KR20200115233A - An antistatic agent for active energy-ray curable resin composition, active energy-ray curable resin composition, cured film and film - Google Patents

Abstract

Provided is a novel antistatic agent capable of providing a cured film having excellent antistatic properties, transparency, and wet heat resistance. The antistatic agent for an active energy ray-curable resin composition comprises the antistatic agent for the active energy ray-curable resin composition containing a polymer (A). The polymer (A) contains: a structural unit (a1) derived from a vinyl monomer having a quaternary ammonium salt structure; a vinyl monomer-derived structural unit (a2) that is a ring-opening adduct of a hydroxyl group-containing vinyl monomer and a lactone and has a weight-average molecular weight of 1,000-10,000; a structural unit (a3) derived from a vinyl monomer containing an alkyl ester group having 1-18 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, active energy ray-curable resin composition, cured film and film TECHNICAL FIELD BACKGROUND OF THE INVENTION 1.

The present invention relates to an antistatic agent for an active energy ray-curable resin composition, an active energy ray-curable resin composition, a cured film and a film.

As a coating agent for various substrates, for example, as a hard coating agent used for the front plate of various display devices such as a liquid crystal display, a plasma display, and an organic EL display (hereinafter referred to as a flat panel display), for example, pentaeryth A composition comprising as a main component a compound having a large number of (meth)acryloyl groups in a molecule such as litol poly(meth)acrylate and ditrimethylolpropane poly(meth)acrylate (so-called active energy ray-curable resin) is known. Since the composition is instantaneously cured by irradiation with ultraviolet rays or electron beams, productivity is high, and a cured film excellent in hardness and scratch resistance is formed on the surface of various substrates.

However, in the case of providing the active energy ray-curable resin composition for a flat panel display, the cured film has high transparency, as well as preventing trouble caused by static electricity during assembly or operation of the display, or realizing a high-definition image. In order to do this, good antistatic properties are required.

As a method of 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 in Patent Document 1, using zinc antimonate fine particles as a conductive filler Is proposed. However, in order to obtain a sufficient antistatic effect, it is necessary to use a large amount of the conductive filler, but in such a case, the transparency or hardness of the cured film may be adversely affected. In addition, when the conductive filler is zinc antimonate fine particles, coloration derived from visible light is observed in the cured film, and thus, it is not particularly suitable for use in flat panel displays.

In addition, it is also conceivable to use organic substances such as poly(thiophene) or poly(aniline) (π-conjugated conductive polymer) as an antistatic agent, but since they are generally strongly colored, it is difficult to color the cured film. there was.

On the other hand, even if it is a conductive polymer, if a copolymer having a quaternary ammonium salt structure is used, it is said that the above coloring problem does not occur. However, the copolymer has a problem in that compatibility with an organic compound such as an active energy ray-curable resin is generally insufficient, and the transparency (haze) of the resulting cured film is also lowered. Regarding these problems, in Patent Document 2, the grafting of the lactone chain at the end of the hydroxyl group and the alicyclic alkyl ester chain to a copolymer containing a quaternary ammonium salt structure is compatible with active energy ray-curable resin (poly(meth)acrylate compound). It has excellent properties and proposes what can impart excellent antistatic properties and transparency to a cured film.

Japanese Laid-Open Patent Publication No. Hei 9-051116 Japanese Unexamined Patent Publication No. 2012-31297

However, as a result of investigation by the present inventors, when the antistatic agent in Patent Document 2 bleeds out (bleed out) in the resulting cured film under a high temperature and high humidity environment, and a decrease in transparency or poor appearance of the cured film is observed There was, and there was a problem in the moist heat resistance of the cured film.

The present invention makes it a subject to provide a novel antistatic agent capable of providing a cured film excellent in antistatic properties, transparency, and moist heat resistance.

As a result of intensive examination, the present inventors found that an antistatic agent containing a predetermined quaternary ammonium salt structure-containing copolymer solved the above problem. That is, the present invention relates to the following antistatic agents for active energy ray-curable resin compositions, active energy ray-curable resin compositions, cured films and films.

1. Constituent unit (a1) derived from a vinyl monomer having a quaternary ammonium salt structure,

It is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and lactone, and

Constituent unit (a2) derived from a vinyl monomer having a weight average molecular weight of 1,000 to 10,000,

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

An antistatic agent for an active energy ray-curable resin composition containing a polymer (A) containing a structural unit (a4) derived from a polyazo compound having a polyoxyethylene structure and/or a polyperoxide compound having a polyoxyethylene structure .

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

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

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

5. A film containing the cured film according to item 4 above.

The antistatic agent of the present invention can provide a cured film having excellent moist heat resistance because bleeding out of the antistatic agent in a high temperature and high humidity environment is suppressed in a cured film containing the same. In addition, the antistatic agent has excellent compatibility with various active energy ray-curable resins, and in particular, the compatibility with urethane-modified poly(meth)acrylate, which was difficult to be used in conventional antistatic agents, is improved. A cured film excellent in transparency can be provided by combination with a wide range of active energy ray-curable resins. Moreover, the cured film containing the said antistatic agent is excellent in antistatic property, and since it is high hardness, it is also excellent in scratch resistance.

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

Since the film of the present invention is excellent in antistatic properties, transparency, moist heat resistance and scratch resistance, it is suitable for use in flat panel displays such as liquid crystal displays, plasma displays, and organic EL displays.

The antistatic agent for the active energy ray-curable resin composition of the present invention (hereinafter referred to as an antistatic agent) is a structural unit (a1) derived from a vinyl monomer containing a quaternary ammonium salt structure (hereinafter referred to as a structural unit (a1)) , Constituent unit (a2) derived from a vinyl monomer (hereinafter referred to as constituent unit (a2)), which is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and lactone, and has a weight average molecular weight of 1,000 to 10,000, and alkyl having 1 to 18 carbon atoms. Constituent unit (a3) derived from a vinyl monomer containing an ester group (hereinafter referred to as constituent unit (a3)) and a polyazo compound having a polyoxyethylene structure and/or a constitution derived from a polyperoxide compound having a polyoxyethylene structure It contains a polymer (A) containing a unit (a4) (hereinafter referred to as a structural unit (a4)) (hereinafter, component (A)).

<Polymer (A)>

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

The component (a1') can be used without particular limitation, as long as it is a vinyl monomer having a quaternary ammonium salt structure in its molecule. Specifically, for example, general formula (1): [CH ₂ = C(R ¹ )-C(=O)-ABN ⁺ (R ² )(R ³ )(R ⁴ )] _n ·X ^n-

(Wherein, R ¹ is H or CH ₃ , R ² to R ⁴ is an alkyl group having 1 to 3 carbon atoms, A is O or NH, B is an alkylene group having 1 to 3 carbon atoms, X ^n- is (Meth)acrylate compounds, etc. which represent counter anionic species by n represents an integer of 1 or more are mentioned. Also, X is _{^{n-, Cl -, SO 4 2-,}} SO 3 2-, C 2 H 5 SO 4 -, Br - and the like, in terms of Cl antistatic effect ^- is most preferable. In addition, as a commercial item of the component (a1'), "Light ester DQ-100" by Kyoeisha Chemical Co., Ltd., "DMAEA-Q" by Kojin Co., Ltd. is mentioned, for example.

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. Moreover, a methylene group, an ethylene group, a propylene group, and an isopropylene group are illustrated as said C1-C3 alkylene group.

Although the content of the structural unit (a1) in the component (A) is not particularly limited, it is about 30 to 60 mass% with respect to 100 mass% of the component (A) from the viewpoint of excellent transparency and antistatic performance of the cured film. It is desirable.

The structural unit (a2) is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and a vinyl monomer (a2') having a weight average molecular weight of 1,000 to 10,000 (hereinafter referred to as a component (a2')) is used to form a polymer. It is a structural unit contained in a polymer chain at the time of manufacturing. The component (a2') may be used alone or in combination of two or more.

The component (a2') is produced by using a hydroxyl group-containing vinyl monomer and lactone, and performing a ring-opening polyaddition reaction by a known method. The hydroxyl-containing vinyl monomer may be used alone or in combination of two or more, and lactone may be used alone or in combination of two or more.

As the hydroxyl group-containing vinyl monomer, various known ones can be used without particular limitation. Specifically, a hydroxyl group-containing (meth)acrylic compound, a hydroxyl group-containing vinyl ether, etc. are mentioned, for example. Among these, a hydroxyl group-containing (meth)acrylic compound is particularly preferable from the viewpoint of radical copolymerization.

The hydroxyl group-containing (meth)acrylic compound includes, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acrylamide. Can be lifted.

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

As the lactone, various known ones can be used without particular limitation. Specifically, β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone, etc. are mentioned, for example. Among these, in particular from the viewpoint of the reactivity of ring-opening polymerization, one selected from the group consisting of ε-caprolactone and δ-valerolactone is preferable.

The weight average molecular weight of the component (a2') is 1,000 to 10,000. When the weight average molecular weight is less than 1,000, there is a tendency that the antistatic properties and moist heat resistance of the cured film are lowered. When the weight average molecular weight exceeds 10,000, synthesis of the component (a2') becomes difficult. The weight average molecular weight is preferably about 1,000 to 5,000 from the viewpoint that the cured film is excellent in transparency, antistatic properties, and moist heat resistance, and synthesis becomes easy. In addition, in the present specification, the weight average molecular weight of the component (a2') refers to a value in terms of polystyrene in the gel permeation chromatography method, but the measurement method is not particularly limited, and various known means can be employed. In addition, a commercially available measuring instrument can also be used. It is the same below.

Although the content of the structural unit (a2) in the component (A) is not particularly limited, it is preferably about 25 to 55% by mass with respect to 100% by mass of the component (A) from the viewpoint of excellent transparency of the cured film.

The component (a2') can be obtained by various known methods. Specifically, for example, a method of reacting the lactone with a ring-opening polyaddition using the hydroxyl group-containing vinyl monomer as an initiator may be mentioned. Further, the weight average molecular weight can be adjusted by appropriately selecting the injection ratio of both, the reaction temperature, and the catalyst species and amount during the reaction.

In the above reaction, a catalyst may be used. Examples of the catalyst include mineral acids such as sulfuric acid and phosphoric acid; Alkali metals such as lithium, sodium, and potassium; alkyl metal compounds such as n-butyllithium and t-butyllithium; Metal alkoxides such as titanium tetrabutoxide; And tin compounds such as dibutyltin dilaurylate, dibutyltin dioctorate, 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 mass based on 100% by mass of the total amount of the hydroxyl group-containing vinyl monomer and lactone.

The structural unit (a3) is a structural unit contained in the 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 component (a3')). . The component (a3') can be used alone or in combination of two or more. In addition, the component (a3') preferably does not have an alicyclic structure from the viewpoint of good compatibility between the antistatic agent of the present invention and the active energy ray-curable resin. In this case, the structural unit (a3) has an alicyclic structure. It becomes something you don't have.

As long as the component (a3') is a vinyl monomer having an alkyl ester group having 1 to 18 carbon atoms, various known ones can be used without particular limitation. In addition, in this specification, a "C1-C18 alkyl ester group" is an ester group represented by -C(=O)-O-R, and it means that R is a C1-C18 alkyl group.

The alkyl ester groups having 1 to 18 carbon atoms are, for example, methyl ester group, ethyl ester group, propyl ester group, butyl ester group, pentyl ester group, hexyl ester group, heptyl ester group, octyl ester group, 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, isomirystyl ester group, isopentadecyl ester group, iso A hexadecyl ester group, an isoheptadecyl ester group, an isostearyl ester group, etc. are mentioned.

As the component (a3'), the mono(meth)acrylate containing the aforementioned alkyl ester group having 1 to 18 carbon atoms is mentioned, for example.

The 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, isomyristoyl (meth)acrylate, isopentadecyl (meth)acrylate, isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate And isostearyl (meth)acrylate.

By including the structural unit (a3) in the component (A), the cured film containing the component (A) will have good antistatic properties over time. The component (a3') is particularly preferably one member selected from the group consisting of tert-butyl (meth)acrylate and isobutyl (meth)acrylate for the same reason.

The content of the structural unit (a3) in the component (A) is not particularly limited, but from the viewpoint of excellent transparency of the cured film, it is preferably about 5 to 30 mass% with respect to 100 mass% of the component (A).

The structural unit (a4) is a polyazo compound (a4'-1) having a polyoxyethylene structure (hereinafter referred to as a component (a4'-1)) and/or a polyperoxide compound (a4) having a polyoxyethylene structure. It is a structural unit contained in a polymer chain when a polymer is produced using'-2) (hereinafter referred to as a component (a4'-2)). The component (a4'-1) and the component (a4'-2) can be used alone or in combination of two or more.

In the synthesis of component (A), the component (a4'-1) and the component (a4'-2) function as a polymerization initiator, and the structural unit (a4) is introduced into the terminal portion of the component (A). As a result of intensive examination by the present inventors, by introducing the polyoxyethylene structure of the structural unit (a4) into the terminal portion of the component (A), bleeding of the antistatic agent containing the component (A) from the cured film in a high temperature and high humidity environment I found out to be suppressed. On the other hand, in the case where the polyoxyethylene structure is contained in the structural units (a1) to (a3) or the structural units (a5) described later in the component (A), bleed out of the antistatic agent is prevented in a high temperature and high humidity environment. They also found it difficult to contain. That is, in the component (A), it is not preferable to have a polyoxyethylene structure other than the structural unit (a4).

As the component (a4'-1), as long as it is a polyazo compound containing a polyoxyethylene structure, various known ones can be used without limitation. Specifically, for example, General Formula (2):

[Formula 1]

(In the formula, R ¹ is the same or different, and a group in which an alkylene group having 1 to 20 carbon atoms which may have a substituent, a carbonyl group, a carboxyl group, or an alkylene group having 1 to 20 carbon atoms which may have a substituent is bonded to a carbonyl group or a carboxyl group R ² is the same or different and represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a carboxyl group, a phenyl group or a substituted phenyl group R ³ is the same or different and having 1 to 20 carbon atoms Represents an alkyl group, 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, represents the average number of moles added of the oxyethylene group, and is an integer of 1 to 1000 The polyazo compound which has a repeating unit represented by .) is mentioned.

Examples of the substituent for R ¹ in the general formula (2) 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 general formula (2), from the viewpoint of easy handling, general formula (3):

[Formula 2]

(In the formula, n1 represents an integer of 3 to 200, m1 represents an integer of 3 to 50.) Polyazo compound having a structure represented by, and/or general formula (4):

[Formula 3]

(In the formula, n2 represents an integer of 3 to 200, and m2 represents an integer of 3 to 50.) A polyazo compound having a structure represented by is preferred.

The polyazo compound having a repeating unit represented by the general formula (2) is more preferably a polyazo compound having a structure represented by the general formula (4) from the viewpoint of ease of handling.

Since n2 in the said general formula (4) is excellent in moist heat resistance and antistatic performance of a cured film, it is preferable that it is an integer of 3-20. Moreover, it is preferable that the number average molecular weight of the polyoxyethylene structural part in said general formula (4) is 1,500-6,600 from the same point. In addition, m2 in the general formula (4) is preferably an integer of 4 to 15 from the viewpoint of excellent moist heat resistance and antistatic performance of the cured film. In addition, in this specification, the number average molecular weight refers to a polystyrene conversion value in a gel permeation chromatography method, but the measurement method is not particularly limited, and various known means can be employed, and commercially available measuring instruments are also available. Can be used. It is the same below.

A commercial product of a polyazo compound having a structure represented by the general formula (4) is, for example, "VPE-0201" manufactured by Wako Pure Chemical Industries, Ltd. (the number average molecular weight of the polyoxyethylene structural moiety is about 2,000, n2 = about 45, m2 = about 10), ``VPE-0401'' (the number average molecular weight of the polyoxyethylene structural moiety is about 4,000, n2 = about 90, m2 = about 7), ``VPE-0601'' (the number of polyoxyethylene structural moieties VPE series such as an average molecular weight of about 6,000, n2 = about 135, m2 = about 5) can be mentioned.

The component (a4'-2) can be used without limitation, as long as it is a polyperoxide compound containing a polyoxyethylene structure. Specifically, for example, general formula (5):

[Formula 4]

(In the formula, n3 represents an integer of 3 to 50, m3 represents an integer of 2 to 10.) A polyperoxide compound having a structure represented by.

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

Although the content of the structural unit (a4) in the component (A) is not particularly limited, from the viewpoint of excellent moist heat resistance and antistatic performance of the cured film, about 5 to 30% by mass relative to 100% by mass of the component (A) It is preferable to be. In addition, the content of the structural unit (a4) relative to the structural units (a1) to (a3) and the structural unit (a5) described later is also not particularly limited, but since the cured film has excellent moist heat resistance and antistatic performance, the structural unit ( It is preferable that it is about 7-25 mass% with respect to 100 mass% of the total amount of a1)-(a3) and structural unit (a5) mentioned later.

The component (A) may further contain structural units (a5) other than the structural units (a1) to (a4) (hereinafter, also referred to as structural units (a5)). The constitutional unit (a5) is a constitution included in the polymer chain when a polymer is produced using a monomer (a5′) other than the monomers (a1′) to (a3′) (hereinafter referred to as (a5′) component). Unit. The component (a5') can be used alone or in combination of two or more.

Examples of the component (a5') include mono(meth)acrylates and vinyl monomers containing an aromatic ring structure that do not correspond to the component (a3).

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

The mono (meth) acrylate containing an alkyl ester group having 19 or more carbon atoms is, for example, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, henicosyl (meth) acrylate, docosyl (meth) Acrylate, tricosyl (meth)acrylate, tetracosyl (meth)acrylate, pentacosyl (meth)acrylate, hexacosyl (meth)acrylate, heptacosyl (meth)acrylate and octacosyl (meth)acrylic Rate, etc. are mentioned.

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

The content of the structural unit (a5) in the component (A) is not particularly limited, but is about 0 to 20% by mass relative to 100% by mass of the component (A) from the viewpoint of excellent antistatic properties and transparency of the cured film. It is desirable.

The content ratio of the structural units (a1) to (a4) in the component (A) is not particularly limited, but considering the compatibility of the component (A) with the active energy ray-curable resin, antistatic properties and transparency of the cured film , In that order, about 35 to 45: 35 to 45: 5 to 15: 6 to 22 (mass ratio) is preferable. In addition, when the structural unit (a5) is included in the component (A), the content ratio of the structural units (a1) to (a5) in the component (A) is also not particularly limited, but for the same reason, in order from 35 to 45: 35 to 45: 5 to 15: 6 to 22: 0 to 15 (mass ratio) degree is preferable.

The physical properties of the component (A) are not particularly limited. The weight average molecular weight of the component (A) is preferably 300,000 or less, and more preferably about 150,000 to 300,000. When the weight average molecular weight is 150,000 or more, since bleeding out of the antistatic agent from the cured film is more suppressed, the moist heat resistance of the cured film becomes more excellent. Moreover, when the weight average molecular weight is 300,000 or less, since the (A) component becomes a thing more excellent in compatibility with the poly(meth)acrylate mentioned later and a reactive diluent, the transparency of the cured film becomes more excellent. In addition, the weight average molecular weight of the component (A) refers to the value in terms of polyethylene oxide in the gel permeation chromatography method, but the measurement method is not particularly limited, and various known means can be employed, and a commercially available measuring device Can also be used. It is the same below.

(A) component, the (a1') component, (a2') component, (a3') component, and (a4'-1) component and/or (a4'-2) component, if necessary, (a5' ) It is obtained by radical copolymerizing the component by various known methods (bulk polymerization, solution polymerization, emulsion polymerization, etc.). The reaction temperature is usually about 40 to 160°C, and the reaction time is about 2 to 12 hours.

In synthesizing the component (A), various known radical polymerization initiators other than the component (a4'-1) and the component (a4'-2) may be used within the range in which the effect of the present invention is obtained. Examples of such radical polymerization initiators include azo polymerization initiators other than component (a4'-1) and peroxide polymerization initiators other than component (a4'-2). The radical polymerization initiator may be used alone or in combination of two or more.

As the azo polymerization initiator, for example, azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylbutyronitrile) [for example, Nippon Hydrazine Industries Co., Ltd. product, brand name" ABN-E", etc.], 2,2-azobis (2,4-dimethylvaleronitrile) [for example, Nippon Hydrazine Industrial Co., Ltd. product, a brand name "ABN-V", etc.], etc. are mentioned.

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. Organic peroxides are, for example, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butylperoxyoctoate, tert-butylperoxybenzoate, laur Royl peroxide, tert-butylperoxy-2-ethylhexanoate, didodecanoyl peroxide [for example, Nichiyu Co., Ltd. product, brand name "Paroyl (registered trademark) L", etc.], and the like. have.

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

Further, in the synthesis of component (A), chain transfer agents such as lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, and bromtrichlormethane may be used. The amount used is not particularly limited, but is usually about 0.01 to 10 mass% with respect to the total mass of the component (a1') to the component (a3') and the component (a5').

Further, 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; Acetate esters such as ethyl acetate and butyl acetate; Organic solvents such as chloroform and dimethylformamide can be used. Among these, glycol ethers are preferred from the viewpoint of the dissolving power of the (a1') component to the (a3') component, and the (a5') component. 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 the component (A). In addition, the antistatic agent may contain a diluting solvent other than the component (A).

The diluting solvent is, for example, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, Diacetone alcohol, acetylacetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol Monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. The diluting solvent may be used alone or in combination of two or more.

The content of the diluent solvent in the antistatic agent is not particularly limited. When a diluting solvent is included in the antistatic agent, the content of the diluting solvent is preferably contained in an amount of about 25 to 1900 parts by mass per 100 parts by mass of the antistatic agent from the viewpoint of coatability. Moreover, it is preferable to contain the content of a diluting solvent in a range in which the solid content concentration of the said antistatic agent becomes about 5-50 weight% from a viewpoint of coatability.

The antistatic agent may contain, as an additive, an agent other than the component (A) and a diluting solvent. Additives may be used alone or in combination of two or more. Examples of the additives include antioxidants, ultraviolet absorbers, light stabilizers, defoaming agents, surface modifiers, antifouling agents, antifogging agents, hydrophilic agents, pigments, metal oxide fine particles dispersion, organic fine particles dispersion, and the like.

The content of the additive in the antistatic agent is not particularly limited. The content of the additive is preferably from 0 to 50 parts by mass per 100 parts by mass of the antistatic agent. Moreover, the content of the additive to the component (A) is also not particularly limited. The content of the additive is preferably from 0 to 333 parts by mass with respect to 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 a composition) of the present invention is the antistatic agent, poly(meth)acrylate having at least three (meth)acryloyl groups in the molecule (hereinafter, poly(meth)acrylate Also referred to as), 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, but is preferably about 3 to 15% by mass based on 100% by mass of the composition in terms of solid content.

The poly(meth)acrylate is, for example, 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. And poly(meth)acrylate. Poly(meth)acrylate may be used alone or in combination of two or more.

The non-urethane-modified poly(meth)acrylate includes at least three (meth)acryloyl groups in molecules such as dipentaerythritol poly(meth)acrylate and tripentaerythritol poly(meth)acrylate. Polypentaerythritol poly(meth)acrylates; And pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

The urethane-modified poly(meth)acrylate includes, for example, a component having one or more hydroxyl groups in the non-urethane-modified poly(meth)acrylate or a hydroxyl group having two or less (meth)acryloyl groups in the molecule ( Reaction products of meth)acrylate and various known polyisocyanates are mentioned. Further, the urethane-modified poly(meth)acrylate may be a mixture containing an unreacted monomer component.

Examples of the polyisocyanate include an aromatic diisocyanate, an alicyclic diisocyanate, and an aliphatic diisocyanate, and a biuret body, isocyanurate body, allophanate body, and adduct body of these diisocyanates. The polyisocyanate is preferably an alicyclic diisocyanate, an aliphatic diisocyanate, and a biuret body, an isocyanurate body, an allophanate body, and an adduct body of these diisocyanates from the viewpoint of weather resistance of the cured film.

The aromatic diisocyanate is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyl-diphenylmethanedi Isocyanate and 1,5-naphthalene diisocyanate, etc. are illustrated.

Examples of the alicyclic diisocyanate include dicyclohexylmethane diisocyanate and isophorone diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate.

Examples of the aliphatic diisocyanate include hexamethylene diisocyanate.

The physical properties of the poly(meth)acrylate are not particularly limited. The molecular weight of the poly(meth)acrylate is preferably about 550 to 10,000, and about 550 to 7,000 in terms of compatibility with the component (A) and excellent antistatic properties, transparency, and hardness of the cured film. More preferable.

In addition, in this specification, when describing simply as "molecular weight", it has the following meaning. That is, when the structure of the compound can be uniquely expressed by a specific chemical formula, such as dipentaerythritol poly(meth)acrylate, the molecular weight means food. On the other hand, when the structure of the compound cannot be uniquely expressed by a specific chemical formula, such as polymer poly(meth)acrylate, the molecular weight means a weight average molecular weight.

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

The 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 above "poly(meth)acrylate". Reactive diluents may be used alone or in combination of two or more. By using a reactive diluent together, the compatibility between the component (A) and the poly(meth)acrylate becomes more favorable. As a result, the transparency of the composition of the present invention is improved, and a cured film having particularly excellent antistatic properties, transparency, hardness and scratch resistance, and the like can be obtained.

Reactive diluents include, for example, di(meth)acrylate, the components (a1') to (a3'), mono (meth)acrylates containing an alkyl ester group having 19 or more carbon atoms, vinyl monomers containing the aromatic ring structure, etc. Can be mentioned. In particular, di(meth)acrylate is preferable from the viewpoint of the compatibilization action and cured film performance (hardness, scratch resistance, etc.).

The di(meth)acrylate is, for example, 1,6-hexanedioldi(meth)acrylate, 1,9-nonandioldi(meth)acrylate, neopentylglycoldi(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, etc. are mentioned.

In the above composition, when the poly(meth)acrylate and a reactive diluent are used in combination, the total content of both in the composition is preferably about 80 to 97% by mass based on 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, but usually, when the total of both is 100% by mass, the poly(meth)acrylate is 20 to 100 The mass% or so and the reactive diluent are about 0 to 80 mass %. However, considering the transparency of the resulting active energy ray-curable resin composition, antistatic properties, transparency, hardness and scratch resistance of the cured film, poly(meth)acrylate is about 50 to 95 mass%, and the reactive diluent is 5 to 50. It is preferably about mass%.

The composition may contain a photopolymerization initiator. Two or more types of photoinitiators may be used together. The photoinitiator is, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like. . In addition, the photoinitiator is used when performing ultraviolet curing, but is not necessarily required when performing electron beam curing.

The content of the photopolymerization initiator in the composition is not particularly limited. The content of the photoinitiator is preferably about 0.5 to 15 parts by mass in terms of solid content from the viewpoint of progress of the reaction of the (meth)acryloyl group, based on 100 parts by mass of the composition.

In consideration of coating workability, etc., the said composition may contain the said diluting solvent. Among them, considering the surface smoothness of the cured film obtained from the composition, at least one selected from the group consisting of glycol ethers, alcohols, and ketones is preferable.

The content of the diluting solvent in the composition is not particularly limited. When a diluting solvent is included in the composition, the content of the diluting solvent is preferably contained in a range in which the solid content concentration of the composition is about 1 to 60% by weight from the viewpoint of coatability.

In the composition, any of the antistatic agent, diluent solvent, poly(meth)acrylate, reactive diluent, and photopolymerization initiator may be included as an additive. Additives may be used alone or in combination of two or more. As for the additive, the thing mentioned above, etc. are illustrated.

The content of the additive in the composition is not particularly limited. The content of the additive is preferably contained in an amount of 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/m2, preferably about 0.1 to 20 g/m2, and after drying, ultraviolet rays and electron beams , It is obtained by curing by irradiating active energy rays such as radiation.

Active energy rays used for the curing reaction include ultraviolet rays and electron rays, for example. As the light source of ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, or a metal halide lamp can be used. In addition, the amount of light, the arrangement of the light source, and the conveying speed can be adjusted as necessary. For example, when a high-pressure mercury lamp is used, the conveying speed is 5 to 50 for lamp 1 having a lamp output of about 80 to 160 W/cm. It is preferable to cure in the order of m/min. On the other hand, in the case of an electron beam, it is preferable to cure at a conveyance speed of about 5 to 50 m/min in an electron beam accelerating device having an acceleration voltage of about 10 to 300 kV.

[film]

The film of this invention contains the said cured film. This film is an article comprising the cured film and various base films as constituent elements.

Examples of the base film include plastic films, and various known ones can be used. The plastic film is, for example, 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. Type resin film, etc. are mentioned. The plastic film is preferably one type of film selected from the group consisting of a polycarbonate film, a triacetyl cellulose film, an acrylic resin film, and an alicyclic polyolefin resin film from the viewpoint of transparency and adhesion to the cured film. In addition, 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 film can be prepared by various known methods. Examples of the method for producing the film include applying the active energy ray-curable resin composition to at least one surface of the base film, drying as necessary, and then irradiating the active energy ray. Further, a laminated film can also be produced by applying the resin composition of the present invention to the non-coated surface of the obtained base film, bonding another base film thereon, and then irradiating an active energy ray.

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

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. In addition, the cured film formed on the base film has an average film thickness of usually about 0.05 to 30 µm, preferably about 0.1 to 20 µm.

(Example)

Hereinafter, the present invention will be described in more detail by examples. However, the present invention is not limited to these examples. In addition, in Examples, "%" and "part" mean "mass%" and "mass part" unless otherwise specified.

In addition, the weight average molecular weight of the component (A) is an actual measured value measured under the following conditions using a commercially available molecular weight analyzer.

Molecular weight meter: Product name "HLC-8220GPC", manufactured by Tosoh Corporation

Column: Product name "TSKGel G6000PW _XL -CP", "TSKGel G3000PW _XL -CP", manufactured by Tosoh Corporation

Development solvent: 0.1 M NaNO ₃ and 0.1 M acetic acid solution

Flow rate: 0.5 ml/min

Sample concentration: 0.5 g/ℓ

Standard material: Polyethylene oxide (TSKgel standard polyethylene oxide SE-kit manufactured by Tosoh Corporation)

<Synthesis of component (a2)>

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 device equipped with a stirring device and a cooling tube, the temperature was raised to 150° C., kept warm for 6 hours, and then cooled, A ring-opening polyadduct (hereinafter referred to as the component (a2-1)) of a hydroxyl group-containing vinyl monomer and lactone having a weight average molecular weight of 2,760 was obtained.

Synthesis Example 2

To a reaction device equipped with a stirring device and a cooling tube, 130 parts of hydroxyethyl methacrylate, 500 parts of ε-caprolactone, and 1.3 parts of tin octylate were added, the temperature was raised to 150° C., kept warm for 6 hours, and then cooled, A ring-opening polyadduct (hereinafter referred to as (b-1) component) of a hydroxyl group-containing vinyl monomer and lactone having a weight average molecular weight of 800 was obtained.

In addition, the weight average molecular weight of component (a2-1) and component (b-1) is a commercially available molecular weight meter (body product name "HLC-8220GPC", manufactured by Tosoh Corporation; column product names "TSKGel G1000H", "TSKGel G2000H. ", Tosoh Corporation make; using the developing solvent tetrahydrofuran),

Developing solvent: tetrahydrofuran,

Flow rate: 0.35 ml/min,

Sample concentration: 0.5%,

Standard material: Polystyrene (standard polystyrene kit PStQuickA, B, C manufactured by Tosoh Corporation),

It is a value obtained by measuring under the condition of (hereinafter, the same). The composition and the weight average molecular weight are shown in Table 1 (the same as below).

<Synthesis of component (A)>

Example 1

In the same reaction apparatus as in Synthesis Example 1, (a2-1) component 94 parts, tert-butyl methacrylate (t-BMA) (hereinafter referred to as (a3-1) component) 24 parts, polyoxyethylene structure 22 parts of a polyazo compound (Wako Pure Chemical Industries, Ltd. product name "VPE-0201". A compound represented by the general formula (4). Hereinafter, it is referred to as VPE-0201.), and propylene glycol monomethyl ether ( Hereinafter, it is called PGM.) 508 parts were added, and it heated up to 80 degreeC. Then, 100 parts of methacryloyloxyethyltrimethylammonium chloride (DMC) (hereinafter referred to as the component (a1-1)) and 455 parts of PGM were added, and the mixture was kept at 80°C for 1 hour. Thereafter, 5 parts of VPE-0201 and 15 parts of PGM were added, the mixture was kept warm for 1 hour, and then cooled after being kept warm at 113° C. for 2 hours, and a solution of the quaternary ammonium salt structure-containing polymer (A-1) (fire Volatile content 20%) was obtained. The weight average molecular weight of the obtained polymer was 210,000.

Example 2

In Example 1, instead of the component (a3-1), 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 the component (a3-2)) were used. Then, a solution (non-volatile content 20%) of the quaternary ammonium salt structure-containing polymer (A-2) was obtained. The weight average molecular weight of the obtained polymer was 210,500.

Example 3

In Example 1, instead of the component (a3-1), 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 the component (a3-3)) were used. It implemented and obtained the solution (non-volatile content 20%) of the quaternary ammonium salt structure-containing polymer (A-3). The weight average molecular weight of the obtained polymer was 200,500.

Example 4

In Example 1, 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, respectively, and a solution of the quaternary ammonium salt structure-containing polymer (A-4) (non-volatile content 20%) was obtained. The weight average molecular weight of the obtained polymer was 200,000.

Comparative Example 1

In the same reaction apparatus as in Synthesis Example 1, 100 parts of the component (a1-1), 60 parts of the component (a2-1), 40 parts of the component (a3-1), and 800 parts of PGM were added, and the temperature was raised to 80°C. Made it. Next, 8 parts of 2,2-azobis(2-methylbutyronitrile) (hereinafter referred to as ABN-E) and 32 parts of PGM were added to initiate the polymerization reaction, and the mixture was kept at 80° C. for 3 hours, and then It cooled after keeping the temperature at 113 degreeC for 2 hours, and the solution (non-volatile content 20%) of the quaternary ammonium salt structure-containing polymer (?-1) was obtained. The weight average molecular weight of the obtained polymer was 220,000.

Comparative Example 2

In the same reaction apparatus as in Synthesis Example 1, 100 parts of the component (a1-1), 78 parts of the component (a2-1), 17 parts of the component (a3-1), and methoxypolyethylene glycol methacrylate (Nichiyu ( Note) The production brand name "Brenmar PME-400." Hereinafter, it is referred to as PME400.) 21 parts and 832 parts of PGM were added, and the temperature was raised to 80°C. Subsequently, 8 parts of ABN-E and 32 parts of PGM were added, the polymerization reaction was initiated, the temperature was kept at 80°C for 3 hours, and then kept warm at 113°C for 2 hours, and then cooled, and the quaternary ammonium salt structure-containing polymer (α- The solution of 2) (non-volatile content 20%) was obtained. The weight average molecular weight of the obtained polymer was 210,000.

Comparative Example 3

In the same reaction apparatus as in Synthesis Example 1, 100 parts of the component (a1-1), 100 parts of the component (a3-1), and 800 parts of PGM were added, and the temperature was raised to 80°C. Subsequently, 8 parts of VPE-0201 and 32 parts of PGM were added, the polymerization reaction was initiated, the temperature was kept at 80°C for 3 hours, and then kept warm at 113°C for 2 hours, and then cooled, and the quaternary ammonium salt structure-containing polymer (α- The solution of 3) (non-volatile content 20%) was obtained. The weight average molecular weight of the obtained polymer was 220,000.

Comparative Example 4

In Example 1, 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 instead of the component (a3-1), and 4 A solution (non-volatile content of 20%) of the quaternary ammonium salt structure-containing polymer (?-4) was obtained. The weight average molecular weight of the obtained polymer was 100,000.

Comparative Example 5

In Example 1, the reaction was carried out in the same manner as in Example 1, except that 60 parts of the component (b-1) was used instead of the component (a2-1), and the quaternary ammonium salt structure-containing polymer (α-5) was A solution (non-volatile content 20%) was obtained. The weight average molecular weight of the obtained polymer was 100,000.

The used amount of each component in Table 1 is a value of parts by mass converted to solid content. The abbreviations in Table 1 are as follows.

VPE-0201: Polyazo compound having a polyoxyethylene structure represented by the general formula (4) (Wako Pure Chemical Industries, Ltd. product brand name "VPE-0201")

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

PME400: Methoxy polyethylene glycol methacrylate (Nichiyu Co., Ltd. product brand name "Brenma PME-400")

CHMA: Cyclohexyl methacrylate

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

Synthesis 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 (trade name ``Colonate HXR'' manufactured by Tosoh Corporation), 0.03 tin octylate. After 177 parts of a mixture of parts, pentaerythritol triacrylate and pentaerythritol tetraacrylate were injected, the temperature in the system was raised to about 80°C over about 1 hour. Next, at the same temperature, after holding the reaction system for 1 hour, it is cooled, and a mixture of a urethane-modified poly(meth)acrylate having a solid content of 100% by mass and an unreacted monomer (urethane-modified poly(meth)acrylate (UA)). Hereinafter, it is called UA.) was obtained. The obtained UA was a mixture containing a urethane-modified poly(meth)acrylate having 9 (meth)acryloyl groups in the molecule, and the urethane-modified poly(meth)acrylate molecular weight was 1,500.

<Preparation of an active energy ray-curable resin composition>

Example 5

5 parts of antistatic agent consisting of component (A-1) in solution, dipentaerythritol polyacrylate (hereinafter referred to as DPHA) (mixture of 5 and 6 (meth)acryloyl groups: Doa Synthesis (Note) ) 95 parts of manufacture, brand name "Aronix M400") and 5 parts of 1-hydroxy-cyclohexyl-phenylketone (manufactured by IGM Resins BV, brand name "Omnirad184", hereinafter referred to as Omni184)) in a solid content ratio of 5 parts. It blended and diluted with PGM to prepare an active energy ray-curable resin composition containing 50% of nonvolatile matter.

Example 6

In Example 5, instead of DPHA, preparation was carried out in the same manner as in Example 5, except that 95 parts of UA of Synthesis Example 3 were used, to prepare an active energy ray-curable resin composition having 50% of non-volatile content.

Example 7

In Example 5, instead of DPHA, 47.5 parts of DPHA and 47.5 parts of UA of Synthesis Example 3 were used. Prepared.

Example 8

In Example 5, except that 80 parts of DPHA and 10 parts of an antistatic agent composed of the component (A-1) in a solution were used, preparation was carried out in the same manner as in Example 5, and active energy ray curability of 50% of non-volatile content A resin composition was prepared.

Example 9

In Example 5, preparation was carried out in the same manner as in Example 5, except that PGM of the diluting solvent was used in place of the mixed solvent of the mass ratio of methyl ethyl ketone (MEK) and PGM 1/1, and the non-volatile content of 50% An active energy ray-curable resin composition was prepared.

Example 10

In Example 5, it was prepared in the same manner as in Example 5 except that 5 parts of the antistatic agent composed of the component (A-2) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Example 11

In Example 5, it was prepared in the same manner as in Example 5, except that 5 parts of the antistatic agent composed of the component (A-3) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Example 12

In Example 5, a preparation was carried out in the same manner as in Example 5, except that 5 parts of the antistatic agent composed of the component (A-4) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Example 13

In Example 5, it was prepared in the same manner as in Example 5, except that 97 parts of DPHA and 3 parts of the antistatic agent composed of the component (A-1) in the solution were used, and active energy ray curing property of 50% of non-volatile content A resin composition was prepared.

Example 14

In Example 5, preparation was carried out in the same manner as in Example 5, except that 90 parts of DPHA and 10 parts of the antistatic agent composed of the component (A-1) in the solution were used, and active energy ray curing properties of 50% of non-volatile content A resin composition was prepared.

Example 15

In Example 5, except for using 85 parts of DPHA and 15 parts of an antistatic agent composed of the component (A-1) in a solution, preparation was carried out in the same manner as in Example 5, and active energy ray curability of 50% of non-volatile content A resin composition was prepared.

Comparative Example 6

In Example 5, a preparation was carried out in the same manner as in Example 5, except that 5 parts of the antistatic agent composed of the component (α-1) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Comparative Example 7

In Comparative Example 6, instead of DPHA, preparation was carried out in the same manner as in Comparative Example 6, except that 95 parts of UA of Synthesis Example 3 were used, and an active energy ray-curable resin composition having 50% of non-volatile content was prepared.

Comparative Example 8

In Example 5, a preparation was carried out in the same manner as in Example 5, except that 5 parts of the antistatic agent composed of the component (α-2) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Comparative Example 9

In Example 5, a preparation was carried out in the same manner as in Example 5, except that 5 parts of the antistatic agent composed of the component (α-3) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Comparative Example 10

In Example 5, a preparation was carried out in the same manner as in Example 5, except that 5 parts of the antistatic agent composed of the component (α-4) in the solution was used instead of the antistatic agent composed of the component (A-1) in the solution. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

Comparative Example 11

In Example 5, instead of the antistatic agent consisting of the component (A-1) in the solution, 5 parts of the antistatic agent consisting of the component (α-5) in the solution was used, and the preparation was carried out in the same manner as in Example 5. , An active energy ray-curable resin composition containing 50% of a non-volatile content was prepared.

The blending amount in Table 2 is a value of parts by mass converted to solid content. Abbreviations and annotations in Table 2 are as follows.

※ Since the antistatic agent and the poly(meth)acrylate were not mixed and a uniform active energy ray-curable resin composition was not obtained, evaluation could not be performed.

DPHA: Dipentaerythritol poly(meth)acrylate (a mixture of 5 compounds and 6 compounds with (meth)acryloyl groups in a molecule, molecular weight 500 to 600) (manufactured by Doa Synthesis Co., Ltd., brand name ``Aronix M400 」)

UA: Urethane-modified poly(meth)acrylate (UA) of Synthesis Example 3 (a mixture containing a urethane-modified poly(meth)acrylate having 9 (meth)acryloyl groups in the molecule, the urethane-modified poly(meth)acrylic Rate of molecular weight 1,500)

Omni184: 1-hydroxy-cyclohexyl-phenylketone (manufactured by IGM Resins B.V, brand name "Omnirad184")

<Production of film>

On a PET film having a film thickness of 100 µm (trade name "Lumira 100U483" manufactured by Toray Co., Ltd.), the active energy ray-curable resin composition of Examples 5 to 15 and Comparative Examples 6 to 11 was applied to It applied with a #15 bar coater so that it might become 5 micrometers, and it dried at 80 degreeC for 1 minute, and produced the film. Subsequently, the obtained film was used with an ultraviolet curing device (manufactured by Multiply Co., Ltd., brand name "UBT-080-7A/BM", high pressure mercury lamp 600 mJ/cm 2) to obtain a film with a cured film. Table 2 shows the following evaluation results for the produced film.

(Surface resistance test)

The surface resistance value (Ω/□) immediately after the production of the film was obtained using a commercial resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., brand name ``Hyresta MCP-HT-450''), according to JIS K 6911, It was measured with an applied voltage of 500 V.

(Measurement of transparency)

The haze value of the film was measured according to JIS K 5400 using a color haze meter manufactured by Murakami Color Research Institute. In addition, each haze value is a numerical value including the haze value of the polyester film which is a base material.

(Moisture heat resistance test)

The film was allowed to stand in an environment at a temperature of 80° C. and a humidity of 95%Rh for 24 hours, and then the presence or absence of surface precipitates on the film surface was visually confirmed.

No surface precipitate... ○

There is surface precipitate… ×

(Pencil hardness test)

The cured film of the film was evaluated by a pencil scratch test (according to JIS K 5400) with a load of 500 g.

Claims (5)

Constituent unit (a1) derived from a vinyl monomer having a quaternary ammonium salt structure,
It is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and lactone, and
Constituent unit (a2) derived from a vinyl monomer having a weight average molecular weight of 1,000 to 10,000,
Structural unit (a3) derived from a vinyl monomer containing an alkyl ester group having 1 to 18 carbon atoms, and
An antistatic agent for an active energy ray-curable resin composition containing a polymer (A) containing a structural unit (a4) derived from a polyazo compound having a polyoxyethylene structure and/or a polyperoxide compound having a polyoxyethylene structure . The method of claim 1,
The above structural unit (a4) is a structural unit derived from a polyazo compound having a polyoxyethylene structure, an antistatic agent for an active energy ray-curable resin composition. An 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 three (meth)acryloyl groups in a molecule. A cured film comprising the active energy ray-curable resin composition according to claim 3. A film containing the cured film according to claim 4.