JP2016056250A - Active energy ray curable hard coat agent and hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable hard coat agent capable of manufacturing a hard coat film excellent in transparency, excoriation resistance and processability and having less curvature deformation amount and the hard coat film.SOLUTION: There are provided an active energy ray curable hard coat agent containing a (meth)acrylic block copolymer (A) consisting of a (meth)acrylic polymer block (a) having an active energy ray curable group containing a partial structure represented by the following general formula (1) and a (meth)acrylic polymer block (b) having no active energy ray curable group and a hard coat film having a hard coat layer by curing the active energy ray curable hard coat agent on a plastic film. (1), where Rrepresents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable hard coat agent and a hard coat film. Specifically, the present invention relates to an active energy ray-curable hard coat agent that can be rapidly cured by irradiation with active energy rays to obtain a hard coat film with a small amount of warp deformation, and the active energy ray-curable hard coat agent. The present invention relates to a hard coat film having a hard coat layer which is cured and has excellent scratch resistance and does not cause whitening or cracks due to processing.

  In recent years, plastic films have been used for various applications because of their processability, transparency, lightness, and the like. For the purpose of protecting the surface and improving the appearance, a hard coat film provided with a hard coat layer having excellent scratch resistance on the surface of a plastic film may be used for application to various casings.

  This hard coat layer is an active energy ray curing based on polyfunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It can be formed by applying a hard coating agent on the surface of a plastic film and curing it.

Under the present circumstances, curvature deformation may generate | occur | produce in the hard coat film obtained by volume shrinkage accompanying hardening of an active energy ray hardening hard coat agent.
In addition, when the obtained hard coat film is subjected to processing such as bending and stretching along the surface shape of the casing, for example, for the purpose of sticking to the surface of the casing, the hard coat layer is whitened or cracked. May occur.

  As means for solving these problems, a radiation curable resin composition mainly composed of a polyfunctional (meth) acrylic acid ester and a polyfunctional urethane acrylate has been proposed (see Patent Document 1). However, even if such a radiation curable resin composition is used, it cannot be said that the above problem can be sufficiently solved.

JP 2001-113648 A

  An object of the present invention is a hard coat film having a small amount of warpage deformation and free from whitening or cracking due to processing such as bending and stretching (that is, excellent in workability) and active energy ray curing suitable for a hard coat layer of the hard coat film It is in providing an adhesive hard coat agent.

According to the invention, the object is
[1] A (meth) acrylic polymer block (a) having an active energy ray-curable group containing a partial structure represented by the following general formula (1) (hereinafter referred to as “partial structure (1)”) , Simply referred to as “(meth) acrylic polymer block (a)”) and (meth) acrylic polymer block (b) having no active energy ray-curable group (hereinafter simply referred to as “(meth) acrylic”). An activity containing a (meth) acrylic block copolymer (A) (hereinafter simply referred to as “(meth) acrylic block copolymer (A)”) comprising a polymer block (b) ”) Energy ray curable hard coating agent;
[2] The active energy ray-curable hard coat agent according to the above [1], wherein the active energy ray-curable group is represented by the following general formula (2):
[3] The active energy ray-curable hard coat agent according to the above [1] or [2], further containing a reactive diluent;
[4] 1 to 30 of the (meth) acrylic block copolymer (A) with respect to 100 parts by mass of the total amount of the (meth) acrylic block copolymer (A) and the reactive diluent. [3] active energy ray-curable hard coat agent containing part by mass;
[5] The active energy ray-curable hard coat agent according to [3] or [4] above, wherein the reactive diluent is a compound having a plurality of (meth) acryloyloxy groups; and [6] the above [1] to [1] It can be achieved by a hard coat film comprising a hard coat layer formed by curing the active energy ray-curable hard coat agent according to any one of [5] on the surface of a plastic film.

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表す）

(Wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ²およびＲ³はそれぞれ独立して水素原子または炭素数１〜６の炭化水素基を表し、ＸはＯ、Ｓ、またはＮ（Ｒ⁶）（Ｒ⁶は水素原子または炭素数１〜６の炭化水素基を表す）を表し、ｎは１〜２０の整数を表す）

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and X represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20)

  When the active energy ray-curable hard coat agent of the present invention is coated on a plastic film and cured to produce the hard coat film of the present invention, the amount of warp deformation is small. Moreover, the hard coat film of the present invention is excellent in transparency and scratch resistance, and does not cause whitening or cracking due to processing such as stretching, that is, it has excellent workability.

It is the figure which looked at the hard coat film put on the horizontal stand from the side.

Hereinafter, the present invention will be described in detail.
The active energy ray-curable hard coat agent of the present invention contains a (meth) acrylic block copolymer (A). In the present specification, “(meth) acryl” means a generic name of “methacryl” and “acryl”, and “(meth) acryloyl” described later means a generic name of “methacryloyl” and “acryloyl”. “(Meth) acrylate”, which will be described later, is a generic term for “methacrylate” and “acrylate”.

  The content of the (meth) acrylic block copolymer (A) in the active energy ray-curable hard coat agent of the present invention is preferably 3% by mass or more, and more preferably 5% by mass or more. . Moreover, the (meth) acrylic block in 100 parts by mass of the main component ((meth) acrylic block copolymer (A) and optional reactive diluent described later) contained in the active energy ray-curable hard coat agent. 1-30 mass parts is preferable and, as for content of a copolymer (A), 2-15 mass parts is more preferable.

The (meth) acrylic block copolymer (A) has a (meth) acrylic polymer block (a) having an active energy ray-curable group containing the partial structure (1).
The active energy ray-curable group containing the partial structure (1) exhibits polymerizability upon irradiation with an active energy ray. As a result, the active energy ray-curable hard coat agent of the present invention is cured to become a cured product (hard coat layer). In addition, in this specification, an active energy ray means a light beam, electromagnetic waves, particle beams, and a combination thereof. Examples of light rays include far ultraviolet rays, ultraviolet rays (UV), near ultraviolet rays, visible rays, and infrared rays, electromagnetic waves include X-rays and γ rays, and particle beams include electron beams (EB) and proton rays (α Line) and neutron beam. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable, from the viewpoints of curing speed, availability of an irradiation apparatus, price, and the like.
The partial structure (1) is represented by the following general formula (1).

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表す）

(Wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)

In the general formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group Alkyl groups such as n-hexyl group, 2-methylpentyl group, 3-methylpentyl group and n-decyl; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; phenyl group, naphthyl group and the like Aralkyl groups such as aryl group, benzyl group, and phenylethyl group. Among these, from the viewpoint of active energy ray curability, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

  The (meth) acrylic polymer block (a) in the (meth) acrylic block copolymer (A) has the viewpoint of enhancing the curing rate and coating properties of the active energy ray-curable hard coat agent of the present invention. The active energy ray-curable group containing the partial structure (1) is preferably represented by the general formula (2) (the active energy ray-curable group represented by the following general formula (2) is hereinafter referred to as “active energy ray-curable”. Sex group (2) ").

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ²およびＲ³はそれぞれ独立して水素原子または炭素数１〜６の炭化水素基を表し、ＸはＯ、Ｓ、またはＮ（Ｒ⁶）（Ｒ⁶は水素原子または炭素数１〜６の炭化水素基を表す）を表し、ｎは１〜２０の整数を表す）

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and X represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20)

Specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ in the general formula (2) include the same hydrocarbon groups as R ^{1 in the} general formula (1).
In the general formula (2), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a monomer containing di (meth) acrylate (3) described later. From the viewpoint that it can be easily and directly introduced, a hydrocarbon group having 1 to 6 carbon atoms is preferred. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group An alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; and an aryl group such as a phenyl group. Among these, from the viewpoint of the curing rate of the active energy ray-curable hard coat agent, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

In the general formula (2), X represents O, S or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). Preferably there is. When X is N (R ⁶ ), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group And alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group, and phenyl group.

In the general formula (2), the integer of 1 to 20 represented by n is preferably 2 to 5 from the viewpoints of fluidity and curing speed of the active energy ray-curable hard coat agent.
The content of the partial structure (1) with respect to all the monomer units forming the (meth) acrylic polymer block (a) is preferably in the range of 0.2 to 100 mol%, more preferably in the range of 10 to 90 mol%. The range of 25-80 mol% is more preferable.

  The (meth) acrylic polymer block (a) includes a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester. As the (meth) acrylic acid ester, a monofunctional (meth) acrylic acid ester having one (meth) acryloyl group and a polyfunctional (meth) acrylic acid ester having two or more (meth) acryloyl groups are used. be able to.

  Examples of the monofunctional (meth) acrylic acid ester that can form the (meth) acrylic polymer block (a) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( (Meth) acrylic acid isopropyl, (meth) acrylic acid n-butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isobornyl, (meth) Dodecyl acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, (meth) acrylic acid 2 -Aminoethyl, N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylate N, N-diethylaminoethyl acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) acrylate, 3- (trimethylsilyloxy) propyl (meth) acrylate, ( Glycidyl acrylate, γ-((meth) acryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethyl methyl (meth) acrylate, 2-trifluoro (meth) acrylic acid Methylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, permethacrylate (meth) acrylate Fluoromethyl, (meth) acrylic acid diperfluoro Methylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic acid Examples include 2-perfluorohexadecylethyl. Among them, preferred are alkyl methacrylates having an alkyl group having 5 or less carbon atoms, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, Most preferred is methyl methacrylate.

Moreover, as polyfunctional (meth) acrylic acid ester which can form (meth) acrylic-type polymer block (a), bifunctional (meth) acrylic acid ester (henceforth "di (meta) is shown by following General formula (3)." ) Acrylate (3) ”) is used to carry out living anion polymerization under the conditions described later, whereby one (meth) acryloyloxy group (“ CH ₂ ═C (R ⁵ ) in the following general formula (3) ”is used. (Meth) acryloyloxy group represented by C (O) O ”is selectively polymerized, R ¹ is R ⁴ , R ² is R ^{2 ′} , R ³ is R ^{3 ′} , A (meth) acrylic polymer block (a) having an active energy ray-curable group (2) in which X is O can be formed.

（式中、Ｒ^2'およびＲ^3'はそれぞれ独立して炭素数１〜６の炭化水素基を表し、Ｒ⁴およびＲ⁵はそれぞれ独立して水素原子またはメチル基を表し、ｎは１〜２０の整数を表す）

(Wherein R ^{2 ′} and R ^{3 ′} each independently represent a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and n represents 1 to 1) Represents an integer of 20)

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ^{2 ′} and R ^{3 ′ in} general formula (3) include the same hydrocarbon groups as R ² and R ^{3 in} general formula (2). .
From the viewpoint of increasing the selectivity of polymerization, R ⁴ is preferably a methyl group. From the viewpoint of productivity of di (meth) acrylate (3), R ⁴ and R ⁵ are preferably the same. From the above viewpoints, it is most preferable that R ⁴ and R ⁵ are both methyl groups.

  Specific examples of the di (meth) acrylate (3) include, for example, 1,1-dimethylpropane-1,3-diol di (meth) acrylate, 1,1-dimethylbutane-1,4-diol di (meth) acrylate, 1 , 1-dimethylpentane-1,5-diol di (meth) acrylate, 1,1-dimethylhexane-1,6-diol di (meth) acrylate, 1,1-diethylpropane-1,3-diol di (meth) acrylate, 1,1-diethylbutane-1,4-diol di (meth) acrylate, 1,1-diethylpentane-1,5-diol di (meth) acrylate, 1,1-diethylhexane-1,6-diol di (meth) acrylate 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethyl Tan-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, 1,1-dimethylhexane-1,6-diol dimethacrylate, 1,1-diethylpropane-1,3 -Diol dimethacrylate, 1,1-diethylbutane-1,4-diol dimethacrylate, 1,1-diethylpentane-1,5-diol dimethacrylate, and 1,1-diethylhexane-1,6-diol dimethacrylate 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, and 1 1,1-dimethylhexane-1,6-diol dimethacrylate is more preferred Arbitrariness.

These (meth) acrylic acid esters may be used alone or in combination of two or more.
The content of the monomer unit formed from the (meth) acrylic acid ester in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a). The range of 90-100 mol% is preferable with respect to the unit, the range of 95-100 mol% is more preferable, and 100 mol% may be sufficient. When the (meth) acrylic polymer block (a) contains a monomer unit formed from di (meth) acrylate (3), a single unit formed from di (meth) acrylate (3) is used. The content of the monomer unit is preferably in the range of 0.2 to 100 mol%, more preferably in the range of 10 to 90 mol%, based on all monomer units forming the (meth) acrylic polymer block (a). More preferably, the range of 25 to 80 mol% is more preferable. Furthermore, when the (meth) acrylic polymer block (a) contains a monomer unit formed from methyl methacrylate and a monomer unit formed from di (meth) acrylate (3) The sum of the content of monomer units formed from methyl methacrylate and the content of monomer units formed from di (meth) acrylate (3) is formed from (meth) acrylic ester. The range of 80-100 mol% is preferable with respect to all monomer units, the range of 90-100 mol% is more preferable, the range of 95-100 mol% is more preferable, and 100 mol% may be sufficient.

  The (meth) acrylic polymer block (a) may have a monomer unit formed from a monomer other than the (meth) acrylic acid ester. Examples of the other monomer include α-alkoxy acrylate esters such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate; crotonic acid esters such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid. 3-alkoxyacrylic acid esters such as esters; N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like ( (Meth) acrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, methyl 2-bromomethylacrylate, ethyl 2-bromomethylacrylate, methyl vinyl ketone, ethyl vinyl ketone Methyl isopropenyl ketone And ethyl isopropenyl ketone. These other monomers may be used alone or in combination of two or more.

  The content of the monomer units formed from the other monomers in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a). The total content is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit.

  The number average molecular weight (Mn) per (meth) acrylic polymer block (a) is not particularly limited, but from the viewpoint of improving the workability of the hard coat film of the present invention, 500 to 1,000,000 Is preferably in the range of 1,000, more preferably in the range of 1,000 to 300,000. In addition, in this specification, Mn and the molecular weight distribution mentioned later mean the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  The (meth) acrylic block copolymer (A) has a (meth) acrylic polymer block (b). The (meth) acrylic polymer block (b) is composed of a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester and has an active energy ray-curable group. There are no polymer blocks.

In the present specification, the active energy ray-curable group means a functional group that exhibits polymerizability upon irradiation with the active energy ray. Examples of the active energy ray-curable group include ethylenic double groups such as (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyl ether group vinyloxy group, 1,3-dienyl group, and styryl group. A functional group having a bond (particularly an ethylenic double bond represented by the general formula CH ₂ ═CR— (wherein R is an alkyl group or a hydrogen atom); an epoxy group, an oxetanyl group, a thiol group, a maleimide group, etc. It is done.

  Examples of the (meth) acrylic acid ester that can form the (meth) acrylic polymer block (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) Isopropyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid Dodecyl, trimethoxysilylpropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) Phenyl acrylate, (meth) acrylic acid naphthyl, (meth) acrylic acid 2- (trimethyl Rushiriruokishi) ethyl include mono (meth) acrylic acid esters such as (meth) acrylic acid 3- (trimethylsilyloxy) propyl. Among them, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, alkyl acrylate having 4 or more carbon atoms such as dodecyl acrylate; 2-ethylhexyl methacrylate, dodecyl methacrylate, etc. A methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms is preferred. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  The content of the monomer unit formed by the (meth) acrylic ester in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b). The amount is preferably 90 mol% or more, more preferably 95 mol% or more, based on the unit.

  The (meth) acrylic polymer block (b) may have a monomer unit formed from a monomer other than the (meth) acrylic acid ester. Examples of the other monomers include α-alkoxy acrylates such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate; crotonates such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid. 3-alkoxyacrylic acid esters such as esters; N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like ( (Meth) acrylamide; methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone and the like. These other monomers may be used alone or in combination of two or more.

  The content of the monomer unit formed by the other monomer in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b). The total content is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit.

  Although there is no restriction | limiting in particular in Mn per (meth) acrylic-type polymer block (b), From a viewpoint of making the workability of the hard coat film of this invention favorable, the range of 3,000-2,000,000. Preferably, it is within the range, and more preferably within the range of 5,000 to 1,000,000.

  The (meth) acrylic block copolymer (A) is a block copolymer in which at least one (meth) acrylic polymer block (a) and at least one (meth) acrylic polymer block (b) are bonded to each other. There are no particular restrictions on the number and order of bonding of each polymer block, but from the viewpoint of active energy ray curability, the (meth) acrylic polymer block (a) is a (meth) acrylic block copolymer ( It is preferable to form at least one terminal of A), and from the viewpoint of ease of production of the (meth) acrylic block copolymer (A), it is more preferably a linear polymer. Diblock copolymer in which (meth) acrylic polymer block (a) and one (meth) acrylic polymer block (b) are bonded, and one (meth) acrylic polymer Both ends (meth) acrylic polymer block (a) triblock copolymer attached one each turn, each of the lock (b) is more preferred.

  Ratio of mass of (meth) acrylic polymer block (a) composing (meth) acrylic block copolymer (A) to mass of (meth) acrylic polymer block (b) [(meth) acrylic The polymer block (a) :( meth) acrylic polymer block (b)] is not particularly limited, but is preferably 90:10 to 5:95, and 80:20 to 7:93. Is more preferable, and 75:25 to 10:90 is more preferable. When the ratio of the mass of the (meth) acrylic polymer block (a) to the total mass of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) is 5% or more. When the curing rate is 90% or less, the workability of the hard coat film of the present invention is improved, which is preferable.

  In the (meth) acrylic block copolymer (A), the content of the monomer unit formed from the methacrylic acid ester is preferably 5 to 85% by mass, and preferably 7 to 80% by mass. More preferably, it is more preferably 10 to 75% by mass. In the (meth) acrylic block copolymer (A), the content of the monomer unit formed from the acrylate ester is preferably 15 to 95% by mass, and 20 to 93% by mass. It is more preferable that the content is 25 to 90% by mass.

  Although there is no restriction | limiting in particular in Mn of a (meth) acrylic block copolymer (A), From points, such as the handleability of a (meth) acrylic block copolymer (A), fluidity | liquidity, a mechanical characteristic, 4,000. Is preferably 3,000,000, more preferably 7,000 to 2,000,000, and still more preferably 10,000 to 1,000,000.

  The molecular weight distribution of the (meth) acrylic block copolymer (A), that is, the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably in the range of 1.02 to 2.00, 1.05 to 1.80. The range is more preferable, and the range of 1.10 to 1.50 is more preferable.

  The content of the partial structure (1) in the (meth) acrylic block copolymer (A) is 0.1 to all monomer units forming the (meth) acrylic block copolymer (A). The range is preferably 30 mol%, more preferably 1 to 20 mol%, and still more preferably 3 to 15 mol%.

  The number of the partial structures (1) contained per molecule of the (meth) acrylic block copolymer (A) is preferably 3 or more, more preferably 4 or more from the viewpoint of the curing rate. Preferably, it is 8 or more.

  The (meth) acrylic block copolymer (A) is obtained by forming the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) in a desired order. The method for producing the (meth) acrylic block copolymer (A) is not particularly limited, but an anionic polymerization method and a radical polymerization method are preferable, and a living anion polymerization method or a living radical polymerization method is more preferable from the viewpoint of polymerization control. An anionic polymerization method is more preferable. The monomer used for the production of the (meth) acrylic block copolymer (A) is preferably dried in advance under an inert gas atmosphere from the viewpoint of allowing the polymerization to proceed smoothly. In the drying treatment, a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.

  Living radical polymerization methods include a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, a polymerization method using a nitroxide (see International Publication No. 2004/014926), and a high-cycle heterogeneity such as an organic tellurium compound. Polymerization method using elemental compounds (see Japanese Patent No. 3839829), reversible addition / elimination chain transfer polymerization method (RAFT) (see Japanese Patent No. 3639859), atom transfer radical polymerization method (ATRP) (Japanese Patent No. 3040172) , International Publication No. 2004/013192). Among these living radical polymerization methods, an atom transfer radical polymerization method is preferred, and a metal complex having an organic halide or a sulfonyl halide compound as an initiator and at least one selected from Fe, Ru, Ni, and Cu as a central metal is used. An atom transfer radical polymerization method using a catalyst is more preferable.

  Living anionic polymerization methods include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP 06-93060 A), an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator, etc. A living anion polymerization in the presence of a mineral acid salt (see JP 05-507737 A), and a living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (Japanese Patent Laid-Open No. Hei 5). 11-335432 and International Publication No. 2013/141105). Among these living anionic polymerization methods, living anionic polymerization is carried out using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound from the viewpoint that the (meth) acrylic polymer block (a) can be directly and efficiently formed. And a living anion polymerization using an organolithium compound as a polymerization initiator in the presence of an organoaluminum compound and a Lewis base is more preferred.

  Examples of the organolithium compound include t-butyllithium, 1,1-dimethylpropyllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, ethyl α-lithioisobutyrate, butyl α-lithioisobutyrate, methyl α-lithioisobutyrate, isopropyl lithium, sec-butyl lithium, 1-methylbutyl lithium, 2-ethylpropyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, α- Examples include methyl benzyl lithium, methyl lithium, n-propyl lithium, n-butyl lithium, n-pentyl lithium and the like. Among them, from the viewpoint of availability and anion polymerization initiating ability, secondary grades such as isopropyl lithium, sec-butyl lithium, 1-methylbutyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, α-methylbenzyl lithium, etc. C3-C40 organolithium compounds having a chemical structure with a carbon atom as an anion center are preferred, and sec-butyllithium is particularly preferred. These organolithium compounds may be used alone or in combination of two or more.

The amount of the organic lithium compound used can be determined by the ratio to the amount of the monomer used depending on the Mn of the target (meth) acrylic block copolymer (A).
As said organoaluminum compound, the organoaluminum compound shown by the following general formula (A-1) or (A-2) is mentioned.
AlR ⁷ (R ⁸ ) (R ⁹ ) (A-1)
Wherein R ⁷ represents a monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group, aryloxy group or N, N-disubstituted amino group, and R ⁸ and R ⁹ are each independently Or R ⁸ and R ⁹ are bonded to each other to form an aryleneoxy group)
AlR ¹⁰ (R ¹¹ ) (R ¹² ) (A-2)
(Wherein R ¹⁰ represents an aryloxy group, R ¹¹ and R ¹² each independently represent a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, or an N, N-disubstituted amino group. Represents a group)

In the general formulas (A-1) and (A-2), examples of the aryloxy group that R ⁷ , R ⁸ , R ^9, and R ¹⁰ each independently represent include a phenoxy group, a 2-methylphenoxy group, and 4 -Methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di-t-butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,6-di-t-butyl-4-methyl Phenoxy group, 2,6-di-t-butyl-4-ethylphenoxy group, 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, Examples include 7-methoxy-2-naphthoxy group.

In the above general formula (A-1), examples of the aryleneoxy group formed by bonding R ⁸ and R ⁹ to each other include 2,2′-biphenol, 2,2′-methylenebisphenol, 2,2 ′. -Methylenebis (4-methyl-6-tert-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2- Examples thereof include functional groups excluding hydrogen atoms of the two phenolic hydroxyl groups in a compound having two phenolic hydroxyl groups such as naphthol.

  In addition, one or more hydrogen atoms contained in the above aryloxy group and aryleneoxy group may be substituted with a substituent. Examples of the substituent include a methoxy group, an ethoxy group, an isopropoxy group, Examples thereof include alkoxy groups such as t-butoxy group; halogen atoms such as chlorine atom and bromine atom.

In the general formulas (A-1) and (A-2), examples of the monovalent saturated hydrocarbon group represented by R ⁷ , R ^11, and R ¹² independently include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; cyclohexyl group, etc. The monovalent aromatic hydrocarbon group includes, for example, an aryl group such as a phenyl group; the aralkyl group such as a benzyl group; and the alkoxy group includes, for example, a methoxy group and an ethoxy group. , Isopropoxy group, t-butoxy group and the like. Examples of the N, N-disubstituted amino group include dimethylamino group, diethylamino group, diisopropylamino group, and the like. Dialkylamino groups such as bis (trimethylsilyl) amino group and the like. One or more hydrogen atoms contained in the above-described monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group and N, N-disubstituted amino group may be substituted with a substituent. Examples of the substituent include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and t-butoxy group; halogen atoms such as chlorine atom and bromine atom.

  Examples of the organoaluminum compound (A-1) include ethylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-t-butylphenoxy) aluminum, ethyl [2 , 2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-t) -Butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-di-t-butylphenoxy) aluminum, n-octyl [2,2′-methyl Bis (4-methyl-6-t-butylphenoxy)] aluminum, methoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum, methoxybis (2,6-di-t-butylphenoxy) aluminum, Methoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, ethoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, ethoxybis (2,6-di-) t-butylphenoxy) aluminum, ethoxy [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, isopropoxybis (2,6-di-t-butyl-4-methylphenoxy) aluminum , Isopropoxybis (2,6-di-t-butylphenoxy) aluminum, isopropoxy [ 2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, t-butoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, t-butoxybis (2,6- Di-t-butylphenoxy) aluminum, t-butoxy [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, tris (2,6-di-t-butyl-4-methylphenoxy) ) Aluminum, tris (2,6-diphenylphenoxy) aluminum and the like. Among them, from the viewpoints of polymerization initiation efficiency, living property of polymerization terminal anion, availability and handling, etc., isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6 -Di-t-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum and the like are preferable.

  Examples of the organoaluminum compound (A-2) include diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-t-butylphenoxy) aluminum, diisobutyl (2 , 6-Di-t-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-t-butylphenoxy) aluminum, di-n-octyl (2,6-di-t-butyl-4-methylphenoxy) ) Aluminum, di-n-octyl (2,6-di-t-butylphenoxy) aluminum and the like. These organoaluminum compounds may be used alone or in combination of two or more.

  The amount of the organoaluminum compound used can be appropriately selected in accordance with the type of solvent, other various polymerization conditions, etc., but is generally 1.0 to 10 with respect to 1 mol of the organic lithium compound from the viewpoint of the polymerization rate. It is preferably used in the range of 0.0 mol, more preferably in the range of 1.1 to 5.0 mol, and still more preferably in the range of 1.2 to 4.0 mol. If the amount of the organoaluminum compound used exceeds 10.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and if it is less than 1.0 mol, the polymerization initiation efficiency tends to decrease.

Examples of the Lewis base include compounds having an ether bond and / or a tertiary amine structure in the molecule.
Examples of the compound having an ether bond in the molecule used as the Lewis base include ether. The ether is a cyclic ether having two or more ether bonds in the molecule or an acyclic ether having one or more ether bonds in the molecule from the viewpoint of high polymerization initiation efficiency and living property of the polymerization terminal anion. Is preferred. Examples of the cyclic ether having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6. Examples of the acyclic ether having one or more ether bonds in the molecule include acyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; 1,2-dimethoxyethane, 1,2-diethoxy Ethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxypropane 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, , 3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane, , 4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane and the like acyclic diethers; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl Ether, dibutylene glycol diethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether Tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, acyclic polyethers such as tetramethylammonium butylene glycol diethyl ether. Of these, acyclic ethers having 1 to 2 ether bonds in the molecule are preferable, and diethyl ether or 1,2-dimethoxyethane is more preferable from the viewpoints of suppression of side reactions and availability.

  The compound having a tertiary amine structure in the molecule used as the Lewis base includes tertiary polyamine. The tertiary polyamine means a compound having two or more tertiary amine structures in the molecule. Examples of the tertiary polyamine include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyl. Linear polyamines such as diethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino) ethyl] amine; 1,3,5-trimethylhexahydro-1, 3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16 -Non-aromatic heterocyclic compounds such as hexaazacyclooctadecane; aromatic heterocyclic compounds such as 2,2'-bipyridyl and 2,2 ': 6', 2 "-terpyridine .

  A compound having one or more ether bonds and one or more tertiary amine structures in the molecule may be used as the Lewis base. Examples of such a compound include tris [2- (2-methoxyethoxy) ethyl] amine.

These Lewis bases may be used alone or in combination of two or more.
The amount of the Lewis base used is preferably in the range of 0.3 to 5.0 mol with respect to 1 mol of the organic lithium compound from the viewpoints of polymerization initiation efficiency, stability of the polymerization terminal anion, and the like. The range of 3.0 mol is more preferable, and the range of 1.0 to 2.0 mol is more preferable. When the amount of the Lewis base used exceeds 5.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and when it is less than 0.3 mol, the polymerization initiation efficiency tends to decrease.

  The amount of Lewis base used is preferably in the range of 0.2 to 1.2 mol, more preferably in the range of 0.3 to 1.0 mol, with respect to 1 mol of the organoaluminum compound. .

  The living anionic polymerization is preferably performed in the presence of an organic solvent from the viewpoint of temperature control and uniformizing the inside of the system to facilitate the polymerization. Organic solvents include hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane from the viewpoints of safety, separation from water in washing of the reaction solution after polymerization, ease of recovery / reuse, etc .; chloroform, chloride Halogenated hydrocarbons such as methylene and carbon tetrachloride; esters such as dimethyl phthalate are preferred. These organic solvents may be used alone or in combination of two or more. In addition, it is preferable to deaerate the organic solvent in advance in the presence of an inert gas while performing a drying treatment from the viewpoint of allowing the polymerization to proceed smoothly.

  In the living anion polymerization, if necessary, other additives may be present in the reaction system. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.

  The living anionic polymerization is preferably performed at -30 to 25 ° C. When it is lower than −30 ° C., the polymerization rate is lowered and the productivity tends to be lowered. On the other hand, when the temperature is higher than 25 ° C., it tends to be difficult to polymerize the (meth) acrylic polymer block (a) including the partial structure (1) with good living property.

  The living anionic polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium. Moreover, it is preferable to carry out on sufficient stirring conditions so that a reaction system may become uniform. Moreover, it is preferable that the monomer to be used is previously dried in an inert gas atmosphere from the viewpoint of allowing living anion polymerization to proceed smoothly. In the drying treatment, a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.

  In the above living anionic polymerization, the organic lithium compound, organoaluminum compound, Lewis base and monomer can be added to the reaction system of the anionic polymerization by contacting the Lewis base with the organoaluminum compound before contacting with the organolithium compound. It is preferable to add so as to. The organoaluminum compound may be added to the anionic polymerization reaction system prior to the monomer or simultaneously. When the organoaluminum compound is added to the anionic polymerization reaction system simultaneously with the monomer, the organoaluminum compound may be added after separately mixing with the monomer.

  The living anionic polymerization can be stopped by adding a polymerization terminator such as methanol; acetic acid or hydrochloric acid in methanol; a protic compound such as aqueous solution of acetic acid or hydrochloric acid to the reaction solution. The amount of the polymerization terminator used is usually preferably in the range of 1 to 100 mol with respect to 1 mol of the organic lithium compound used.

  As a method for separating and obtaining the (meth) acrylic block copolymer (A) from the reaction solution after the anionic polymerization is stopped, a known method can be adopted. For example, the reaction solution is poured into a poor solvent of the (meth) acrylic block copolymer (A) to precipitate the (meth) acrylic block copolymer (A), and the organic solvent is distilled off from the reaction solution. Examples thereof include a method for obtaining a (meth) acrylic block copolymer (A).

  In addition, if the metal component derived from the organolithium compound and the organoaluminum compound remains in the (meth) acrylic block copolymer (A) obtained separately, the physical properties of the (meth) acrylic block copolymer Decrease, poor transparency, etc. may occur. Therefore, it is preferable to remove the metal component derived from the organolithium compound and the organoaluminum compound after the anionic polymerization is stopped. As a method for removing the metal component, it is effective to perform a washing treatment using an acidic aqueous solution, an adsorption treatment using an adsorbent such as an ion exchange resin, celite, activated carbon or the like. Here, as acidic aqueous solution, hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution etc. can be used, for example.

  As a method for introducing the active energy ray-curable group containing the partial structure (1) in the production of the (meth) acrylic block copolymer (A), a simple substance containing the di (meth) acrylate (3) described above can be used. In addition to a method of polymerizing a monomer to form a (meth) acrylic polymer block (a), a partial structure (hereinafter referred to as “precursor structure”) that is a precursor of the partial structure (1) is included. A method of converting the precursor structure into the partial structure (1) after forming the polymer block is also included. A polymer block containing a precursor structure is obtained by polymerizing a monomer containing a polymerizable functional group and a compound containing a precursor structure. Examples of the polymerizable functional group include a styryl group, a 1,3-dienyl group, a vinyloxy group, a (meth) acryloyl group, and a (meth) acryloyl group is preferable. The precursor structure includes a hydroxyl group protected by a hydroxyl group and a protecting group (silyloxy group, acyloxy group, alkoxy group, etc.), an amino group, an amino group protected by a protecting group, a thiol group, and a thiol group protected by a protecting group. As well as isocyanate groups.

  A polymer block containing a hydroxyl group as a precursor structure is reacted with a compound having a partial structure (1) and a partial structure (carboxyl group, ester, carbonyl halide, etc.) capable of reacting with a hydroxyl group, thereby forming a (meth) acrylic polymer. Block (a) can be formed. In addition, a polymer block containing a hydroxyl group protected by a protecting group as a precursor structure can form a (meth) acrylic polymer block (a) after removing the protecting group to form a hydroxyl group.

  The polymer block containing an amino group as a precursor structure has a partial structure (1) and a partial structure capable of reacting with the amino group (carboxyl group, carboxylic acid anhydride, ester, carbonyl halide, aldehyde group, isocyanate group, etc.). The (meth) acrylic polymer block (a) can be formed by reacting with a compound. A polymer block containing an amino group protected by a protecting group as a precursor structure can form a (meth) acrylic polymer block (a) in the same manner after removing the protecting group to form an amino group.

  The polymer block containing a thiol group as a precursor structure comprises a partial structure (1) and a partial structure capable of reacting with a thiol group (carboxyl group, carboxylic acid anhydride, ester, carbonyl halide, isocyanate group, carbon-carbon double bond) Etc.) can be reacted with a compound having (meth) acrylic polymer block (a). A polymer block containing a thiol group protected by a protective group as a precursor structure can form a (meth) acrylic polymer block (a) in the same manner after removing the protective group to form a thiol group.

  A polymer block containing an isocyanate group as a precursor structure is reacted with a compound having a partial structure (1) and a partial structure (hydroxyl group, amino group, etc.) capable of reacting with an isocyanate group, to form a (meth) acrylic polymer block. (A) can be formed.

  In the production of the (meth) acrylic block copolymer (A), as a method of forming the (meth) acrylic polymer block (a), the viewpoint that the active energy ray-curable group (2) can be easily introduced directly. From the above, a method of polymerizing a monomer containing di (meth) acrylate (3), typically a method of living anion polymerization is preferred.

The active energy ray-curable hard coat agent of the present invention may contain a photopolymerization initiator in addition to the (meth) acrylic block copolymer (A). Examples of the photopolymerization initiator include acetophenones (for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1). -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, etc.), benzophenones (for example, benzophenone, benzoylbenzoic acid, hydroxybenzophenone, 3,3′-dimethyl-4- Carbonyl compounds such as methoxybenzophenone, acrylated benzophenone), Michler ketones (eg Michler ketone) and benzoins (eg benzoin, benzoin methyl ether, benzoin isopropyl ether); tetramethylthiuram monosulfide, thioxa Sulfur compounds such as thionesone (eg thioxanthone, 2-chlorothioxanthone); acylphosphine oxides (eg 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide and the like; titanocenes (for example, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1) -Yl) -phenyl) titanium and the like, and azo compounds (for example, azobisisobutylnitrile and the like). Of these, acetophenones and benzophenones are preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  When the active energy ray-curable hard coat agent of the present invention contains a photopolymerization initiator, the content thereof is the main agent ((meth) acrylic block copolymer) contained in the active energy ray-curable hard coat agent of the present invention. 0.01-10 mass parts is preferable with respect to 100 mass parts of union (A) and the reactive diluent mentioned later which is an arbitrary component, and 0.05-8 mass parts is more preferable. If it is 0.01 part by mass or more, the curability of the active energy ray-curable hard coat agent tends to be good, and if it is 10 parts by mass or less, the resulting cured product tends to have good heat resistance.

  Moreover, the active energy ray-curable hard coat agent of the present invention may contain a sensitizer in addition to the photopolymerization initiator. Examples of the sensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine, diethylaminoethyl methacrylate and the like. Of these, diethylaminoethyl methacrylate and triethylamine are preferable.

  When a photopolymerization initiator and a sensitizer are mixed and used, the mass ratio of the photopolymerization initiator and the sensitizer is preferably in the range of 10:90 to 90:10, and 20:80 to 80: A range of 20 is more preferred.

  The active energy ray-curable hard coat agent of the present invention may contain a reactive diluent exhibiting polymerizability other than the (meth) acrylic block copolymer (A). Examples of the reactive diluent include styrene such as styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, and divinylbenzene. Derivatives; Fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Propyl, (meth) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, ( Hexyl (meth) acrylate, heptyl (meth) acrylate, (me ) Octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, ( (Meth) acrylate dodecyl, (meth) acrylate dodecyl, (meth) acrylate stearyl, (meth) acrylate isostearyl, (meth) acrylate benzyl, (meth) acrylate isobornyl, (meth) acrylate bornyl, ( (Meth) acrylic acid tricyclodecanyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid 4-butylcyclohexyl, (meth) acrylic acid 2-hydroxyethyl, (Meth) acrylic acid 2-hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, phenoxy (meth) acrylate Ethyl, (meth) acrylic acid polyethylene glycol monoester, (meth) acrylic acid polypropylene glycol monoester, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid methoxypolyethylene glycol, (meta ) Methoxypolypropylene glycol acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 4- (meth) acryloylmorpholine, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, tetra Ethylene glycol di (meth) acrylate, tricyclodecanediyldimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol Diglycidyl ether end (meth) acrylic acid adduct, pentaerythritol tetra (meth) acrylate, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanoltri (Meth) acrylate, N, N′-bis [2-((meth) acryloyloxy) ethyl] -N ″-(2-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, ethylene oxide or propylene oxide of hydrogenated bisphenol A Di (meth) acrylates of diols that are adducts of (Meth) acrylic acid derivatives such as xanthanimethanol di (meth) acrylate; epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin; COOH group-modified epoxy acrylate type Resin: Polyol (polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc. ) And organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphe Urethane resins obtained from methane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) (hydroxy) -containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol Urethane acrylate resin obtained by reaction with triacrylate, etc .; resin in which (meth) acrylic group is introduced into the above polyol via ester bond; polyester (meth) acrylate resin; epoxidized soybean oil, epoxy stearic acid And epoxy compounds such as benzyl.

  Among them, from the viewpoint of scratch resistance of the obtained hard coat film, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, Triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyldimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Bisphenol A diglycidyl ether end (meth) acrylic acid adduct, pentaerythritol tetra (meth) acrylate, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3 5-trisethanol tri (meth) acrylate, N, N′-bis [2-((meth) acryloyloxy) ethyl] -N ″-(2-hydroxyethyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, hydrogenated bisphenol A Di (meth) acrylate of diol, which is an adduct of ethylene oxide or propylene oxide Compounds having multiple (meth) acryloyloxy group rate and the like are preferable. These reactive diluents may be used alone or in combination of two or more.

  When a reactive diluent is contained in the active energy ray-curable hard coat agent of the present invention, the content is obtained from the flowability of the active energy ray-curable hard coat agent and the active energy ray-curable hard coat agent. From the viewpoint of increasing the mechanical strength of the resulting cured product (hard coat layer), 70 to 99 parts by mass are preferable in 100 parts by mass of the main agent ((meth) acrylic block copolymer (A) and reactive diluent), 85-98 mass parts is more preferable.

  The active energy ray-curable hard coat agent of the present invention may contain a solvent. By containing a solvent in the active energy ray-curable hard coat agent of the present invention, the viscosity can be adjusted and the coating property can be improved. Moreover, it can be made easy to melt | dissolve or disperse | distribute the metal oxide, additive, etc. which are mentioned later by using a solvent.

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and chlorobenzene; aliphatic or alicyclic hydrocarbons such as pentane, hexane, cyclohexane and heptane; halogenated carbons such as carbon tetrachloride, chloroform and ethylene dichloride. Nitro compounds such as nitromethane and nitrobenzene; ethers such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; esters such as methyl acetate, ethyl acetate, isopropyl acetate and amyl acetate; dimethylformamide and methanol Alcohols such as ethanol and propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; and the like can be used.

  When the active energy ray-curable hard coat agent of the present invention contains a solvent, the content thereof is preferably 80 parts by mass or less and more preferably 50 parts by mass or less with respect to 100 parts by mass of the main agent. When the content of the solvent exceeds 80 parts by mass, it may take time or may remain in the hard coat layer when the solvent is distilled off after coating the active energy ray-curable hard coat agent. .

  The active energy ray-curable hard coat agent of the present invention may contain particles made of a metal oxide. Examples of the purpose of containing such particles include further increasing the hardness of the hard coat layer formed from the active energy ray-curable hard coat agent of the present invention and decreasing the light reflectance.

The metal oxide constituting such particles preferably contains at least one metal element selected from the group consisting of Si, Ti, Zr, Zn, Sn, In, La and Y, and includes SiO, SiO ₂ , TiO ₂ , ZrO ₂ , ZnO, SnO ₂ , In ₂ O ₃ , La ₂ O ₃ , Y ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , SiO ₂ —Zr ₂ O ₃ , SiO ₂ —Ti ₂ O ₃ , Al ₂ O ₃ —ZrO ₂ and TiO ₂ —ZrO ₂ are more preferable, and SiO ₂ , TiO ₂ , ZrO ₂ , and ZnO ₂ are more preferable. The particles made of these metal oxides may be used alone or in combination of two or more.

  The average particle diameter of the particles made of such metal oxide is preferably in the range of 1 to 300 nm, more preferably in the range of 1 to 50 nm. When the average particle diameter exceeds 300 nm, the transparency of the hard coat layer may be impaired. In addition, this average particle diameter means the volume average particle diameter calculated | required by measuring using a dynamic light scattering type particle size distribution measuring apparatus.

  When the active energy ray-curable hard coat agent of the present invention contains particles composed of a metal oxide, the blending amount is preferably 1 to 80% by mass with respect to the total amount of the active energy ray-curable hard coat agent. More preferably, it is 5-50 mass%. If the amount of fine particles exceeds 80% by mass, the hard coat layer may become brittle.

  The active energy ray-curable hard coat agent of the present invention has various active energy ray-curable groups such as plasticizers, fillers, stabilizers, pigments, and dyes, as long as the curability is not significantly inhibited. Additives may be included.

  The purpose of including the plasticizer in the active energy ray-curable hard coat agent of the present invention is, for example, adjustment of the viscosity of the active energy ray-curable hard coat agent. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate. Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinoleate; Esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol esters; Tricresyl phosphate, tributyl phosphate, and the like Trimellitic acid ester; Polybutadiene, butadiene-acrylonitrile copolymer, diene (co) polymer such as polychloroprene; Polyisobutylene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the hydroxyl groups of these polyether polyols Polyethers such as derivatives converted to groups, ether groups, etc .; 2 basic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, and 2 such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol Polyester obtained from a monohydric alcohol; and the like. The (co) polymer is a general term for a homopolymer and a copolymer. These plasticizers may be used alone or in combination of two or more.

  The molecular weight or number average molecular weight of these plasticizers is preferably 400 to 15000, more preferably 800 to 10000, and more preferably 1000 to 8000. Such a plasticizer may or may not have a functional group other than the active energy ray-curable group (for example, a hydroxyl group, a carboxyl group, a halogen group, etc.). When the molecular weight or Mn of the plasticizer is 400 or more, the plasticizer does not flow out from the hard coat layer formed from the active energy ray-curable hard coat agent of the present invention over time, and the hard coat film of the present invention is The initial physical properties can be maintained for a long time. Moreover, when the molecular weight or Mn of the plasticizer is 15000 or less, the handleability of the active energy ray-curable hard coat agent tends to be improved.

  When the plasticizer is contained in the active energy ray-curable hard coat agent of the present invention, the content is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the (meth) acrylic block copolymer (A), 10-120 mass parts is more preferable, and 20-100 mass parts is further more preferable. When the amount is 5 parts by mass or more, the fluidity is excellent, and when the amount is 150 parts by mass or less, the hard coat layer formed from the active energy ray-curable hard coat agent of the present invention tends to have excellent scratch resistance.

  The hard coat film of the present invention is obtained by applying the active energy ray-curable hard coat agent of the present invention to the surface of a plastic film and then irradiating and curing the active energy ray to form a hard coat layer. . As the coating method, conventionally known methods such as hand coating such as brush coating, roll coating, gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, spray coating, and dipping can be selected. The thickness to be applied is preferably in the range of 1 to 500 μm, and more preferably in the range of 2 to 200 μm.

  Examples of the material for the plastic film include polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), polyacrylate, polyvinyl alcohol (PVA), polystyrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate ( PBT), ethylene-vinyl acetate copolymer (EVA), acrylonitrile-butadiene-styrene copolymer (ABS), triacetyl cellulose (TAC), cycloolefin polymer (COP), polycarbonate (PC), polyether ketone (PEEK) ), Polyamide imide (PAI), polyimide (PI), polyether amide (PEI), nylon (NY), polyvinyl chloride (PVC), polyvinylidene chloride, and other plastic materials And the like. The thickness of the plastic film is usually in the range of 30 to 300 μm.

  The hard coat film is an antistatic layer, an adhesive layer, an adhesive layer, an easy adhesion layer, a strain relaxation layer, an antiglare (non-glare) layer, a photocatalyst layer, an antifouling layer, an antireflection layer, depending on the purpose. Various functional layers such as an ultraviolet shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier property may be further provided. Note that the stacking order of the hard coat layer and the functional layer is not particularly limited, and the stacking method is not particularly limited. The laminate may include a plurality of the hard coat layers and functional layers.

The active energy ray used when the active energy ray-curable hard coat agent of the present invention is cured can be irradiated using a known apparatus.
For ultraviolet irradiation, sunlight rays that emit light in the wavelength range of 150 to 450 nm, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, gallium lamp, xenon lamp, xenon flash lamp, chemical lamp, LED, etc. Can be used.

Integrated light quantity of active energy rays, usually in the range of 0.01 to 10 J / cm ^2, preferably in the range of 0.1~5J / cm ^2, further preferably in the range of 0.2~1J / cm ^2. If it is less than 0.01 J / cm ^{2, the} curability of the active energy ray-curable hard coat agent is insufficient, and if it is more than 10 J / cm ² , the active energy ray-curable hard coat agent may be deteriorated.

  The relative humidity when irradiating the active energy ray-curable hard coat agent of the present invention with active energy rays is preferably 30% or less from the viewpoint of suppressing the decomposition of the active energy ray-curable hard coat agent. More preferably, it is 10% or less.

  The active energy ray-curable hard coat agent of the present invention can be further heated during or after irradiation with ultraviolet rays as necessary to promote curing. The heating temperature is preferably in the range of 40 to 130 ° C, more preferably in the range of 50 to 100 ° C. In addition, heating can be performed by infrared rays, far infrared rays, hot air, high frequency heating, or the like.

  For example, when the active energy ray-curable hard coat agent of the present invention does not contain a polymerization initiator, it can be cured by irradiation with an electron beam (EB). The acceleration voltage in the case of irradiation with EB is preferably in the range of 0.1 to 10 MeV, more preferably in the range of 10 to 500 keV, and still more preferably in the range of 20 to 300 keV. The irradiation dose is preferably in the range of 10 to 500 kGy, more preferably in the range of 30 to 300 kGy, and still more preferably in the range of 40 to 200 kGy. The active energy ray-curable hard coat agent can be further heated during the electron beam irradiation or after irradiation to accelerate the curing as necessary. In addition, heating can be performed by infrared rays, far infrared rays, hot air, high frequency heating, or the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this Example.
In the following Examples and Comparative Examples, the raw materials were dried and purified by a conventional method and degassed with nitrogen, and the transfer and supply were performed under a nitrogen atmosphere.

[Monomer consumption rate]
In the following Examples and Comparative Examples, the consumption rate of each monomer after polymerization was determined by collecting 0.5 ml of the reaction solution, mixing it in 0.5 ml of methanol, and then collecting 0.1 ml from the mixture solution. Then, ¹ H-NMR measurement was performed by dissolving in 0.5 ml of deuterated chloroform, and a peak derived from a proton directly connected to a carbon-carbon double bond of (meth) acrylic acid ester used as a monomer (chemical shift) The value was calculated from the change in the ratio of the integral value of the peak (chemical shift value: 7.00 to 7.38 ppm) derived from the proton directly linked to the aromatic ring of toluene (value 6.08 to 6.10).
¹ H-NMR measurement condition apparatus: nuclear magnetic resonance apparatus “JNM-ECX400” manufactured by JEOL Ltd.
Solvent: Deuterated chloroform Temperature: 25 ° C

[Number average molecular weight, molecular weight distribution]
In the following examples and comparative examples, GPC (gel permeation chromatography) measurement of the obtained polymer was performed to determine the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of standard polystyrene.
Equipment: GPC equipment "HLC-8220GPC" manufactured by Tosoh Corporation
Separation column: “TSKgel SuperMultipore HZ-M (column diameter = 4.6 mm, column length = 15 cm)” manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Eluent flow rate: 0.35 ml / min Column temperature: 40 ° C
Detection method: differential refractive index (RI)

[Initiation efficiency of polymerization]
When the number average molecular weight of the polymer actually obtained in the step (1) is Mn (R1) and the number average molecular weight of the polymer obtained in the step (1) is theoretically Mn (I1), the step (1 ) Polymerization initiation efficiency (F1) is calculated from the following equation.
F1 (%) = 100 × Mn (I1) / Mn (R1)

[Block efficiency from step (1) to step (2)]
When the number average molecular weight of the block copolymer actually obtained in the step (2) is Mn (R2) and the number average molecular weight of the block copolymer obtained in the step (2) is theoretically Mn (I2). The block efficiency (F2) from step (1) to step (2) is calculated from the following equation.
F2 (%) = 10000 · {Mn (I2) −Mn (I1)} / [F1 · {Mn (R2) −Mn (R1)}]

[Production Example 1]
(Process (1))
After 1.5L of toluene was added to a 3L flask which had been dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylene was added as a Lewis base while stirring the solution in the flask. Tetramine 2.2 ml (8.2 mmol), 25.1 ml (11.3 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the organoaluminum compound. After adding sequentially, it cooled to -20 degreeC. To this was added 6 ml (7.8 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 59.0 ml (246 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. ) And 60.9 ml (573 mmol) of a methyl methacrylate mixture were added all at once to initiate anionic polymerization. After 280 minutes from the end of the addition of the above mixture, the reaction solution changed from the original yellow color to colorless. After stirring for another 20 minutes, the reaction solution was sampled. The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (1) was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 15,100, and Mw / Mn was 1.19. Furthermore, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Process (2))
Subsequently, while stirring the reaction solution at −20 ° C., 13.9 ml of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as an organoaluminum compound (6. 2 mmol), and 1 minute later, 327 ml (2.27 mol) of n-butyl acrylate was added as a monomer at a rate of 3.6 ml / min. The reaction solution was sampled immediately after completion of the addition of n-butyl acrylate. The consumption rate of n-butyl acrylate in the step (2) was 100%. Moreover, Mn (Mn (R2)) of the obtained polymer was 54,800, and Mw / Mn was 1.27. Furthermore, the block efficiency (F2) from step (1) to step (2) was 95.0%.

(Process (3))
Subsequently, while stirring the reaction solution at −20 ° C., a mixture of 55.5 ml (231 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and 57.3 ml (539 mmol) of methyl methacrylate 112. After 8 ml was added all at once, the temperature was raised to 20 ° C. at a rate of 2 ° C./min. The reaction solution was sampled 720 minutes after the addition of the above mixture.
The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (3) was 100%.

(Process (4))
Subsequently, while stirring the reaction solution at 20 ° C., 100 ml of methanol was added to stop anionic polymerization. The obtained solution was poured into 10 L of methanol, the polymer was precipitated, recovered by filtration, dried at 100 ° C. and 30 Pa, and dried with 447 g of (meth) acrylic block copolymer (A) (hereinafter “(meta ) Acrylic block copolymer (A1) ”). Mn of the obtained (meth) acrylic block copolymer (A1) was 70,900, and Mw / Mn was 1.34.

[Example 1, Comparative Examples 1-2]
In the compounding ratio shown in Table 1, (meth) acrylic block copolymer (A), reactive diluent (B), photopolymerization initiator (C) and solvent (D) are mixed, and active energy ray curing is performed. A hard coating agent was prepared. The prepared active energy ray-curable hard coat agent was applied to a polyethylene terephthalate film (trade name: Toray Co., Ltd., Lumirror) with a thickness of 100 μm by a bar coating method so that the coating thickness was 10 μm. A hard coat film comprising a polyethylene terephthalate film provided with a hard coat layer after being dried at 80 ° C. for 1 minute in an air circulation dryer and then irradiated with ultraviolet rays so as to obtain an integrated irradiation light quantity of 300 mJ / cm ^2. Got.
The obtained hard coat film was evaluated by the following performance evaluation test method. The results are shown in Table 1.

<Performance evaluation test method>
(1) Pencil hardness Pencil hardness was measured based on JIS-K5600-5-4 using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The load was 1,000 g.

(2) Warpage deformation amount The hard coat films obtained in Examples and Comparative Examples were cut into 10 cm × 10 cm and placed on a horizontal table. FIG. 1 is a side view of a hard coat film 1 placed on a horizontal table 2. All the lengths between two adjacent points of the four corners of the hard coat film were measured, an average value L was calculated, and used as an index of the amount of warp deformation. In addition, this length is not the value measured along the hard coat film, but means the length 4 of the line segment connecting the corners 3.

(3) Peeling resistance The hard coat films obtained in the examples and comparative examples were cut with crosses marked with a 1 cm length and intersecting at right angles. Next, after a tape (manufactured by Nichiban, Cellotape (registered trademark), CT-15, 15 mm width) was applied on the cut of the hard coat layer, it was peeled off in a direction perpendicular to the hard coat layer. The operation of peeling after applying the tape on the cut of the hard coat layer was repeated 5 times, and then the state of the surface after peeling was observed, and the result was evaluated according to the following criteria.
○: No peeling.
(Triangle | delta): It peels along the part which made the notch.
X: Peeling regardless of the depth of cut.

(4) Scratch resistance The hard coat film obtained was rubbed back and forth 20 times with a Gakushin abrasion tester equipped with steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0000) at a weight of 500 g. The presence or absence was observed, and the results were evaluated according to the following criteria.
A: No scar remains.
○: The scar remains thin.
Δ: A clear mark remains.
X: The ground is exposed.

(5) Workability The obtained hard coat film is cut into a dumbbell shape and stretched at 10 mm / min by a tensile tester (Autograph AG-2000B (manufactured by Shimadzu Corporation)), and the state of the hard coat layer being stretched is determined. Observation was made and the workability was evaluated according to the following criteria.
A: The hard coat layer is followed and stretched until the hard coat film breaks, and there is no cloudiness or crack.
○: It becomes cloudy before the hard coat film breaks.
Δ: A crack occurs before the hard coat film breaks.
X: The hard coat layer peels off before the hard coat film breaks.

(6) Transparency The haze value (H1) of the hard coat film was measured under a measurement condition in accordance with JIS K7136 with a haze meter (NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the polyester film film before forming the hard coat layer was measured. Transparency was evaluated by a difference value (ΔH = H1−H0) with respect to the haze value (H0).
A: ΔH ≦ 1
○: 1 <ΔH ≦ 2 Difference in haze value is 2 or less.
Δ: 2 <ΔH ≦ 5
×: 5 <ΔH

Abbreviations in Table 1 indicate the following.
Reactive diluent (B1): Urethane acrylate resin (manufactured by Kyoeisha Chemical Co., Ltd., urethane acrylate UA-306I, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer)
Reactive diluent (B2): Pentaerythritol tetraacrylate (Toagosei Co., Ltd., Aronix M-450)
Reactive diluent (B3): 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-315)
Photopolymerization initiator (C1): 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184)
Solvent (D1): Methyl ethyl ketone

  From Table 1, it can be seen that a hard coat film provided with a hard coat layer obtained by curing the active energy ray-curable hard coat agent of the present invention has a small amount of warp deformation and high peel resistance. This can be presumed to be due to the suppression of volume shrinkage associated with curing. Table 1 also shows that the hard coat film is excellent in processability.

  A hard coat film provided with a hard coat layer formed by curing the active energy ray-curable hard coat agent of the present invention on the surface of a plastic film is applied to the surface of a housing such as home appliances for the purpose of surface protection or appearance improvement. Suitable for application.

1: Hard coat film 2: Horizontal base 3: Corner of hard coat film 4: Length of adjacent corner

Claims (6)

(Meth) acrylic polymer block (a) having an active energy ray-curable group containing a partial structure represented by the following general formula (1) and (meth) acrylic polymer having no active energy ray-curable group An active energy ray-curable hard coat agent containing the (meth) acrylic block copolymer (A) comprising the block (b).

(Wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) The active energy ray-curable hard coat agent according to claim 1, wherein the active energy ray-curable group is represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and X represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20)   The active energy ray-curable hard coat agent according to claim 1 or 2, further comprising a reactive diluent.   1-30 mass parts of said (meth) acrylic block copolymers (A) are contained with respect to 100 mass parts of total amounts of the said (meth) acrylic block copolymer (A) and the said reactive diluent. The active energy ray-curable hard coat agent according to claim 3.   The active energy ray-curable hard coat agent according to claim 3 or 4, wherein the reactive diluent is a compound having a plurality of (meth) acryloyloxy groups.   A hard coat film provided with a hard coat layer formed by curing the active energy ray-curable hard coat agent according to claim 1 on the surface of a plastic film.

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