP”、“TSKGel G3000PW_XL-CP "manufactured by imperial ソー (strain)

Developing solvent: 0.1M NaNO₃And 0.1M acetic acid solution

Flow rate: 0.5mL/min

Sample concentration: 0.5g/L

Standard substance: polyethylene oxide (TSKgel Standard polyethylene oxide SE-kit manufactured by imperial ソー (strain))

(a2) The weight average molecular weight of the component (d) is an actual value measured under the following conditions by a commercially available molecular weight measuring instrument.

Molecular weight analyzer: manufactured by DONG ソー, product name "HLC-8220 GPC

Column: the product names "TSKGel G1000H" and "TSKGel G2000H" manufactured by Chinese imperial ソー (strain)

Developing solvent: tetrahydrofuran (THF)

Flow rate: 0.35mL/min

Sample concentration: 0.5g/L

Standard substance: polystyrene (Standard polystyrene kit PStQuickA, B, C, manufactured by imperial ソー strain)

The weight average molecular weight of the component (B) is an actual value measured under the following conditions by a commercially available molecular weight measuring instrument.

Molecular weight analyzer: manufactured by DONG ソー, product name "HLC-8220 GPC

Column: the product name "TSKGel guardcolumn SuperHZ-L", manufactured by Egyo ソー

Developing solvent: tetrahydrofuran (THF)

Flow rate: 0.35mL/min

Sample concentration: 0.5g/L

Standard substance: polystyrene (Standard polystyrene kit PStQuickA, B, C, manufactured by imperial ソー strain)

(Synthesis of component (a2))

Synthesis example 1

130 parts of hydroxyethyl methacrylate, 1140 parts of epsilon-caprolactone and 1.3 parts of tin octylate were charged into a reaction apparatus equipped with a stirring apparatus and a cooling tube, and the mixture was heated to 150 ℃ and kept warm for 6 hours and then cooled to obtain a ring-opening addition polymer of a hydroxyl group-containing vinyl monomer having a weight-average molecular weight of 2,760 and lactone (hereinafter referred to as component (a 2-1)).

< Synthesis of component (A) >

Production example 1

100 parts of methacryloyloxyethyltrimethyl ammonium chloride (DMC) (hereinafter referred to as component (a 1-1)), 60 parts of component (a2-1), 40 parts of t-butyl methacrylate (t-BMA) (hereinafter referred to as component (a 3-1)), and 800 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were charged into the same reaction apparatus as in Synthesis example 1, and the temperature was raised to 80 ℃. Then, 8 parts of 2, 2-azobis (2-methylbutyronitrile) (hereinafter referred to as ABN-E) and 32 parts of PGM were added to start the polymerization reaction, and the mixture was held at 80 ℃ for 3 hours, then held at 113 ℃ for 2 hours, and then cooled to obtain a solution (nonvolatile fraction: 20%) of the polymer (A-1) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 220,000.

Synthesis of component (urethane (meth) acrylate) of (B)

Production example 2

After 177 parts of an isocyanurate-modified form of hexamethylene diisocyanate (manufactured by imperial ソー, product name "コロネ - ト HXR"), 70 parts of tin octoate, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by osaka organic chemical industry, product name "ビスコート # 300") were added to a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, the temperature in the system was raised to about 80 ℃ over about 1 hour. Subsequently, the reaction system was kept at the same temperature for 1 hour and then cooled to obtain a mixture of a urethane (meth) acrylate and an unreacted monomer (urethane (meth) acrylate (B-1); hereinafter referred to as component (B-1)) having a solid content of 100 mass%. The component (B-1) is a mixture containing a urethane (meth) acrylate having 9 (meth) acryloyl groups in the molecule, and the urethane (meth) acrylate has a weight average molecular weight of 16,000.

Production example 3

After adding 177 parts of an isocyanurate-modified form of hexamethylene diisocyanate (manufactured by imperial ソー, product name "コロネ - ト HXR"), 0.03 part of tin octylate, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by shin-kamura chemical industry, product name "NK エステル a-9550W") to a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, the temperature in the system was raised to about 80 ℃ over about 1 hour. Subsequently, the reaction system was kept at the same temperature for 1 hour and then cooled to obtain a mixture of a urethane (meth) acrylate and an unreacted monomer (urethane (meth) acrylate (B-2); hereinafter referred to as component (B-2)) having a solid content of 100 mass%. The component (B-2) is a mixture containing a urethane (meth) acrylate having 9 (meth) acryloyl groups in the molecule, and the urethane (meth) acrylate has a weight average molecular weight of 44,000.

Comparative production example 1

After adding 177 parts of an isocyanurate-modified form of xylylenediisocyanate (product name "Takenate D-131N" manufactured by mitsui chemical corporation) and 0.03 part of tin octylate and 177 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "ビスコート # 300" manufactured by osaka organic chemical industry corporation) to a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, the temperature in the system was raised to about 80 ℃ over about 1 hour. Subsequently, the reaction system was kept at the same temperature for 1 hour and then cooled to obtain a mixture of a urethane (meth) acrylate and an unreacted monomer (urethane (meth) acrylate (b-1); hereinafter referred to as component (b-1)) having a solid content of 100 mass%. The component (b-1) is a mixture containing a urethane (meth) acrylate having 9 (meth) acryloyl groups in the molecule, and the urethane (meth) acrylate has a weight average molecular weight of 9,000.

< preparation of active energy ray-curable resin composition >

Example 1

An active energy ray-curable resin composition containing 50% of a nonvolatile component was prepared by diluting 6 parts of (A-1) component, 26 parts of (B-1) component, hydroxyl group-containing polypentaerythritol polyacrylate (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, having a hydroxyl value of 90mgKOH/g, available from New Mediterranean chemical Co., Ltd., product name "NK エステル A-9570W") (hereinafter referred to as (C-1) component) 46 parts, ethylene glycol dimethacrylate (available from Kyoeisha chemical Co., Ltd., product name "LIGHT ESTER (ライトエステル) EG") 22 parts, and 1-hydroxy-cyclohexyl-phenyl ketone (available from IGM Resins B.V., product name "Omnirad 184", hereinafter referred to as Omni184) with PGM in a solid content ratio.

Example 2

An active energy ray curable resin composition having a nonvolatile content of 50% was prepared in the same manner as in example 1 except that 5 parts of component (A-1) in solution, 43 parts of component (B-2) instead of component (B-1), 29 parts of component (C-1) and 23 parts of ethylcarbitol acrylate (product name "ビスコート # 190" manufactured by Osaka organic chemical Co., Ltd.) instead of ethylene glycol dimethacrylate were used in comparison with example 1.

Example 3

In comparison with example 2, an active energy ray curable resin composition having a nonvolatile content of 50% was prepared in the same manner as in example 2 except that 29 parts of a hydroxyl group-containing pentaerythritol polyacrylate (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value 120mgKOH/g, product name "ビスコート # 300", manufactured by Osaka organic chemical industries, Ltd.) (hereinafter referred to as component (C-2)) was used in place of component (C-1).

Example 4

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 2 except that 43 parts of a product name "AX-4-HC-NS-M" (hereinafter referred to as component (B-3)) prepared by Japanese catalyst Kabushiki Kaisha (product name: AX-4-HC-NS-M ") having a weight-average molecular weight of 22,000 and at least 2 (meth) acryloyl groups in the molecule was used in place of component (B-2) in example 2.

Comparative example 1

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 2, except that 43 parts of component (B-1) was used instead of component (B-2) in example 2.

Comparative example 2

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 1 except that 46 parts of hydroxyl group-containing polypentaerythritol polyacrylate (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 45mgKOH/g, product name "NK エステル A-9550W" manufactured by Ninghamura chemical Co., Ltd.) (hereinafter referred to as component (C-1)) was used in place of component (C-1) in example 1.

Comparative example 3

An actinic-energy-ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 1 except that 46 parts of hydroxyl-containing pentaerythritol polyacrylate (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value: 290mgKOH/g, product name "ARONIX (アロニックス) MT-3548" manufactured by Toyo Synthesis Co., Ltd.) (hereinafter referred to as component (C-2)) was used in place of component (C-1) in example 1.

[ Table 1]

The blending amount in table 1 is a value converted into parts by mass of the solid component.

< preparation of film >

The active energy ray-curable resin compositions of examples 1 to 4 and comparative examples 1 to 3 were applied to a PET film (product name "ルミラー 100U 483" manufactured by DONG レ, Inc.) having a film thickness of 100 μm by a #15 bar coater so that the film thickness of the cured film was 5 μm, and the cured film was dried at 80 ℃ for 1 minute to prepare a film. Next, the obtained film was subjected to ultraviolet curing by means of an ultraviolet curing apparatus (manufactured by Tokaki Kaisha マルチプライ, product name "UBT-080-7A/BM", high pressure mercury lamp 600mJ/cm²) Thus, a film having a cured coating film was obtained. The following evaluation results for the produced film are shown in table 1.

(surface resistance test)

The surface resistance value (omega/□) of the film immediately after production was measured at an applied voltage of 500V according to JIS K6911 using a commercially available resistivity meter (product name "ハイレスタ MCP-HT-450" manufactured by Mitsubishi ケミカルアナリテック, Ltd.).

(Wet Heat resistance test)

The film was allowed to stand at 80 ℃ and 95% Rh for 24 hours, and then the presence or absence of surface precipitates on the film surface was visually confirmed.

Has no surface precipitate

Has surface precipitate

(Pencil hardness test)

The cured film of the above film was evaluated by a pencil scratch test (according to JIS K5400) with a load of 500 g.