CN111748235A

CN111748235A - Antistatic agent for active energy ray-curable resin composition, cured film, and film

Info

Publication number: CN111748235A
Application number: CN202010211991.3A
Authority: CN
Inventors: 佐佐木理绪; 平崎正和; 大河亮太
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2019-03-26
Filing date: 2020-03-24
Publication date: 2020-10-09
Also published as: KR20200115233A; JP2020164829A

Abstract

[ problem ] to provide a novel antistatic agent capable of providing a cured film excellent in antistatic properties, transparency and moist heat resistance. [ means of solution ] an antistatic agent for an active energy ray-curable resin composition, comprising a polymer (A) containing: 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; a structural unit (a3) derived from a vinyl monomer having an alkyl ester group having 1 to 18 carbon atoms; and a structural unit (a4) derived from a polyazo compound having a polyoxyethylene structure and/or a polyperoxide compound having a polyoxyethylene structure.

Description

Antistatic agent for active energy ray-curable resin composition, cured film, and film

Technical Field

The present invention relates to an antistatic agent for an active energy ray-curable resin composition, a cured film (hardened film), and a film (フィルム).

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, for example, a method of adding a conductive filler to an active energy ray-curable resin composition is known, and patent document 1 proposes the use of zinc antimonate fine particles as a conductive filler. However, in order to obtain a sufficient antistatic effect, it is necessary to use a large amount of conductive filler, and in such a case, transparency, hardness, and the like of the cured film may be adversely affected. In addition, when the conductive filler is zinc antimonate fine particles, coloration due to visible light is observed in the cured film, and therefore, the conductive filler is not particularly suitable for flat panel display applications.

Further, although it is also conceivable to use an organic substance (pi-conjugated conductive polymer) such as poly (thiophene) or poly (aniline) as an antistatic agent, since these are generally strongly colored, there is still a problem in coloring of a cured film.

On the other hand, even in the case of a conductive polymer, if a copolymer having a quaternary ammonium salt structure is used, the above-mentioned problem concerning coloring does not occur. However, the copolymer generally has insufficient compatibility with organic compounds such as active energy ray-curable resins, and the cured film obtained therefrom also has a problem of reduced transparency (haze). In view of these problems, patent document 2 proposes that a copolymer obtained by grafting a lactone chain having a hydroxyl group terminal and an alicyclic alkyl ester chain onto a copolymer having a quaternary ammonium salt structure has excellent compatibility with an active energy ray-curable resin (poly (meth) acrylate compound), and that a cured film can be provided with excellent antistatic properties and transparency.

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 inventors of the present invention have found that the antistatic agent 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 the cured film may have a problem in terms of wet heat resistance due to a decrease in transparency and poor appearance.

The invention aims to provide a novel antistatic agent capable of providing a cured film with excellent antistatic property, transparency and humidity resistance.

Means for solving the problems

As a result of intensive studies by the present inventors, it was found that an antistatic agent containing a specific copolymer having a quaternary ammonium salt structure solves the above-mentioned technical problems. That is, the present invention relates to the following antistatic agent for an active energy ray-curable resin composition, cured film and film.

1. An antistatic agent for an active energy ray-curable resin composition, comprising a polymer (A) containing:

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;

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

a structural unit derived from a polyazo compound having a polyoxyethylene structure and/or a polyperoxide compound having a polyoxyethylene structure (a 4).

2. The antistatic agent for an active energy ray-curable resin composition according to the above item 1, wherein the structural unit (a4) is a structural unit derived from a polyazo compound having a polyoxyethylene structure.

3. The active energy ray-curable resin composition comprising the antistatic agent for an active energy ray-curable resin composition according to the above item 1 or 2 and a poly (meth) acrylate having at least 3 (meth) acryloyl groups in a molecule.

4. A cured film comprising the active energy ray-curable resin composition according to the above item 3.

5. A film comprising the cured film as described in the aforementioned item 4.

Advantageous effects

Since bleeding of the antistatic agent under a high-temperature and high-humidity environment is suppressed in the cured film containing the antistatic agent of the present invention, the antistatic agent of the present invention can provide a cured film excellent in moist heat resistance. Further, since the antistatic agent is excellent in compatibility with various active energy ray-curable resins, particularly, is improved in compatibility with urethane-modified poly (meth) acrylate (which is difficult to be compatible with conventional antistatic agents), a cured film having excellent transparency can be provided by combining the antistatic agent with a wide range of active energy ray-curable resins. Further, a cured film containing the antistatic agent is excellent in antistatic properties and also excellent in scratch resistance due to high hardness.

The active energy ray-curable resin composition of the present invention can provide a cured film having excellent antistatic properties, transparency, moist heat resistance and scratch resistance, and thus can be suitably used as a coating agent for front panels of various flat panel displays.

The film of the present invention is excellent in antistatic properties, transparency, 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

The antistatic agent for an active energy ray-curable resin composition (hereinafter referred to as antistatic agent) of the present invention contains a polymer (a) (hereinafter referred to as component (a)) containing: 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; and a structural unit (a4) (hereinafter referred to as structural unit (a4)) derived from a polyazo compound having a polyoxyethylene structure and/or a polyperoxide compound having a polyoxyethylene structure.

< Polymer (A) >

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) and the like are exemplified:

[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 may be made of Cl^-、SO₄ ^2-、SO₃ ^2-、C₂H₅SO₄ ^-、Br^-Etc., from the viewpoint of antistatic effect, Cl is most preferable^-. 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. Specific examples thereof include hydroxyl group-containing (meth) acrylic compounds and hydroxyl group-containing vinyl ethers. Among these, hydroxyl group-containing (meth) acrylic compounds are preferable 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.

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

The component (a 2') has a weight-average molecular weight 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 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. The same applies hereinafter.

(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 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, from the viewpoint that the compatibility of the antistatic agent of the present invention with the active energy ray-curable resin becomes good, it is preferable that the component (a 3') does not have an alicyclic structure, 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, An isopentadecanyl ester group, an isohexadecyl ester group, an isoheptadecyl ester group, and an isooctadecyl ester group.

The component (a 3') is, for example, a mono (meth) acrylate containing the 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 of the cured film.

The structural unit (a4) is a structural unit contained in a polymer chain in the production of a polymer using a polyazo compound (a4 '-1) having a polyoxyethylene structure (hereinafter referred to as a component (a 4' -1)) and/or a polyperoxide compound (a4 '-2) having a polyoxyethylene structure (hereinafter referred to as a component (a 4' -2)). The component (a4 '-1) and the component (a 4' -2) may be used alone in 1 kind or in combination of 2 or more kinds.

In the synthesis of component (A), component (a4 '-1) and component (a 4' -2) function as polymerization initiators, and a structural unit (a4) is introduced into the terminal portion of component (A). As a result of intensive studies, the present inventors have found that bleeding of an antistatic agent containing the component (a) from a cured film under a high-temperature and high-humidity environment is suppressed by introducing a polyoxyethylene structure of the structural unit (a4) into an end portion of the component (a). On the other hand, it was found that when the structural unit (a1) to the structural unit (a3) or the structural unit (a5) described later in the component (a) contains a polyoxyethylene structure, it is difficult to suppress the bleeding of the antistatic agent under a high-temperature and high-humidity environment. That is, it is not preferable that the component (a) has a polyoxyethylene structure in addition to the structural unit (a 4).

The component (a 4' -1) can be any known polyazo compound without limitation as long as it has a polyoxyethylene structure. Specifically, for example, a polyazo compound having a repeating unit represented by the following general formula (2):

[ solution 1]

(in the formula, R¹The same or different, represent an optionally substituted alkylene group having 1 to 20 carbon atoms, a carbonyl group, a carboxyl group, or a group in which an optionally substituted alkylene group having 1 to 20 carbon atoms is bonded to a carbonyl group or a carboxyl groupAnd (4) clustering. R²The same or different, represent alkyl with 1-20 carbon atoms, alkyl with 1-10 carbon atoms substituted by carboxyl, phenyl or substituted phenyl. R³The same or different, represent an alkyl group having 1 to 20 carbon atoms, a cyano group, an acetoxy group, a carbamoyl group, or a carbonyl group substituted with an alkoxy group having 1 to 10 carbon atoms. n is the same or different and represents the average addition mole number of the oxyethylene groups and is an integer of 1 to 1000).

As R in the above general formula (2)¹Examples of the substituent(s) include an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group and an amino group.

Among the polyazo compounds having a repeating unit represented by the above general formula (2), from the viewpoint of easy handling, a polyazo compound having a structure represented by the following general formula (3) and/or a polyazo compound having a structure represented by the following general formula (4) is preferable:

[ solution 2]

(wherein n1 represents an integer of 3 to 200, and m1 represents an integer of 3 to 50.)

[ solution 3]

(in the formula, n2 represents an integer of 3 to 200, and m2 represents an integer of 3 to 50).

From the viewpoint of easy handling, the polyazo compound having the repeating unit represented by the above general formula (2) is more preferably a polyazo compound having a structure represented by the above general formula (4).

From the viewpoint of excellent wet heat resistance and antistatic property of the cured film, n2 in the general formula (4) is preferably an integer of 3 to 20. From the same viewpoint, the number average molecular weight of the polyoxyethylene moiety in the general formula (4) is preferably 1,500 to 6,600. In addition, m2 in the general formula (4) is preferably an integer of 4 to 15 from the viewpoint of excellent wet heat resistance and antistatic property of the cured film. In the present specification, the number average molecular weight refers to 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. The same applies hereinafter.

Examples of commercially available polyazo compounds having a structure represented by the above general formula (4) include VPE series such as "VPE-0201" (the number average molecular weight of the polyoxyethylene moiety is about 2,000, n2 is about 45, m2 is about 10), and "VPE-0401" (the number average molecular weight of the polyoxyethylene moiety is about 4,000, n2 is about 90, m2 is about 7), and "VPE-0601" (the number average molecular weight of the polyoxyethylene moiety is about 6,000, n2 is about 135, and m2 is about 5), which are manufactured by wako pure chemical industries (ltd.).

As the component (a 4' -2), any known ones can be used without limitation as long as they are a polyperoxide compound having a polyoxyethylene structure. Specifically, for example, a polyperoxide compound having a structure represented by the following general formula (5) and the like are exemplified:

[ solution 4]

(in the formula, n3 represents an integer of 3 to 50, and m3 represents an integer of 2 to 10).

The structural unit (a4) is preferably a structural unit derived from the component (a 4' -1) from the viewpoint of excellent transparency and moist heat resistance of the cured film.

(A) The content of the structural unit (a4) 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 wet heat resistance and antistatic property of the cured film. The content of the structural unit (a4) relative to the structural units (a1) to (a3) and the structural unit (a5) described later is not particularly limited, and is preferably about 7 to 25 mass% relative to 100 mass% of the total amount of the structural units (a1) to (a3) and the structural unit (a5) described later, from the viewpoint of excellent moisture-heat resistance and antistatic property of the cured film.

(A) Component (b) may further contain a structural unit (a5) (hereinafter also referred to as a structural unit (a5)) other than the structural units (a1) to (a 4). The structural unit (a5) is a structural unit contained in a polymer chain in the production of a polymer using a monomer (a5 ') (hereinafter referred to as the (a 5') component) other than the monomer (a1 ') to the monomer (a 3'). The component (a 5') may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the component (a 5') 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 containing an alkyl ester group having 19 or more carbon atoms include nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, docosyl (meth) acrylate, tricosyl (meth) acrylate, 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 (a5) 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 and transparency of the cured film.

(A) The content ratio of the structural units (a1) to (a4) in the component (A) is not particularly limited, but is preferably (35 to 45): (5 to 15): 6 to 22) (mass ratio) in order from the viewpoint of compatibility of the component (A) with the active energy ray-curable resin and antistatic property and transparency of the cured film. When the component (A) contains the structural unit (a5), the content ratio of the structural unit (a1) to the structural unit (a5) in the component (A) is not particularly limited, and for the same reason, it is preferably (35 to 45): (5 to 15): (6 to 22): 0 to 15) (mass ratio) in this order.

(A) The physical properties of the components are not particularly limited. (A) The weight average molecular weight of the 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, 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 a poly (meth) acrylate 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. The same applies hereinafter.

(A) Component (c) can be obtained by radical copolymerization of the above-mentioned component (a1 '), (a 2'), (a3 ') and component (a 4' -1) and/or component (a4 '-2), and if necessary component (a 5'), 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 other than the component (a4 '-1) and the component (a 4' -2) may be used as long as the effects of the present invention are obtained. Examples of such a radical polymerization initiator include azo polymerization initiators other than the component (a4 '-1) and peroxide polymerization initiators other than the component (a 4' -2). 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 NIPPHI HYDRAZINE INDUSTRY (ヒドラジン, Inc. , trade name "ABN-E", etc. ], 2-azobis (2, 4-dimethylvaleronitrile) [ for example, manufactured by NIPPHI HYDRAZINE INDUSTRY, trade name "ABN-V", etc. ], 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 Nichiya oil Co., Ltd., trade name "PEROYL (パーロイル, registered trademark) ], and the like.

The amount of the radical polymerization initiator other than the component (a4 ' -1) and the component (a4 ' -2) is not particularly limited, and is usually about 0.01 to 30% by mass based on the total mass of the components (a1 ') to (a3 ') and (a5 ').

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 (a5 ').

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 (a5 '). In addition, in the case of emulsion polymerization, various known anionic, nonionic and cationic surfactants can be used.

[ antistatic agent for active energy ray-curable resin composition ]

The antistatic agent of the present invention contains component (A). The antistatic agent may further contain a diluting solvent in addition to the component (A).

Examples of the diluting 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.

The content of the diluting solvent in the above antistatic agent is not particularly limited. When the antistatic agent contains a diluent solvent, the content of the diluent solvent is preferably about 25 to 1900 parts by mass per 100 parts by mass of the antistatic agent from the viewpoint of coatability. From the viewpoint of coatability, the content of the diluting solvent is preferably in a range such that the solid content concentration of the antistatic agent is about 5 to 50 wt%.

The above antistatic agent may contain an agent other than the (a) component and the diluting solvent as an additive. 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 antioxidants, ultraviolet absorbers, light stabilizers, defoaming agents, surface conditioning agents, antifouling agents, antifogging agents, hydrophilizing agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.

The content of the above additive in the above antistatic agent is not particularly limited. The content of the additive is preferably about 0 to 50 parts by mass with respect to 100 parts by mass of the antistatic agent. The content of the additive to the component (a) is not particularly limited. The content of the additive is preferably about 0 to 333 parts by mass based on 100 parts by mass of the component (A).

[ active energy ray-curable resin composition ]

The active energy ray-curable resin composition (hereinafter also referred to as composition) of the present invention contains the above antistatic agent, a poly (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule (hereinafter also referred to as poly (meth) acrylate), and if necessary, a reactive diluent, a photopolymerization initiator, and an additive.

The content of the antistatic agent in the composition is not particularly limited, and is preferably about 3 to 15% by mass in terms of solid content with respect to 100% by mass of the composition.

Examples of the poly (meth) acrylate include a non-urethane-modified poly (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule, and a urethane-modified poly (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule. The poly (meth) acrylate may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the non-urethane-modified poly (meth) acrylate include polypentaerythritol poly (meth) acrylates having at least 3 (meth) acryloyl groups in the molecule, such as dipentaerythritol poly (meth) acrylate and tripentaerythritol poly (meth) acrylate; pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like.

Examples of the urethane-modified poly (meth) acrylate include a reaction product of a component having 1 or more hydroxyl groups in the non-urethane-modified poly (meth) acrylate or a hydroxyl group-containing (meth) acrylate having 2 or less (meth) acryloyl groups in the molecule and various known polyisocyanates. The urethane-modified poly (meth) acrylate may be a mixture containing unreacted monomer components.

Examples of the polyisocyanate include aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates; and the biuret, isocyanurate, allophanate, adduct forms, etc., of these diisocyanates. From the viewpoint of weather resistance of the cured film, the above-mentioned polyisocyanate is preferably an alicyclic diisocyanate, an aliphatic diisocyanate, and a biuret form, an isocyanurate form, an allophanate form, an adduct form of these diisocyanates.

The aromatic diisocyanate includes, for example, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 1, 3-xylylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 3-methyl-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and the like.

The above alicyclic diisocyanate is exemplified by dicyclohexylmethane diisocyanate and isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, and the like.

Examples of the aliphatic diisocyanate include hexamethylene diisocyanate.

The physical properties of the above poly (meth) acrylate are not particularly limited. The molecular weight of the poly (meth) acrylate is preferably about 550 to 10,000, more preferably about 550 to 7,000, from the viewpoint of excellent compatibility with the component (a) and antistatic properties, transparency and hardness of the cured film.

In addition, in the present specification, in the case of simply describing "molecular weight", the following meanings are given. That is, when the structure of the compound can be uniquely represented by a specific chemical formula, such as dipentaerythritol poly (meth) acrylate, the molecular weight means the formula weight. On the other hand, in the case where the structure of the compound cannot be uniquely represented by a specific chemical formula as in the case of the polymer poly (meth) acrylate, the above molecular weight means a weight average molecular weight.

The content of the poly (meth) acrylate in the composition is not particularly limited, and is preferably about 80 to 97% by mass in terms of solid content with respect to 100% by mass of the composition.

The composition may comprise 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 above-mentioned "poly (meth) acrylate". 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 of the component (a) with the poly (meth) acrylate becomes better. As a result, the composition of the present invention has improved transparency, and a cured film particularly excellent in antistatic properties, transparency, hardness, scratch resistance, and the like can be obtained.

Examples of the reactive diluent include di (meth) acrylates, the components (a1 ') to (a 3'), the mono (meth) acrylates having an alkyl ester group having 19 or more carbon atoms, and the aromatic ring structure-containing vinyl monomers. 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 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, bisphenol a ethylene oxide-modified di (meth) acrylate (ビスフェノール a エチレンオキシド variation ジ (メタ) アクリレート), and the like.

When the poly (meth) acrylate and the reactive diluent are used in combination in the composition, the total content of both is preferably about 80 to 97% by mass with respect to 100% by mass of the composition.

In the composition, the content ratio of the poly (meth) acrylate and the reactive diluent is not particularly limited, and usually, when the total of the two is 100% by mass, the poly (meth) acrylate 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 poly (meth) acrylate is about 50 to 95% by mass and the reactive diluent is about 5 to 50% by mass.

The 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 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.

The composition may contain the diluting solvent in consideration of coating workability and the like. Among them, at least 1 kind selected from the group consisting of the above glycol ethers, alcohols and ketones is preferable in view of the surface smoothness of the cured film obtained from the composition.

The content of the diluting solvent in the above composition is not particularly limited. When the composition contains a diluting solvent, the content of the diluting 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.

The composition may contain, as an additive, a reagent other than any one of the antistatic agent, a diluting solvent, a poly (meth) acrylate, a reactive diluent, and a photopolymerization initiator. The additive may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The additives include, for example, the above additives.

The content of the additive in the 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 above-mentioned active energy ray-curable resin compositionAnd (4) obtaining. 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 laminated film (the body frame portions 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 substrate film with active energy rays.

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, more preferably 1g/m²～20g/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.

The weight average molecular weight of the component (a) 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))

< Synthesis of component (a2) >

Synthesis example 1

130 parts of hydroxyethyl methacrylate, -1140 parts of 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 example 2

130 parts of hydroxyethyl methacrylate, -500 parts of caprolactone and 1.3 parts of tin octylate were charged into a reaction apparatus equipped with a stirring apparatus and a cooling tube, 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 and lactone having a weight average molecular weight of 800 (hereinafter referred to as component (b-1)).

The weight average molecular weights of the component (a2-1) and the component (b-1) were determined by using a commercially available molecular weight measuring instrument (the main product name "HLC-8220 GPC", manufactured by Chinese imperial ソー (strain); the column product names "TSKGel G1000H", "TSKGel G2000H", manufactured by Chinese imperial ソー (strain); the developing solvent: tetrahydrofuran) under the following conditions (the same applies hereinafter):

developing solvent: the reaction mixture of tetrahydrofuran and water is taken as a reaction mixture,

flow rate: the concentration of the active carbon is 0.35mL/min,

sample concentration: 0.5 percent of the total weight of the mixture,

standard substance: polystyrene (standard polystyrene kit PStQuickA, B, C, manufactured by imperial ソー).

The composition and weight average molecular weight (the same below) are shown in table 1.

< Synthesis of component (A) >

Example 1

94 parts of component (a2-1), 24 parts of t-butyl methacrylate (t-BMA) (hereinafter referred to as component (a 3-1)), a polyazo compound having a polyoxyethylene structure (product name "VPE-0201" manufactured by Wako pure chemical industries, Ltd.; a compound represented by the above general formula (4); hereinafter referred to as VPE-0201)22 parts, and 508 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 ℃. Subsequently, 100 parts of methacryloyloxyethyltrimethyl ammonium chloride (DMC) (hereinafter referred to as component (a 1-1)) and 455 parts of PGM were added thereto, and the mixture was incubated at 80 ℃ for 1 hour. Then, 5 parts of VPE-0201 and 15 parts of PGM were charged, and the mixture was incubated for 1 hour, then 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 210,000.

Example 2

The reaction was carried out in the same manner as in example 1 except that 24 parts of Stearyl Methacrylate (SMA) (hereinafter referred to as component (a 3-2)) was used in place of component (a3-1) in example 1 to obtain a solution (20% nonvolatile content) of polymer (A-2) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 210,500.

Example 3

The reaction was carried out in the same manner as in example 1 except that 24 parts of Methyl Methacrylate (MMA) (hereinafter referred to as (a 3-3)) was used in place of the component (a3-1) in example 1 to obtain a solution (nonvolatile content: 20%) of the polymer (A-3) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 200,500.

Example 4

The reaction was carried out in the same manner as in example 1 except that 44 parts and 10 parts of VPE-0201 were used in example 1, respectively, to obtain a solution (nonvolatile content: 20%) of the polymer (A-4) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 200,000.

Comparative example 1

100 parts of component (a1-1), 60 parts of component (a2-1), 40 parts of component (a3-1) and 800 parts of 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 kept at 80 ℃ for 3 hours, then at 113 ℃ for 2 hours, and then cooled to obtain a solution (nonvolatile fraction: 20%) of a polymer (. alpha. -1) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 220,000.

Comparative example 2

100 parts of the component (a1-1), 78 parts of the component (a2-1), 17 parts of the component (a3-1), 21 parts of methoxypolyethylene glycol methacrylate (product name: ブレンマー PME-400 manufactured by Nichisu oil Co., Ltd.; hereinafter referred to as PME400) and 832 parts of PGM were charged into the same reaction apparatus as in Synthesis example 1, and the temperature was raised to 80 ℃. Next, 8 parts of ABN-E and 32 parts of PGM were added to start the polymerization reaction, and the mixture was kept at 80 ℃ for 3 hours, then at 113 ℃ for 2 hours and then cooled to obtain a solution (20% nonvolatile matter) of the polymer (. alpha. -2) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 210,000.

Comparative example 3

100 parts of component (a1-1), 100 parts of component (a3-1) and 800 parts of PGM were charged into the same reaction apparatus as in Synthesis example 1, and the temperature was raised to 80 ℃. Subsequently, 8 parts of VPE-0201 and 32 parts of PGM were added to start the polymerization reaction, and the mixture was held at 80 ℃ for 3 hours, then at 113 ℃ for 2 hours and then cooled to obtain a solution (20% nonvolatile content) of a polymer (. alpha. -3) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 220,000.

Comparative example 4

The reaction was carried out in the same manner as in example 1 except that 24 parts of cyclohexyl methacrylate (CHMA) (hereinafter referred to as CHMA) was used in place of the component (a3-1) in example 1 to obtain a solution (nonvolatile content: 20%) of the polymer (. alpha. -4) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 100,000.

Comparative example 5

The reaction was carried out in the same manner as in example 1 except that 60 parts of the component (b-1) was used in place of the component (a2-1) in example 1 to obtain a solution (nonvolatile content: 20%) of the polymer (. alpha. -5) having a quaternary ammonium salt structure. The weight average molecular weight of the resulting polymer was 100,000.

[ Table 1]

The amount of each component used in table 1 is a value converted into parts by mass of the solid component. Abbreviations in table 1 are as follows.

VPE-0201: a polyazo compound having a polyoxyethylene structure represented by the general formula (4) (manufactured by Wako pure chemical industries, Ltd., trade name "VPE-0201")

ABN-E: 2, 2-azobis (2-methylbutyronitrile)

The PME 400: methoxypolyethylene glycol methacrylate (manufactured by Nichikoku K.K. 'ブレンマー PME-400')

CHMA: cyclohexyl methacrylate

< Synthesis of urethane-modified Poly (meth) acrylate (UA) >

Synthesis example 3

70 parts of an isocyanurate-modified form of hexamethylene diisocyanate (manufactured by doody ソー, trade name "CORONATE HXR"), 0.03 parts of tin octylate, and 177 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate were put into a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and then 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-modified poly (meth) acrylate and an unreacted monomer (urethane-modified poly (meth) acrylate (UA); hereinafter referred to as UA) having a solid content of 100 mass%. The obtained UA was a mixture containing a urethane-modified poly (meth) acrylate having 9 (meth) acryloyl groups in the molecule, and the molecular weight of the urethane-modified poly (meth) acrylate was 1,500.

< preparation of active energy ray-curable resin composition >

Example 5

An active energy ray curable resin composition having a nonvolatile content of 50% was prepared by blending 5 parts of an antistatic agent comprising a solution-form component (A-1), 95 parts of dipentaerythritol polyacrylate (hereinafter referred to as DPHA) (a mixture of 5 (meth) acryloyl groups and 6 (meth) acryloyl groups; manufactured by Toyo Synthesis Co., Ltd., trade name "ARONIX (アロニックス) M400") and 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by IGM Resins B.V., trade name "Omnirad 184", hereinafter referred to as Omni184) in the solid content ratio, and diluting the mixture with PGM.

Example 6

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in example 5, except that 95 parts of UA in synthesis example 3 was used instead of DPHA in example 5.

Example 7

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in example 5, except that 47.5 parts of DPHA and 47.5 parts of UA in Synthesis example 3 were used in place of DPHA in example 5.

Example 8

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in example 5, except that 80 parts of DPHA and 10 parts of an antistatic agent comprising a solution-like component (A-1) were used instead of DPHA and the antistatic agent comprising a solution-like component (A-1) in example 5.

Example 9

An active energy ray-curable resin composition was prepared in the same manner as in example 5 except that a mixed solvent of Methyl Ethyl Ketone (MEK) and PGM in a PGM mass ratio of 1/1 was used in place of PGM in the diluting solvent in example 5, and the nonvolatile component was 50%.

Example 10

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent comprising the component (A-2) in a solution state was used in place of the antistatic agent comprising the component (A-1) in a solution state in example 5.

Example 11

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent comprising the component (A-3) in a solution state was used in place of the antistatic agent comprising the component (A-1) in a solution state in example 5.

Example 12

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent comprising the component (A-4) in a solution state was used in place of the antistatic agent comprising the component (A-1) in a solution state in example 5.

Example 13

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in example 5, except that 97 parts of DPHA and 3 parts of an antistatic agent comprising a solution-like component (A-1) were used instead of DPHA and the antistatic agent comprising a solution-like component (A-1) in example 5.

Example 14

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in example 5, except that 90 parts of DPHA and 10 parts of an antistatic agent comprising a solution-like component (A-1) were used instead of DPHA and the antistatic agent comprising a solution-like component (A-1) in example 5.

Example 15

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in example 5, except that 85 parts of DPHA and 15 parts of an antistatic agent comprising a solution-like component (A-1) were used instead of DPHA and the antistatic agent comprising a solution-like component (A-1) in example 5.

Comparative example 6

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent composed of a component (. alpha. -1) in a solution state was used in place of the antistatic agent composed of a component (A-1) in a solution state in example 5.

Comparative example 7

An active energy ray-curable resin composition containing 50% nonvolatile components was prepared in the same manner as in comparative example 6, except that 95 parts of UA in synthesis example 3 was used instead of DPHA in comparative example 6.

Comparative example 8

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent composed of a component (. alpha. -2) in a solution state was used in place of the antistatic agent composed of a component (A-1) in a solution state in example 5.

Comparative example 9

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent composed of a component (. alpha. -3) in a solution state was used in place of the antistatic agent composed of a component (A-1) in a solution state in example 5.

Comparative example 10

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent composed of a component (. alpha. -4) in a solution state was used in place of the antistatic agent composed of a component (A-1) in a solution state in example 5.

Comparative example 11

An active energy ray-curable resin composition containing 50% of nonvolatile components was prepared in the same manner as in example 5, except that 5 parts of an antistatic agent composed of a component (. alpha. -5) in a solution state was used in place of the antistatic agent composed of a component (A-1) in a solution state in example 5.

[ Table 2]

The blending amount in table 2 is a value converted into parts by mass of the solid component. Abbreviations and notes in table 2 are as follows.

In addition, the antistatic agent is not mixed with the poly (meth) acrylate, and a uniform active energy ray curable resin composition cannot be obtained, and thus evaluation cannot be made.

DPHA: dipentaerythritol poly (meth) acrylate (a mixture of a compound having 5 (meth) acryloyl groups and a compound having 6 (meth) acryloyl groups in the molecule, molecular weight 500-600) (available under the trade name "aronex M400" from east asia corporation)

UA: synthesis example 3 urethane-modified Poly (meth) acrylate (UA) (a mixture containing urethane-modified Poly (meth) acrylate having 9 (meth) acryloyl groups in the molecule, the molecular weight of the urethane-modified Poly (meth) acrylate being 1,500)

Omni 184: 1-hydroxy-cyclohexyl-phenyl ketone (product of IGM Resins B.V., trade name "Omnirad 184")

< preparation of film >

The active energy ray-curable resin compositions of examples 5 to 15 and comparative examples 6 to 11 were applied to a PET film (manufactured by Bay レ, Inc.' under the trade name "Lumirror (ルミラー)100U 483") having a film thickness of 100 μm by a #15 bar coater so that the film thickness of the cured coating film became 5 μm, and the cured coating film was dried at 80 ℃ for 1 minute to prepare films. Next, the obtained film was subjected to UV curing using a high-pressure mercury lamp (trade name "UBT-080-7A/BM" manufactured by Tokaki Kaisha マルチプライ, high-pressure mercury lamp 600 mJ/cm)²) Thus, a film having a cured coating film was obtained. The following evaluation results for the produced film are shown in table 2.

(surface resistance test)

The surface resistance value (omega/□) immediately after the production of the above-mentioned film was measured at an applied voltage of 500V in accordance with 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.).

(measurement of transparency)

The haze value of the film was measured in accordance with jis k 5400 using a color haze meter (カラーへイズメーター) manufactured by village color technology research. Each haze value is a numerical value including the haze value of the polyester film as the substrate.

(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.

No surface precipitates-

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.

Claims

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;

2. The antistatic agent for an active energy ray-curable resin composition according to claim 1, wherein the structural unit (a4) is a structural unit derived from a polyazo compound having a polyoxyethylene structure.

3. The active energy ray-curable resin composition comprising the antistatic agent for an active energy ray-curable resin composition according to claim 1 or 2 and a poly (meth) acrylate having at least 3 (meth) acryloyl groups in the molecule.

4. A cured film comprising the active energy ray-curable resin composition according to claim 3.

5. A film comprising the cured film of claim 4.