JP7420098B2 - Active energy ray-curable resin compositions, cured films and films - Google Patents

Description

The present invention relates to active energy ray-curable resin compositions, cured films, and films.

Conventionally, coating agents for various substrates, such as hard coating agents 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), have been conventionally used, such as pentaerythritol poly( BACKGROUND ART Compositions containing as a main component compounds having a large number of (meth)acryloyl groups in the molecule (so-called active energy ray-curable resins), such as meth)acrylate and ditrimethylolpropane poly(meth)acrylate, are known. The composition has high productivity because it is instantly cured by irradiation with ultraviolet rays or electron beams, and forms cured films with excellent hardness and scratch resistance on the surfaces of various substrates.

By the way, when the above-mentioned active energy ray-curable resin composition is used for flat panel display applications, the cured film must not only have high transparency but also prevent troubles caused by static electricity during assembly and operation of the display. Good antistatic properties are required in order to achieve 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 (fine particles of zinc antimonate). However, in order to impart a sufficient antistatic effect to the cured film obtained from the composition, it is necessary to use a large amount of conductive filler, but in such a case, the transparency and hardness of the cured film may be adversely affected. There were cases where it caused Additionally, as a method of imparting antistatic properties, it is also possible to use active energy ray-curable resin compositions containing organic substances (π-conjugated conductive polymers) such as poly(thiophene) and poly(aniline). Since these are generally strongly colored, there is a problem in coloring the cured film.

On the other hand, it is said that even if a conductive polymer is used, if a polymer having a quaternary ammonium salt structure is used, the above-mentioned coloring problem will not occur. 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 with excellent antistatic properties and transparency can be obtained.

Japanese Patent Application Publication No. 9-051116 JP2012-31297A

However, the inventors of the present invention have investigated that the active energy ray-curable resin composition in Patent Document 2 causes bleed-out in the resulting cured film in a high-temperature, high-humidity environment. In some cases, a decrease in transparency (haze) and poor appearance were observed, and there were problems with the heat and humidity resistance of the cured film.

An object of the present invention is to provide a novel active energy ray-curable resin composition that can provide a cured film with excellent antistatic properties and heat-and-moisture resistance.

As a result of extensive studies, the present inventors found that the above-mentioned The inventors discovered that the problem could be solved and completed the present invention.

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

1. Polymer (A) having a quaternary ammonium salt structure,
A polyfunctional (meth)acrylate (B) with a weight average molecular weight (Mw) of 10,000 to 50,000 (excluding component (C)), and a hydroxyl group-containing (with a hydroxyl value of 50 to 200 mgKOH/g) An active energy ray-curable resin composition containing meth)acrylate (C).

2. (A) The component is
A structural unit derived from a vinyl monomer having a quaternary ammonium salt structure (a1),
A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and
a vinyl monomer-derived structural unit (a2) having a weight average molecular weight of 1,000 to 10,000;
and a vinyl monomer-derived structural unit (a3) containing an alkyl ester group having 1 to 18 carbon atoms,
The active energy ray-curable resin composition according to item 1 above, which is a polymer containing.

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

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

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

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

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

8. A film comprising the cured film according to item 7 above.

The active energy ray-curable resin composition of the present invention suppresses bleed-out in a high-temperature, high-humidity environment in a cured film obtained therefrom, and therefore can provide a cured film with excellent heat-and-moisture resistance. Moreover, the cured film obtained from the active energy ray-curable resin composition has excellent antistatic properties and high hardness, and therefore also excellent scratch resistance.

The active energy ray-curable resin composition provides a cured film with excellent antistatic properties, heat and humidity resistance, and scratch resistance, and therefore can be suitably used as a coating agent for the front plate of various flat panel displays.

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

[Active energy ray curable resin composition]
The active energy ray-curable resin composition of the present invention includes a polymer (A) having a quaternary ammonium salt structure (hereinafter referred to as component (A)) and a weight average molecular weight (Mw) of 10,000 to 50,000. Polyfunctional (meth)acrylate (B) (excluding component (C)) (hereinafter referred to as component (B)), and hydroxyl group-containing (meth)acrylate (C) with a hydroxyl value of 50 to 200 mgKOH/g ( Hereinafter, it contains (referred to as component (C)).

As used herein, "(meth)acrylic" means "at least one selected from the group consisting of acrylic and methacryl." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate," and "(meth)acryloyl group" means "selected from the group consisting of acryloyl group and methacryloyl group." "at least one".

<Polymer (A) having quaternary ammonium salt structure>
As component (A), various known polymers can be used without particular limitation as long as they are polymers having a quaternary ammonium salt structure. In addition, if component (A) is a monomer having a quaternary ammonium salt structure and a carbon-carbon unsaturated double bond, the antistatic properties and moist heat resistance of the cured film will be insufficient, so preferably do not have.

Component (A) is, for example, a structural unit (a1) derived from a vinyl monomer containing a quaternary ammonium salt structure (hereinafter referred to as structural unit (a1)), or a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone. , and a structural unit (a2) derived from a vinyl monomer having a weight average molecular weight of 1,000 to 10,000 (hereinafter referred to as a structural unit (a2)), derived from a vinyl monomer containing an alkyl ester group having 1 to 18 carbon atoms. Examples include polymers containing the structural unit (a3) (hereinafter referred to as structural unit (a3)).

The structural unit (a1) is a structural unit contained in a polymer chain when a polymer is produced using a vinyl monomer (a1') containing a quaternary ammonium salt structure (hereinafter referred to as the (a1') component). Component (a1') can be used alone or in combination of two or more.

As the component (a1'), any known vinyl monomer having a quaternary ammonium salt structure in its molecule may be used without particular limitation. Specifically, for example, general formula (1):
[CH ₂ =C(R ¹ )-C(=O)-AB-N ⁺ (R ² )(R ³ )(R ⁴ )] _n・X ^n-
(In the formula, R ¹ is H or CH ₃ , R ² to R ⁴ are an alkyl group having about 1 to 3 carbon atoms, A is O or NH, B is an alkylene group having about 1 to 3 carbon atoms, Examples include (meth)acrylate compounds represented by ( ^n- represents a counter anion species and n represents an integer of 1 or more). Further, examples of X ^n- include Cl ^- , SO ₄ ^2- , SO ₃ ^2- , C ₂ H ₅ SO ₄ ^- , Br ^-, etc., and Cl ^- is preferable from the viewpoint of antistatic effect. Commercially available products of component (a1′) include, for example, “Light Ester DQ-100” manufactured by Kyoeisha Kagaku Co., Ltd. and “DMAEA-Q” manufactured by Kojin 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.

The content of the structural unit (a1) in component (A) is not particularly limited, but from the viewpoint of excellent transparency and antistatic performance of the cured film, the content of the structural unit (a1) in component (A) is 30 to 60% by mass based on 100% by mass of component (A). It is preferable that the degree of

The structural unit (a2) is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and has a weight average molecular weight of 1,000 to 10,000 (hereinafter referred to as (a2')). It is a structural unit contained in a polymer chain when a polymer is manufactured using a component). Component (a2') can be used alone or in combination of two or more.

Component (a2') is produced by carrying out a ring-opening polyaddition reaction using a hydroxyl group-containing vinyl monomer and a lactone using 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 also be used alone or in combination of two or more types.

As the above-mentioned hydroxyl group-containing vinyl monomer, various known ones can be used without particular limitation. Specific examples include hydroxyl group-containing (meth)acrylic compounds, hydroxyl group-containing vinyl ethers, and the like. Among these, hydroxyl group-containing (meth)acrylic compounds are preferred from the viewpoint of radical copolymerizability.

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.

As the above-mentioned lactone, various known lactones can be used without 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 from the viewpoint of reactivity in ring-opening polymerization.

The weight average molecular weight (Mw) of component (a2') is 1,000 to 10,000. When the weight average molecular weight is less than 1,000, the antistatic properties and moist heat resistance of the cured film tend to decrease. When the weight average molecular weight exceeds 10,000, it becomes difficult to synthesize component (a2'). The weight average molecular weight is preferably about 1,000 to 5,000, since the cured film has excellent transparency, antistatic properties, scratch resistance, and heat and humidity resistance, and is easy to synthesize. In this specification, the weight average molecular weight of the component (a2') refers to the polystyrene equivalent value determined by gel permeation chromatography, but the measuring method is not particularly limited, and various known means can be employed, and commercially available Measuring equipment is also available.

The content of the structural unit (a2) in the component (A) is not particularly limited, but from the viewpoint of excellent transparency and scratch resistance of the cured film, the content of the structural unit (a2) in the component (A) is 25 to 55% by mass based on 100% by mass of the component (A). It is preferable that the degree of

Component (a2') can be obtained by various known methods. Specifically, for example, a method may be mentioned in which the lactone is subjected to a ring-opening polyaddition reaction using the hydroxyl group-containing vinyl monomer as an initiator. Further, the weight average molecular weight can be adjusted by appropriately selecting the charging ratio of both, the reaction temperature, and the type and amount of catalyst during the reaction.

A catalyst may be used during the above reaction. Catalysts include, for example, 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; dibutyltin dilaurate, Examples include tin compounds such as dibutyltin dioctoate, dibutyltin mercaptide, and tin octylate. The amount of the catalyst to be used is not particularly limited, but is preferably about 0.01 to 10% by weight based on the total of 100% by weight of the hydroxyl group-containing vinyl monomer and lactone.

The structural unit (a3) is a structural unit contained in a polymer chain when a polymer is produced using a vinyl monomer (a3') containing an alkyl ester group having 1 to 18 carbon atoms (hereinafter referred to as the (a3') component). It is. Component (a3') can be used alone or in combination of two or more. In addition, component (a3') is preferably one that does not have an alicyclic structure in order to improve the compatibility between component (A), component (B), component (C), and the reactive diluent described below. Preferably, in this case, the structural unit (a3) does not have an alicyclic structure.

As the component (a3'), any known vinyl monomer having an alkyl ester group having 1 to 18 carbon atoms can be used without particular limitation. In this specification, the term "alkyl ester group having 1 to 18 carbon atoms" refers to an ester group represented by -C(=O)-OR, where R is an alkyl group having 1 to 18 carbon atoms. means something that is.

The alkyl ester group having 1 to 18 carbon atoms is, for example, 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, Decyl ester group, undecyl ester group, lauryl ester group, tridecyl ester group, myristyl ester group, pentadecyl ester group, palmityl ester group, heptadecyl ester group, stearyl ester group, isopropyl ester group, isobutyl ester group, sec -butyl ester group, tert-butyl ester group, 1-methylbutyl ester group, 2-methylbutyl ester group, 3-methylbutyl ester group, 1-ethylpropyl ester group, 1,1-dimethylpropyl ester group, 1, 2-dimethylpropyl ester group, 2,2-dimethylpropyl ester group, isopentyl ester group, isododecyl ester group, isotridecyl ester group, isomyristyl ester group, isopentadecyl ester group, isohexadecyl ester group, iso Examples include heptadecyl ester group and isostearyl ester group.

Examples of the component (a3') include mono(meth)acrylates containing the above-mentioned alkyl ester groups having 1 to 18 carbon atoms.

The above mono(meth)acrylate containing an alkyl ester group having 1 to 18 carbon atoms is, for example, 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, palmityl (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 Examples include acrylate and isostearyl (meth)acrylate.

By including 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, component (a3') is particularly preferably one selected from the group consisting of tert-butyl (meth)acrylate and isobutyl (meth)acrylate.

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

Component (A) may further contain a structural unit (a4) (hereinafter also referred to as structural unit (a4)) other than the above structural units (a1) to (a3). The structural unit (a4) is a structure contained in a polymer chain when a polymer is produced using a monomer (a4') other than the above monomers (a1') to (a3') (hereinafter referred to as the (a4') component). It is a unit. Two or more types of component (a4') can be used in combination.

Examples of the component (a4') include mono(meth)acrylates and aromatic ring structure-containing vinyl monomers that do not fall under the component (a3).

Examples of mono(meth)acrylates that do not fall under component (a3) include mono(meth)acrylates containing an alkyl ester group having 19 or more carbon atoms.

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

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

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

The content ratio of structural units (a1) to (a3) in component (A) is not particularly limited, but the compatibility of component (A) with component (B), component (C) and reactive diluent described below, Considering the antistatic properties and transparency of the cured film, the preferable ratio is about 35 to 45:35 to 45:5 to 15 (mass ratio) in this order. In addition, when the component (A) contains the structural unit (a4), the content ratio of the structural units (a1) to (a4) in the component (A) is also not particularly limited, but for the same reason, the content ratio of the structural units (a1) to (a4) is 35 to 45:35 in order. ~45:5~15:0~15 (mass ratio) is preferred.

<Physical properties and manufacturing method of polymer (A) having quaternary ammonium salt structure>
The physical properties of component (A) are not particularly limited. The weight average molecular weight (Mw) of component (A) 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, bleed-out of the antistatic agent from the cured film is further suppressed, so that the cured film has better moisture and heat resistance. In addition, when the weight average molecular weight is 300,000 or less, component (A) has better compatibility with component (B), component (C), and reactive diluent, which will be described later. The cured film has better transparency. Note that the weight average molecular weight of component (A) refers to the polyethylene oxide equivalent value determined by gel permeation chromatography, but the measuring method is not particularly limited, and various known means can be employed, and commercially available measuring instruments can also be used. can.

Component (A) is the above-mentioned (a1') component, (a2') component, (a3') component, and optionally (a4') component by various known methods (bulk polymerization, solution polymerization, emulsion polymerization, etc.). ) can be obtained by radical copolymerization. The reaction temperature is usually about 40 to 160°C, and the reaction time is about 2 to 12 hours.

When synthesizing component (A), various known radical polymerization initiators may be used. Examples of such radical polymerization initiators include azo polymerization initiators, peroxide polymerization initiators, and the like. The radical polymerization initiator may be used alone or in combination of two or more.

Examples of the azo polymerization initiator include azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylbutyronitrile) [for example, manufactured by Nippon Hydrazine Kogyo Co., Ltd. under the trade name "ABN- E, etc.], 2,2-azobis(2,4-dimethylvaleronitrile) [eg, manufactured by Nippon Hydrazine Kogyo Co., Ltd., trade name "ABN-V", etc.].

Examples of the peroxide-based polymerization initiator include inorganic peroxides, organic peroxides, and the like. Examples of the inorganic peroxide 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, and lauroyl peroxide. oxide, tert-butylperoxy-2-ethylhexanoate, didodecanoyl peroxide (for example, manufactured by NOF Corporation, trade name "Perloyl (registered trademark) L"), and the like.

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 components (a1') to (a3') and (a4'). It is.

Furthermore, during the synthesis of component (A), chain transfer agents such as lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, and bromotrichloromethane may be used. The amount used is not particularly limited, but is usually about 0.01 to 10% by mass based on the total mass of components (a1') to (a3') and component (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; benzene, toluene and aromatic hydrocarbons such as xylene; acetate esters such as ethyl acetate and butyl acetate; organic solvents such as chloroform and dimethylformamide. Among these, glycol ethers are preferred from the viewpoint of the dissolving power of components (a1') to (a3') and component (a4'). Furthermore, in the case of emulsion polymerization, various known anionic, nonionic, and cationic surfactants can be used.

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

<Polyfunctional (meth)acrylate (B)>
Component (B) 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 two (meth)acryloyl groups in the molecule. Note that the component (B) does not include the component (C) described below. In this specification, the weight average molecular weight of component (B) refers to a polystyrene equivalent value determined by gel permeation chromatography, but the measuring method is not particularly limited, and various known means can be employed, and commercially available measuring instruments can be used. Also available.

Conventionally, active energy ray-curable resin compositions containing compounds having a quaternary ammonium salt structure have been formulated with low molecular weight polyfunctional ( It is preferred to use meth)acrylates and hydroxyl group-containing (meth)acrylates with low hydroxyl value, and it has been rare to use high molecular weight polyfunctional (meth)acrylates or hydroxyl group-containing (meth)acrylates with high hydroxyl value. . However, as a result of intensive study by the present inventors, it has been found that by using a composition containing component (A) together with component (B) having a high molecular weight and component (C) having a relatively high hydroxyl value, it is possible to It has been found that bleed-out from the underlying cured film is suppressed, and the cured film has excellent antistatic properties and scratch resistance.

When the weight average molecular weight of the component (B) is 10,000 or more, the above-mentioned bleed-out is suppressed, so that the cured film has excellent moisture and heat resistance. Further, when the weight average molecular weight is 50,000 or less, component (B) has excellent compatibility with other components, and therefore, the cured film has excellent transparency.

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

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

(Urethane (meth)acrylate)
Examples of the urethane (meth)acrylate include a reaction product of a hydroxyl group-containing (meth)acrylate and a polyisocyanate, a reaction product of a hydroxyl group-containing (meth)acrylate, a polyol, and a polyisocyanate, and the like.

As the above-mentioned hydroxyl group-containing (meth)acrylate, any known one can be used without any particular restriction as long as it is a compound having at least one hydroxyl group and at least one (meth)acryloyl group in the molecule. The above hydroxyl group-containing (meth)acrylates can be used alone or in combination of two or more. In addition, the said hydroxyl group containing (meth)acrylate may be the same as (C) component mentioned later.

The above-mentioned hydroxyl group-containing (meth)acrylates include, for example, hydroxyl group-containing glycerin (meth)acrylate, hydroxyl group-containing polyglycerin poly(meth)acrylate, hydroxyl group-containing pentaerythritol poly(meth)acrylate, hydroxyl group-containing polypentaerythritol poly(meth)acrylate, Examples thereof include hydroxyl group-containing trimethylolpropane poly(meth)acrylate, hydroxyl group-containing polytrimethylolpropane poly(meth)acrylate, and hydroxyl group-containing mono(meth)acrylate.

Examples of the above-mentioned 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, and ethylene oxide-modified glycerin. Consists of at least two types selected from the group consisting of di(meth)acrylate, propylene oxide-modified glycerin di(meth)acrylate, and glycerin mono(meth)acrylate, glycerin di(meth)acrylate, and glycerin tri(meth)acrylate. Examples include mixtures.

The above-mentioned hydroxyl group-containing polyglycerin poly(meth)acrylates include, for example, diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, and triglycerin tetra(meth)acrylate. Examples include acrylate.

The above-mentioned hydroxyl group-containing pentaerythritol poly(meth)acrylates include, for example, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol di(meth)acrylate, propylene oxide modified pentaerythritol di(meth)acrylate. acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified pentaerythritol tri(meth)acrylate, and pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate and Examples include a mixture of at least two selected from the group consisting of pentaerythritol tetra(meth)acrylate.

Examples of the hydroxyl group-containing polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and 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 Examples include (meth)acrylate, a mixture of at least two selected from these (meth)acrylates, and a mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

Examples of the 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. It will be done.

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

The above-mentioned hydroxyl group-containing mono(meth)acrylates include, for example, 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 hydroxyl group-containing branched alkyl (meth)acrylate include 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate.

Examples of the hydroxyl group-containing cycloalkyl (meth)acrylate include hydroxycyclohexyl (meth)acrylate.

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

The above-mentioned hydroxyl group-containing (meth)acrylate is preferably a hydroxyl group-containing (meth)acrylate having at least three (meth)acryloyl groups in the molecule, from the viewpoint of excellent curability and scratch resistance of the cured film. More preferred are hydroxyl group-containing (meth)acrylates having 2 hydroxyl groups and at least 3 (meth)acryloyl groups. 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.

As the above-mentioned polyisocyanate, any known polyisocyanate can be used without any particular restriction as long as it is a compound having at least two isocyanate groups in the molecule. The above polyisocyanates may be used alone or in combination of two or more.

The above polyisocyanates include, for example, linear aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, biuret forms, isocyanurates, allophanate forms, adduct forms of these diisocyanates, as well as biuret forms and isocyanurates. Examples include complexes obtained by reacting two or more selected from the group consisting of allophanate, allophanate, and adduct.

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, decamethylene diisocyanate, and the like. .

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

Examples of the above alicyclic diisocyanates include hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, tricyclodecylene diisocyanate, and adamantane diisocyanate. , norbornene diisocyanate, bicyclodecylene diisocyanate, and the like.

The aromatic diisocyanates include, for example, dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, etc. Examples include 4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and 1,5-naphthylene diisocyanate.

（ｎ^ｂ１は、０以上の整数であり、Ｒ^ｂ１～Ｒ^ｂ５はＲ^ｂＡ～Ｒ^ｂＥと同様であり、Ｒ^ｂ’～Ｒ ^ｂ'' はそれぞれ独立に、イソシアネート基又はＲ^ｂα～Ｒ^ｂβ自身の基である。Ｒ^ｂ４～Ｒ^ｂ５、Ｒ ^ｂ''は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^ｂＤ～Ｒ^ｂＥ、Ｒ^ｂβは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が挙げられる。 The biuret form of the diisocyanate is
Structural formula below:
[In the formula, n ^b is an integer of 1 or more, and R ^bA to R ^bE each independently represent a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate. R ^bα to R ^bβ are each independently an isocyanate group or

(n ^b1 is an integer of 0 or more, R ^b1 to R ^b5 are the same as R ^bA to R ^bE , and R ^b ′ to R ^b ″ are each independently an isocyanate group or R ^bα to R ^bβ itself (R ^b4 to R ^b5 and R ^b '' may be different groups for each constituent unit.). R ^bD to R ^bE and R ^bβ may have different groups for each structural unit. Examples include compounds represented by the following.

Specifically, the biuret form of the diisocyanate is Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei Corporation), Desmodur N3200A (biuret form of hexamethylene diisocyanate) ( The above examples include those manufactured by Sumitomo Bayer Urethane Co., Ltd.).

（ｎ^ｉ１は、０以上の整数であり、Ｒ^ｉ１～Ｒ^ｉ５はＲ^ｉＡ～Ｒ^ｉＥと同様であり、Ｒ^ｉ’～Ｒ ^ｉ'' はそれぞれ独立に、イソシアネート基又はＲ^ｉα～Ｒ^ｉβ自身の基である。Ｒ^ｉ4～Ｒ^ｉ５、Ｒ^ｉ''は、各構成単位ごとに基が異なっていてもよい。）である。Ｒ^ｉＤ～Ｒ^ｉＥ、Ｒ^ｉβは、各構成単位ごとに基が異なっていてもよい。］で表される化合物等が挙げられる。 The isocyanurate form of the diisocyanate is
Structural formula below:
[In the formula, n ⁱ is an integer of 0 or more, and R ^iA to R ^iE each independently represent a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate. R ^iα to R ^iβ are each independently an isocyanate group or

(n ⁱ¹ is an integer of 0 or more, R ⁱ¹ to R ⁱ⁵ are the same as R ^iA to R ^iE , and R ⁱ ' to R ⁱ '' are each independently an isocyanate group or R ^iα to R ^iβ themselves. (R ⁱ⁴ to R ⁱ⁵ and R ⁱ '' may be different groups for each constituent unit.) R ^iD to R ^iE and R ^iβ may have different groups for each structural unit. Examples include compounds represented by the following.

Specifically, the isocyanurates of the diisocyanate include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (manufactured by Asahi Kasei Corporation), Coronate HXR, Coronate HX (manufactured by Asahi Kasei Corporation), , isocyanurate of hexamethylene diisocyanate) (manufactured by Tosoh Corporation), Takenate D-127N (isocyanurate of hydrogenated xylylene diisocyanate) (manufactured by Mitsui Chemicals, Ltd.), VESTANAT T1890/100 (manufactured by Mitsui Chemicals, Ltd.) Isocyanurate form of isophorone diisocyanate) (manufactured by Evonik Japan Co., Ltd.), and the like.

The allophanate form of the diisocyanate is
Structural formula below:
[In the formula, n ^a is an integer of 0 or more, R ^aA is an alkyl group, aryl group, polyether group, polyester group, or polycarbonate group, and R ^aB to 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 to R ^aγ each independently represent an isocyanate group. or
(n ^a1 is an integer of 0 or more, R ^a1 to R ^a6 are the same as R ^aB to R ^aG , and R ^a ' to R ^a ''' are each independently an isocyanate group or R ^aα to R ^aγ (R ^a1 to R ^a4 and R ^{a ′} to R ^a ″ may be different groups for each constituent unit.). R ^aB to R ^aE and R ^aα to R ^aβ may have different groups for each constituent unit. Examples include compounds represented by the following.

Specific examples of the allophanate form of the diisocyanate include Coronate 2793 (manufactured by Tosoh Corporation), Takenate D-178N (manufactured by Mitsui Chemicals, Inc.), and the like.

（式中、ｎ^ad’は０以上の整数であり、Ｒ^ad’～Ｒ^ad’’はＲ^adＡ～Ｒ^adＥと同様であり、Ｒ^ad’’’は、Ｒ^ad１～Ｒ^ad２自身の基であり、Ｒ^ad’～Ｒ^ad’’’は、各構成単位ごとに基が異なっていてもよい。）
であり、Ｒ^adＤ～Ｒ^adＥ、Ｒ^ad２は、各構成単位ごとに基が異なっていてもよい。］
で示されるトリメチロールプロパンとジイソシアネートのアダクト体、
下記構造式
［式中、ｎ^ad1は０以上の整数であり、Ｒ^adα～Ｒ^adεは、それぞれ独立に、直鎖脂肪族ジイソシアネート残基、分岐脂肪族ジイソシアネート残基、脂環式ジイソシアネート残基及び芳香族ジイソシアネート残基のいずれかであり、Ｒ^adＡ～Ｒ^adＢは、それぞれ独立に

（式中、ｎ^ad1’は０以上の整数であり、Ｒ^adδ’～Ｒ^adε’はＲ^adα～Ｒ^adεと同様であり、Ｒ^adＢ’は、Ｒ^adＡ～Ｒ^adＢ自身の基であり、Ｒ^adδ’～Ｒ^adε’、Ｒ^adＢ’は、各構成単位ごとに基が異なっていてもよい。）
Ｒ^adδ～Ｒ^adε、Ｒ^adＢは、各構成単位ごとに基が異なっていてもよい。］
で示されるグリセリンとジイソシアネートのアダクト体等が挙げられる。 The adduct of the diisocyanate is
Structural formula below:
[In the formula, n ^ad is an integer of 0 or more, and R ^adA to R ^adE each independently represent a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate. any of the residues, and R ^ad1 to R ^ad2 are each independently

(In the formula, n ^ad' is an integer greater than or equal to 0, R ^ad' to R ^ad'' are the same as R ^adA to R ^adE , and R ^ad''' is the group of ^Rad1 to ^Rad2 itself. (R ^ad' to R ^ad''' may have different groups for each constituent unit.)
and R ^adD to R ^adE and R ^ad2 may have different groups for each structural unit. ]
an adduct of trimethylolpropane and diisocyanate shown by
Structural formula below
[In the formula, n ^ad1 is an integer of 0 or more, and R ^adα to R ^adε each independently represent a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate. any of the residues, and R ^adA to R ^adB are each independently

(In the formula, n ^ad1' is an integer greater than or equal to 0, R ^adδ' to R ^adε' are the same as R ^adα to R ^adε , R ^adB' is a group of R ^adA to R ^adB itself, and R ^adδ' to R ^adε' and R ^adB' may have different groups for each constituent unit.)
R ^adδ to R ^adε and R ^adB may have different groups for each constituent unit. ]
Examples include adducts of glycerin and diisocyanate shown in the following.

Specifically, the adducts of the diisocyanates include Duranate P301-75E (manufactured by Asahi Kasei Corporation), Takenate D-110N, Takenate D-160N (manufactured by Mitsui Chemicals, Inc.), Coronate L, Examples include Coronate HL (manufactured by Tosoh Corporation).

In addition, in each of the above formulas, "linear aliphatic diisocyanate residue, branched aliphatic diisocyanate residue, alicyclic diisocyanate residue, and aromatic diisocyanate residue" refers to the above linear aliphatic diisocyanate, the above branched aliphatic Among the group diisocyanates, the above-mentioned alicyclic diisocyanates, and the above-mentioned aromatic diisocyanates, it means the remaining group after removing the isocyanate group.

The above-mentioned polyisocyanate is preferably a polyisocyanate having at least three isocyanate groups in the molecule, since the cured film has excellent scratch resistance. As the polyisocyanate having at least three isocyanate groups in the molecule, the above-mentioned biuret form, the above-mentioned isocyanurate form, the above-mentioned allophanate form, and the above-mentioned adduct form are preferable.

As the above-mentioned polyol, various known polyols can be used without particular limitation as long as they are compounds having at least two hydroxyl groups in the molecule. The above polyols may be used alone or in combination of two or more.

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

Examples of the aliphatic polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, and 2-butyl-2 -Ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1,6- Hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,8- Aliphatic alcohols containing two hydroxyl groups such as octanediol, sugar alcohols such as xylitol and sorbitol, aliphatic alcohols containing three or more hydroxyl groups such as glycerin, trimethylolpropane, and trimethylolethane, etc. mentioned

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

The above polyether polyols include, for example, 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. Examples include merging.

The above-mentioned polyester polyols include, for example, condensation polymers of polyhydric alcohols and polycarboxylic acids or their anhydrides; ring-opening polymers of cyclic esters (lactones); polyhydric alcohols, polycarboxylic acids, or their anhydrides; and a reaction product of three types of components, such as cyclic ester and cyclic ester.

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, Examples include trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.).

The polyhydric carboxylic acid or anhydride thereof is, for example, an aliphatic dicarboxylic acid such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid; Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, or their anhydrides Examples include things.

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

Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.

Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the polyester polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like.

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

Examples of the above-mentioned polyolefin polyols include those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon skeleton, and having a hydroxyl group at the end of the molecule.

Examples of the above-mentioned polybutadiene-based polyols include those having a copolymer of butadiene as a hydrocarbon skeleton and a hydroxyl group at the end of the molecule. The polybutadiene polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

Examples of the (meth)acrylic polyols include (meth)acrylic acid ester polymers or copolymers having at least two hydroxyl groups in the molecule. Examples of the (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylate. Examples include alkyl (meth)acrylates such as octyl 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) between the isocyanate group contained in the polyisocyanate, the hydroxyl group contained in the hydroxyl group-containing (meth)acrylate, and the hydroxyl group contained in the polyol is not particularly limited. However, in view of the excellent balance between flexibility and scratch resistance of the cured film, the ratio is preferably 1:1 to 10, more preferably 1:1 to 8.

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, if necessary, the polyol, and various known production methods are exemplified. Ru. Specifically, for example, a method may be mentioned in which a hydroxyl group-containing (meth)acrylate, a polyisocyanate, and, if necessary, a polyol are reacted in the presence of a catalyst at an appropriate reaction temperature (for example, 60 to 90° C., etc.). In addition, the order in which the hydroxyl group-containing (meth)acrylate, polyisocyanate, and polyol are reacted is not particularly limited, and examples thereof include a method in which each is optionally mixed and reacted, a method in which all components are mixed at once and reacted, and the like.

Examples of the above-mentioned catalysts include organotin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, organic acid tin catalysts such as tin octylate, organotitanium catalysts such as titanium ethylacetoacetate, and organozirconium catalysts such as zirconium tetraacetylacetonate. Examples include organic iron catalysts such as iron acetylacetonate. The above catalysts may be used alone or in combination of two or more.

(Polyester (meth)acrylate)
Examples of the polyester (meth)acrylate include dehydrated condensates of polyester polyol and (meth)acrylic acid. Examples of the polyester polyol include the above-mentioned polyester polyols.

(Epoxy (meth)acrylate)
Examples of the above-mentioned epoxy (meth)acrylates 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 epoxy resin, bisphenol F epoxy resin, biphenol epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, and naphthalene diol epoxy resin. Examples include resins, phenol dicyclopentadiene novolac type epoxy resins, and hydrogenated products thereof.

The aliphatic epoxy resins include, for example, diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; polyalkylenes such as diglycidyl ethers of polyethylene glycol and polypropylene glycol; Diglycidyl ethers of glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and their alkylene oxide adducts; di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and their alkylene oxide adducts, and pentaerythritol and polyglycidyl ethers of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of their alkylene oxide adducts; di- or polyglycidyl ethers of hydrogenated bisphenol A and their alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone di- Examples include glycidyl ether.

(Polyether (meth)acrylate)
Examples of the polyether (meth)acrylates include dehydrated condensates of polyether polyols and (meth)acrylic acid, and examples of the polyether polyols include the polyether polyols described above. Examples of the polyether (meth)acrylates 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 (meth)acrylate)
The above-mentioned polyacrylic (meth)acrylate is produced by, for example, reacting a homopolymer of epoxy group-containing mono(meth)acrylate or a copolymer of epoxy group-containing mono(meth)acrylate with other monomers with (meth)acrylic acid. things can be mentioned

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

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

Examples of the vinyl group-containing (meth)acrylates include vinyl ether group-containing (meth)acrylates. Vinyl ether group-containing (meth)acrylates include, for example, 2-vinyloxyethyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, and 3-vinyloxyethyl (meth)acrylate. -vinyloxypropyl, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, ( p-vinyloxymethylphenylmethyl meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-[2-(2-vinyloxyethoxy)ethoxy]ethyl (meth)acrylate, ( 2-(2-vinyloxypropoxy)propyl meth)acrylate, 2-(2-vinyloxyisopropoxy)isopropyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol mono(meth)acrylate Examples include vinyl ether.

Component (B) is preferably urethane (meth)acrylate since the cured film has excellent antistatic properties and moist heat resistance.

<Physical properties of polyfunctional (meth)acrylate (B)>
The physical properties of component (B) other than the weight average molecular weight are not particularly limited. Component (B) is preferably a compound having at least three (meth)acryloyl groups in the molecule, since the cured film has excellent scratch resistance.

The content of component (B) in the above active energy ray curable resin composition is not particularly limited, but 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 based on 100 mass of the active energy ray curable resin composition in terms of solid content. It is preferably about 20 to 60 parts by mass.

<Hydroxyl group-containing (meth)acrylate (C)>
Component (C) has a hydroxyl value (JIS K0070, hereinafter referred to as hydroxyl value) of 50 to 200 mgKOH/g, and contains at least one hydroxyl group and at least one (meth)acryloyl group in the molecule. As long as it is a compound having the following, various known compounds can be used without particular limitation. Component (C) can be used alone or in combination of two or more.

When the hydroxyl value of the component (C) is 50 mgKOH/g or more, the above-mentioned bleed-out is suppressed, so that the cured film has excellent moisture and heat resistance. In addition, when the hydroxyl value is 200 mgKOH/g or less, the cured film has excellent antistatic properties and moist heat resistance.

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

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

Component (C) is preferably hydroxyl group-containing polypentaerythritol poly(meth)acrylate or hydroxyl group-containing pentaerythritol poly(meth)acrylate from the viewpoint of excellent antistatic properties, scratch resistance, and moist heat resistance of the cured film; More preferred are 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.

<Physical properties of hydroxyl group-containing (meth)acrylate (C)>

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

The content of component (C) in the active energy ray-curable resin composition is not particularly limited, but since the cured film has excellent antistatic properties, scratch resistance, and moist heat resistance, the content of component (C) in the active energy ray-curable resin composition is It is preferably about 10 to 75 parts by weight based on 100 parts by weight of the curable resin composition.

(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). One type of reactive diluent may be used alone, or two or more types may be used in combination. By using a reactive diluent in combination, the compatibility between components (A) and (B) becomes even better. As a result, the transparency of the active energy ray-curable resin composition is improved, and a cured film having particularly excellent antistatic properties, transparency, hardness, and scratch resistance can be obtained.

Examples of the reactive diluent include di(meth)acrylate, the components (a1') to (a3'), the mono(meth)acrylate containing an alkyl ester group having 19 or more carbon atoms, and the aromatic ring structure-containing vinyl. Examples include monomers, ethyl carbitol acrylate, and the like. Di(meth)acrylate is particularly preferred from the viewpoint of compatibilization effect and cured film performance (hardness, scratch resistance, etc.).

The above di(meth)acrylates include, for example, 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 Type A 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 Examples include di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, hydroxypivalic 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 component (B), component (C), and reactive diluent in the composition is 100% by mass of the composition. It is preferably about 80 to 97% by mass.

In the above-mentioned active energy ray-curable resin composition, the content ratio of the component (B), the component (C), and the reactive diluent is not particularly limited; When the total amount of diluent is 100% by mass, the total amount of component (B) and component (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, the total amount of components (B) and (C) should be 50% It is preferable that the amount of the reactive diluent is about 5 to 50% by weight.

(Photopolymerization initiator)
The active energy ray-curable resin composition may contain a photopolymerization initiator. Two or more types of photopolymerization initiators may be used in combination. Examples of photopolymerization initiators include 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexylphenylketone, 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. Note that a photopolymerization initiator is used when curing with ultraviolet light, but is not necessarily required when curing with electron beams.

The content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited. The content of the photopolymerization initiator is preferably about 0.5 to 15 parts by weight, based on 100 parts by weight of the composition, in terms of solid content, from the viewpoint of the reaction progress of the (meth)acryloyl group.

(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-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol, acetylacetone, toluene, Examples include 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, propylene glycol monomethyl ether acetate, etc. It will be done. The diluting solvent may be used alone or in combination of two or more. Considering 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.

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 within a range such that the solid content concentration of the composition is about 1 to 60% by weight from the viewpoint of coatability.

(Additive)
The above-mentioned active energy ray-curable resin composition may contain an agent other than the above-mentioned solvent, the above-mentioned reactive diluent, or a photopolymerization initiator as an additive, as necessary, as long as the effects of the present invention are not impaired. . The additives may be used alone or in combination of two or more. Additives include, for example, antistatic agents other than component (A), antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifogging agents, hydrophilic agents, antifouling agents, pigments, Examples include metal oxide fine particle dispersions and organic fine particle dispersions.

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 based on 100 parts by mass of the composition in terms of solid content.

[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 onto various base films so that the mass after drying is about 0.05 to 30 g/m ² , preferably about 0.1 to 20 g/m ² . After drying, it is obtained by curing by irradiating active energy rays such as ultraviolet rays, electron beams, and radiation.

Examples of active energy rays used in the curing reaction include ultraviolet rays and electron beams. As the ultraviolet light source, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal halide lamp can be used. Note that the light intensity, light source arrangement, transport speed, etc. can be adjusted as necessary. For example, when using a high-pressure mercury lamp, the transport speed is 5 to 50 m for one lamp with a lamp output of about 80 to 160 W/cm. It is preferable to harden at a rate of about 1/2 min. On the other hand, in the case of electron beams, it is preferable to cure with an electron beam accelerator having an accelerating voltage of about 10 to 300 kV at a transport speed of about 5 to 50 m/min.

[film]
The film of the present invention includes the cured film described above. The film is an article whose constituent elements are the cured film and various base films.

Examples of the base film include plastic films, and various known ones can be used. Examples of the plastic film include polycarbonate film, polyester film, polyolefin film, polystyrene film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS resin film, AS resin film, acrylic resin film, and alicyclic polyolefin film. Examples include resin films. The plastic film is preferably one type of film selected from the group consisting of polycarbonate film, triacetyl cellulose film, acrylic resin film, and alicyclic polyolefin resin film from the viewpoint of transparency and adhesion with the cured film. . Further, the average thickness of the base film is not particularly limited, but is usually about 20 to 1000 μm, preferably 20 to 200 μm.

The above film can be manufactured 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 base film, dried if necessary, and then irradiated with the active energy ray. be done. Alternatively, a laminated film is produced by coating the non-coated surface of the obtained base film with the resin composition of the present invention, laminating another base film thereon, and then irradiating it with active energy rays. You can also do that.

Examples of the coating method include bar coater coating, wire bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexo printing, screen printing, and the like.

The coating amount is not particularly limited, but the mass after drying is preferably about 0.1 to 30 g/m ² , more preferably 1 to 20 g/m ² . Further, the average thickness of the cured film formed on the base film is usually about 0.05 to 30 μm, preferably about 0.1 to 20 μm.

The present invention will be explained in more detail below using 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.

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

Molecular weight measuring device: 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 NaNO ₃ 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)

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

Molecular weight measuring device: Product name “HLC-8220GPC”, Tosoh Co., Ltd. Column: Product name “TSKGel G1000H”, “TSKGel G2000H”, Tosoh Co., Ltd. Developing solvent: Tetrahydrofuran flow rate: 0.35 mL/min,
Sample concentration: 0.5g/L
Standard material: Polystyrene (Standard polystyrene kit PStQuick A, B, C manufactured by Tosoh Corporation)

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

Molecular weight measuring device: Product name “HLC-8220GPC”, Tosoh Co., Ltd. Column: Product name “TSKGel guardcolumn SuperHZ-L”, Tosoh Co., Ltd. Developing solvent: Tetrahydrofuran flow rate: 0.35 mL/min,
Sample concentration: 0.5g/L
Standard material: Polystyrene (Standard polystyrene kit PStQuick A, B, C manufactured by Tosoh Corporation)

((a2) Synthesis of component)
Synthesis example 1
130 parts of hydroxyethyl methacrylate, 1140 parts of ε-caprolactone and 1.3 parts of tin octylate were added to a reaction apparatus equipped with a stirring device and a cooling tube, the temperature was raised to 150°C, the temperature was kept for 6 hours, and then cooled. A ring-opening polyadduct (hereinafter referred to as component (a2-1)) of a hydroxyl group-containing vinyl monomer and lactone having a weight average molecular weight of 2,760 was obtained.

<Synthesis of component (A)>
Manufacturing example 1
In a reaction apparatus similar to Synthesis Example 1, 100 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) (hereinafter referred to as component (a1-1)), 60 parts of component (a2-1), and tert-butyl methacrylate ( t-BMA) (hereinafter referred to as component (a3-1)) and 800 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were added, and the temperature was raised to 80°C. Next, 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, kept at 80°C for 3 hours, and then heated to 113°C. After keeping the temperature for 2 hours, it was cooled to obtain a solution (non-volatile content: 20%) of the polymer (A-1) containing a quaternary ammonium salt structure. The weight average molecular weight of the obtained polymer was 220,000.

<Synthesis of component (B) (urethane (meth)acrylate)>
Manufacturing example 2
In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 70 parts of an isocyanurate modified product of hexamethylene diisocyanate (product name: "Coronate HXR" manufactured by Tosoh Corporation) and 0.03 part of tin octylate were added. After charging 177 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Viscoat #300" manufactured by Osaka Organic Chemical Industry Co., Ltd.), the temperature in the system was raised to about 80°C over about 1 hour. The temperature rose to . Next, the reaction system was maintained at the same temperature for 1 hour, and then cooled to form a mixture of urethane (meth)acrylate and unreacted monomers (urethane (meth)acrylate (B-1) with a solid content of 100% by mass. Hereinafter, (referred to as component (B-1)) was obtained. Component (B-1) was a mixture containing urethane (meth)acrylate having nine (meth)acryloyl groups in the molecule, and the weight average molecular weight of the urethane (meth)acrylate was 16,000. .

Manufacturing example 3
In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 70 parts of an isocyanurate modified product of hexamethylene diisocyanate (product name: "Coronate HXR" manufactured by Tosoh Corporation) and 0.03 part of tin octylate were added. After charging 177 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester A-9550W"), the temperature in the system was adjusted over approximately 1 hour. The temperature was raised to approximately 80°C. Next, the reaction system was maintained at the same temperature for 1 hour, and then cooled to form a mixture of urethane (meth)acrylate and unreacted monomers (urethane (meth)acrylate (B-2)) with a solid content of 100% by mass. (referred to as component (B-2)) was obtained. Component (B-2) was a mixture containing urethane (meth)acrylate having nine (meth)acryloyl groups in the molecule, and the weight average molecular weight of the urethane (meth)acrylate was 44,000. .

Comparative manufacturing example 1
In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 70 parts of an isocyanurate modified product of xylylene diisocyanate (manufactured by Mitsui Chemicals, Inc., trade name "Takenate D-131N") and 0 parts of tin octylate were added. After charging 177 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name "Viscoat #300" manufactured by Osaka Organic Chemical Industry Co., Ltd.), the temperature in the system was lowered over about 1 hour. The temperature was raised to approximately 80°C. Next, the reaction system was maintained at the same temperature for 1 hour, and then cooled to form a mixture of urethane (meth)acrylate and unreacted monomers (urethane (meth)acrylate (b-1)) with a solid content of 100% by mass. (referred to as component (b-1)) was obtained. Component (b-1) was a mixture containing urethane (meth)acrylate having nine (meth)acryloyl groups in the molecule, and the weight average molecular weight of the urethane (meth)acrylate was 9,000. .

<Preparation of active energy ray-curable resin composition>
Example 1
6 parts of component (A-1) in solution form, 26 parts of component (B-1), hydroxyl group-containing polypentaerythritol polyacrylate (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 90 mgKOH/g) 46 parts of ethylene glycol dimethacrylate (trade name "NK Ester A-9570W" manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter referred to as component (C-1)) (trade name "Light" manufactured by Kyoeisha Chemical Co., Ltd.) Ester EG") and 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by IGM Resins B.V., trade name "Omnirad 184", hereinafter referred to as Omni 184) were blended at a solid content ratio, and PGM This was diluted to prepare an active energy ray-curable resin composition with a nonvolatile content of 50%.

Example 2
In Example 1, 5 parts of component (A-1) in solution form, 43 parts of component (B-2) instead of component (B-1), 29 parts of component (C-1), and ethylene glycol di The preparation was carried out in the same manner as in Example 1, except that 23 parts of ethyl carbitol acrylate (trade name "Viscoat #190" manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of methacrylate, and the active energy of non-volatile content was 50%. A line-curable resin composition was prepared.

Example 3
In Example 2, instead of component (C-1), hydroxyl group-containing pentaerythritol polyacrylate (mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value 120 mgKOH/g, product name manufactured by Osaka Organic Chemical Industry Co., Ltd.) An active energy ray-curable resin composition with a nonvolatile content of 50% was prepared in the same manner as in Example 2, except that 29 parts of "Viscoat #300" (hereinafter referred to as component (C-2)) was used. Prepared.

Example 4
In Example 2, instead of component (B-2), polyvinyl acrylate (vinyl polymer of 2-(2-vinyloxyethoxy)ethyl acrylate, weight average molecular weight 22,000, at least two ( Example 2 except that 43 parts of Nippon Shokubai Co., Ltd. product name "AX-4-HC-NS-M" (hereinafter referred to as component (B-3)) having a meth)acryloyl group was used. Preparation was carried out in the same manner to prepare an active energy ray-curable resin composition with a nonvolatile content of 50%.

Comparative example 1
In Example 2, an active energy ray-curable resin with a non-volatile content of 50% 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). A composition was prepared.

Comparative example 2
In Example 1, instead of component (C-1), hydroxyl group-containing polypentaerythritol polyacrylate (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, hydroxyl value 45mgKOH/g manufactured by Shin Nakamura Chemical Industry Co., Ltd.) The product was prepared in the same manner as in Example 1, except that 46 parts of NK Ester A-9550W (trade name: "NK Ester A-9550W") (hereinafter referred to as component (c-1)) was used. A resin composition was prepared.

Comparative example 3
In Example 1, instead of component (C-1), hydroxyl group-containing pentaerythritol polyacrylate (a mixture of pentaerythritol monoacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value 290 mgKOH/g, The preparation was carried out in the same manner as in Example 1 except that 46 parts of Toagosei Co., Ltd. product name "Aronix MT-3548" (hereinafter referred to as component (c-2)) was used. An active energy ray-curable resin composition was prepared.

The blending amounts in Table 1 are values in parts by mass converted to solid content.

<Production of film>
The active energy ray-curable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were applied onto a 100 μm thick PET film (product name: "Lumirror 100U483" manufactured by Toray Industries, Inc.) after curing. The film was coated to a thickness of 5 μm using a #15 bar coater and dried at 80° C. for 1 minute. Next, the obtained film was cured using an ultraviolet curing device (manufactured by Multiply Co., Ltd., trade name "UBT-080-7A/BM" high pressure mercury lamp 600 mJ/cm ² ) to obtain a film with a cured film. Table 1 shows the following evaluation results for the produced films.

(Surface resistance test)
The surface resistance value (Ω/□) of the above film immediately after preparation was applied using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., product name "Hiresta MCP-HT-450") according to JIS K 6911. Measurement was made at a voltage of 500V.

(Moist heat resistance test)
After the film was allowed to stand for 24 hours in an environment with a temperature of 80° C. and a humidity of 95% Rh, the presence or absence of surface precipitates on the film surface was visually confirmed.
No surface precipitates...○Surface precipitates...×

(Pencil hardness test)
The cured film of the above film was evaluated by a pencil scratch test (based on JIS K 5400) with a load of 500 g.

Claims (8)

Polymer (A) having a quaternary ammonium salt structure,
A polyfunctional (meth)acrylate (B) with a weight average molecular weight (Mw) of 10,000 to 50,000 (excluding component (C)), and a hydroxyl group-containing (with a hydroxyl value of 50 to 200 mgKOH/g) An active energy ray-curable resin composition containing meth)acrylate (C). (A) The component is
A structural unit derived from a vinyl monomer having a quaternary ammonium salt structure (a1),
A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and
a vinyl monomer-derived structural unit (a2) having a weight average molecular weight of 1,000 to 10,000;
and a vinyl monomer-derived structural unit (a3) containing an alkyl ester group having 1 to 18 carbon atoms,
The active energy ray-curable resin composition according to claim 1, which is a polymer containing. The active energy ray-curable resin composition according to claim 1 or 2, wherein the weight average molecular weight (Mw) of component (B) is 15,000 to 50,000. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein component (B) is urethane (meth)acrylate. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein component (C) has a hydroxyl value of 90 to 150 mgKOH/g. The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein component (C) is a hydroxyl group-containing (meth)acrylate having at least three (meth)acryloyl groups in the molecule. . A cured film comprising the active energy ray-curable resin composition according to any one of claims 1 to 6. A film comprising the cured film according to claim 7.