JP2016041794A - Active energy ray-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition which cures promptly upon irradiation with an active energy ray and realizes excellent transparency and flexibility of the obtained cured product, without deformation caused by the curing.SOLUTION: An active energy ray-curable composition is produced which comprises: a (meth)acrylic block copolymer (A) comprising a (meth)acrylic polymer block (a) having active energy ray-curable groups including a partial structure represented by the general formula (1) in the figure, and an acrylic polymer block (b) without active energy ray-curable groups; and a methacrylic polymer (B) having active energy ray-curable groups including a partial structure represented by the general formula (1) in the figure. (In the formula, Rrepresents a hydrogen atom or C1-20 hydrocarbon group.)SELECTED DRAWING: None

Description

  The present invention relates to a polymer composition having active energy ray curability. Specifically, the present invention relates to an active energy ray-curable composition that is rapidly cured by irradiation with an active energy ray, and a cured product that is not deformed and has excellent transparency and flexibility can be obtained by such curing.

  Active energy ray-curable compositions that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams are known, and are used for applications such as adhesives, adhesives, paints, inks, coating materials, and optical modeling materials. It has been.

  On the other hand, a (meth) acrylic block copolymer consisting of a methacrylic polymer block and an acrylic polymer block is excellent in tackiness, moldability, weather resistance, etc., making use of these characteristics, adhesives, adhesives, coatings Expansion to applications such as materials and various molding materials is expected.

  Furthermore, as a material having these characteristics, an active energy ray-curable composition comprising a (meth) acrylic block copolymer having an active energy ray-curable functional group, comprising a methacrylic polymer block and an acrylic polymer block A thing is known (refer patent document 1).

  The subject of such an active energy ray-curable composition is an improvement in the curing rate. However, problems such as deformation of the cured product, opacification, and decrease in flexibility may occur as the curing rate increases.

JP 2011-184678 A

  Accordingly, an object of the present invention is to provide an active energy ray-curable composition that is rapidly cured by irradiation with active energy rays, and that the resulting cured product has no deformation and is excellent in transparency and flexibility. That is.

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)”) and active energy A (meth) acrylic block copolymer (A) comprising an acrylic polymer block (b) having no linear curable group, and a methacrylic heavy having an active energy ray curable group containing the partial structure (1) An active energy ray-curable composition containing the combination (B);
[2] The active energy ray-curable composition according to [1], further comprising a photopolymerization initiator; and [3] (meth) acrylic block copolymer (A) and methacrylic polymer ( The active energy ray curable group of [1] or [2], wherein the active energy ray curable group of B) includes a partial structure represented by the following general formula (2) (hereinafter referred to as “partial structure (2)”) By providing a composition.

（ 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 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 composition of the present invention is rapidly cured by irradiation with an active energy ray, and by such curing, a cured product having no deformation and excellent in transparency and flexibility is obtained.

Hereinafter, the present invention will be described in detail.
The active energy ray-curable composition 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 (meth) acrylic block copolymer (A) contains 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 composition of the present invention is cured by irradiation with active energy rays to form a cured product. 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.

（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） The partial structure (1) is represented by the following general formula (1).

(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 Aryl groups such as 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 active energy ray-curable composition of the present invention is applied to a substrate as an adhesive, a coating agent, etc., cured by irradiating active energy rays and used as a cured product, and then disposal of the cured product, etc. May be necessary. At that time, it is desirable that such a cured product can be easily peeled from the substrate, for example, by a wet heat decomposition method. Active energy ray curing comprising the partial structure (1) of the (meth) acrylic polymer block (a) in the (meth) acrylic block copolymer (A) from the viewpoint of excellent wet heat decomposability after curing The sex group preferably includes the partial structure (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） The partial structure (2) 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 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), examples of the hydrocarbon group having 1 to 6 carbon atoms that R ² and R ³ each independently represent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an 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, alkyl group such as 3-methylpentyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; phenyl group, etc. Of the aryl group. Among these, from the viewpoints of active energy ray curability and wet heat decomposability, 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 viewpoint of the fluidity and curing rate of the active energy ray-curable composition.

  The content of the partial structure (1) in the (meth) acrylic polymer block (a) is 0.2 to 100 mol with respect to all monomer units forming the (meth) acrylic polymer block (a). % Range is preferable, the range of 10 to 90 mol% is more preferable, and the range of 25 to 80 mol% is more preferable. In addition, the number of partial structures (1) contained in one (meth) acrylic polymer block (a) is preferably 2 or more, and preferably 4 or more, from the viewpoint of curing speed. More preferred.

  The (meth) acrylic polymer block (a) includes a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester. As such a (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. can do.

  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, 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 Lauryl, dodecyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, ( 2-aminoethyl (meth) acrylate, N, N-dimethyla (meth) acrylate Noethyl, N, N-diethylaminoethyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) acrylate, 3- (trimethylsilyl) (meth) acrylate Oxy) propyl, glycidyl (meth) acrylate, γ-((meth) acryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acrylic 2-trifluoromethylethyl acid, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, ( (Meth) acrylic acid perfluoromethyl, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Examples include (meth) acrylic acid 2-perfluorohexadecylethyl. Among these, preferred are alkyl methacrylates having an alkyl group having 5 or less carbon atoms, such as methyl methacrylate, ethyl methacrylate, 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 to have an active energy ray-curable group containing a partial structure (2) in which R ¹ is R ⁴ and X is O The methacrylic polymer block (a) is preferable because it is obtained.

（式中、Ｒ²およびＲ³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）

(In the formula, 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 is 1 to 20) Represents an integer)

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).

In general formula (3), R ⁴ is preferably a methyl group from the viewpoint of increasing the selectivity of polymerization. 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, 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 acid esters. 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 esters such as esters; N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and other acrylamides; N-isopropylmethacrylamide, Nt-butyl Methacrylamide, such as methacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, 2-bromomethylacrylate Methyl acrylic acid, 2-bromomethyl acrylate, methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, 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 amount 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 the handleability, fluidity and active energy ray curable composition of the resulting active energy ray curable composition are not limited. From the viewpoint of the mechanical properties of the cured product obtained by irradiating the product with active energy rays, the range of 500 to 1,000,000 is preferable, and the range of 1,000 to 300,000 is more preferable. In addition, in this specification, Mn means the number average molecular weight of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  The (meth) acrylic block copolymer (A) contains an acrylic polymer block (b) having no active energy ray-curable group.

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 bonds such as (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyloxy group, 1,3-dienyl group, styryl group (particularly A functional group having a general formula CH ₂ ═CHR— (wherein R is an alkyl group or a hydrogen atom); an epoxy group, an oxetanyl group, a thiol group, a maleimide group, and the like.

  The acrylic polymer block (b) is a polymer block composed of monomer units formed by polymerizing a monomer containing an acrylate ester and having no active energy ray-curable group as described above. is there.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and acrylic acid. Isobornyl, lauryl acrylate, dodecyl acrylate, trimethoxysilylpropyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, 2-methoxyethyl acrylate, phenyl acrylate, naphthyl acrylate Monoacrylates such as 2- (trimethylsilyloxy) ethyl acrylate and 3- (trimethylsilyloxy) propyl acrylate, and n-butyl acrylate, t-butyl acrylate, 2-ethyl acrylate Hexyl, lauryl acrylate, acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms such as dodecyl acrylate are preferred. These acrylic acid esters may be used alone or in combination of two or more.

  The content of the monomer unit formed by the acrylic ester in the acrylic polymer block (b) is 90 mol% or more based on the total monomer units forming the acrylic polymer block (b). It is preferable that it is 95 mol% or more.

  The acrylic polymer block (b) may have a monomer unit formed by a monomer other than the acrylate ester. Examples of the other monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid. Isobornyl acid, lauryl methacrylate, dodecyl methacrylate, trimethoxysilylpropyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2-methoxyethyl methacrylate, phenyl methacrylate, methacrylic acid Monofunctional methacrylates such as naphthyl, 2- (trimethylsilyloxy) ethyl methacrylate, 3- (trimethylsilyloxy) propyl methacrylate; methyl α-methoxyacrylate, α-ethoxy Α-alkoxy acrylates such as methyl acrylate; crotonic esters such as methyl crotonate and ethyl crotonate; 3-alkoxy acrylates such as 3-methoxy acrylate; N-isopropylacrylamide, Nt-butyl Acrylamide such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide; N-isopropylmethacrylamide, Nt-butylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, etc. Methacrylamide; 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 acrylic polymer block (b) is 10 mol with respect to all the monomer units forming the acrylic polymer block (b). % Or less, and more preferably 5 mol% or less.

  The Mn per acrylic polymer block (b) is not particularly limited, but is 3,000 from the viewpoint of the handleability, fluidity, mechanical properties, etc. of the resulting (meth) acrylic block copolymer (A). The range of ˜2,000,000 is preferable, and the range of 5,000 to 1,000,000 is more preferable.

  The (meth) acrylic block copolymer (A) is a block copolymer in which at least one (meth) acrylic polymer block (a) and at least one acrylic polymer block (b) are bonded to each other. The number of each polymer block and the bonding order are not particularly limited, but the (meth) acrylic polymer block (a) is a (meth) acrylic block copolymer (A) from the viewpoint of active energy ray curability. ) At least one terminal is preferable, and from the viewpoint of ease of production of the (meth) acrylic block copolymer (A), a linear polymer is more preferable, and one ( A diblock copolymer in which a (meth) acrylic polymer block (a) and one acrylic polymer block (b) are bonded, and both ends of one acrylic polymer block (b) ( Data) triblock copolymer each one acrylic polymer block (a) is bonded, respectively are more preferred.

  Ratio of mass of (meth) acrylic polymer block (a) and mass of acrylic polymer block (b) constituting (meth) acrylic block copolymer (A) ((meth) acrylic polymer The block (a): acrylic polymer block (b)) is not particularly limited, but is preferably 85:15 to 5:95, more preferably 80:20 to 7:93, and 75: More preferably, it is 25 to 10:90. The mass ratio 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% by mass or more. When the curing rate is 85% by mass or less, the toughness of the cured product is increased.

  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.

The Mn of the (meth) acrylic block copolymer (A) is not particularly limited, but from the viewpoints of handleability, fluidity, mechanical properties and the like of the active energy ray-curable composition of the present invention, 4,000 to 3, The range of 000,000 is preferable, and the range of 7,000 to 2,000,000 is more preferable.
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. In addition, in this specification, Mw means the weight average molecular weight of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  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 20 mol%, more preferably 2 to 15 mol%, still more preferably 3 to 10 mol%.

  From the viewpoint of curing speed, the number of partial structures (1) contained in the (meth) acrylic block copolymer (A) is preferably 4 or more and more than 8 per polymer molecule. Is more preferable.

  The production method of the block copolymer (A) in the present invention is not particularly limited, but an anionic polymerization method or a radical polymerization method is preferred, a living anion polymerization method or a living radical polymerization method is more preferred from the viewpoint of polymerization control, and a living anion polymerization method is preferred. Legal is more preferred.

  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, the (meth) acrylic block copolymer (A) having the (meth) acrylic polymer block (a) containing the partial structure represented by the general formula (1) is directly used for efficiency. From the viewpoint of good polymerization, a method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound is preferable. Initiating polymerization of an organolithium compound in the presence of an organoaluminum compound and a Lewis base A method of living anion polymerization as an agent is more preferable.

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- The functional group which remove | excluded the hydrogen atom of these two phenolic hydroxyl groups in the compound which has two phenolic hydroxyl groups, such as a naphthol, is mentioned.
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 and bromine.

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-mentioned 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 and bromine.

  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 Lewis base includes an ether bond and / or a tertiary amine structure in the molecule (—RN (R ′ —) — R ″ —: R, R ′ and R ″ represent a divalent organic group). The compound which has is mentioned.

  Examples of the compound used as the Lewis base and having an ether bond in the molecule 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. Among these, from the viewpoints of suppressing side reactions and availability, acyclic ether having 1 to 2 ether bonds in the molecule is preferable, and diethyl ether or 1,2-dimethoxyethane is more preferable.

  The compound having a tertiary amine structure in the molecule used as the Lewis base includes tertiary polyamine. A 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.

  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 living anionic polymerization is preferably carried out in the presence of an organic solvent from the viewpoint of controlling the temperature of the anionic polymerization and making the system uniform so that the anionic polymerization proceeds smoothly. Organic solvents include hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane from the viewpoints of safety, separability from water in washing the reaction mixture after anionic polymerization, and ease of recovery and reuse; chloroform Halogenated hydrocarbons such as methylene chloride 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 smoothly proceeding anionic polymerization.

  In the living anionic polymerization, other additives may be present in the anionic polymerization reaction system as necessary. 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 perform polymerization of the (meth) acrylic polymer block (a) including the partial structure represented by the general formula (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 it under sufficient stirring conditions so that a polymerization reaction system may become uniform.

  In the above living anionic polymerization, as a method of adding an organolithium compound, organoaluminum compound, Lewis base and monomer to the reaction system, the Lewis base is brought into contact with the organoaluminum compound before contacting with the organolithium compound. It is preferable to add. The organoaluminum compound may be added to the reaction system before the monomer or simultaneously. When the organoaluminum compound is added to the reaction system simultaneously with the monomer, the organoaluminum compound may be added after separately mixing with the monomer.

  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 can be 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. Precursor structures include hydroxyl groups protected by hydroxyl groups and protecting groups (silyloxy groups, acyloxy groups, alkoxy groups, etc.), amino groups protected by isocyanate groups, amino groups and protecting groups, and protected by thiol groups and protecting groups. The thiol group etc. which were made are mentioned.

  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 (carboxylic acid, ester, carbonyl halide, etc.) capable of reacting with a hydroxyl group, thereby reacting with a (meth) acrylic heavy polymer. The combined 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.

  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 capable of reacting with an isocyanate group (such as a hydroxyl group) to produce a (meth) acrylic polymer block (a). Can be formed.

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

  The polymer block containing a thiol group as a precursor structure has a curable functional group (1) and a partial structure capable of reacting with the thiol group (carboxylic acid, carboxylic anhydride, ester, carbonyl halide, isocyanate group, carbon-carbon dioxygen). The polymer block (a) can be formed by reacting with a compound having a heavy bond or the like. In addition, a polymer block containing a thiol group protected by a protecting group as a precursor structure can form a polymer block (a) in the same manner after removing the protecting group to form a thiol group.

  In the production of the (meth) acrylic block copolymer (A), as a method of forming the (meth) acrylic polymer block (a), from the viewpoint that the partial structure (2) can be easily introduced directly, A method of polymerizing a monomer containing meth) acrylate (3), typically a method of living anion polymerization, is preferred.

  The active energy ray-curable composition of the present invention includes a methacrylic polymer (B) having an active energy ray-curable group containing the partial structure (1). The methacrylic polymer (B) is a polymer mainly composed of monomer units formed from methacrylic acid esters. Even if it is a homopolymer, a copolymer composed of a plurality of monomer units (random Copolymer, alternating copolymer, etc.). The methacrylic polymer (B) is distinguished from the (meth) acrylic block copolymer (A) in that it does not have at least the acrylic polymer block (b).

The definition, specific examples, and preferred examples of R ^{1 in} the above general formula (1) showing the partial structure (1) contained in the active energy ray-curable group of the methacrylic polymer (B) are (meth) acrylic blocks. The same as in the case of the (meth) acrylic polymer block (a) contained in the copolymer (A).

  The content of the partial structure (1) in the methacrylic polymer (B) is preferably in the range of 0.2 to 100 mol% with respect to all monomer units forming the methacrylic polymer (B). The range of 90 mol% is more preferable, and the range of 25 to 80 mol% is more preferable.

  The methacrylic polymer (B) includes a monomer unit formed by polymerizing a monomer containing a methacrylic ester.

  As the methacrylic acid ester contained in such a monomer, a monofunctional methacrylic acid ester having one methacryloyl group and a polyfunctional methacrylic acid ester having two or more methacryloyl groups can be used. Examples of such monofunctional methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and isobornyl methacrylate. , Lauryl methacrylate, dodecyl methacrylate, 2-methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, trimethoxysilylpropyl methacrylate, 2-aminoethyl methacrylate, N-methacrylic acid, N-dimethylaminoethyl, N, N-diethylaminoethyl methacrylate, phenyl methacrylate, naphthyl methacrylate, 2- (trimethylsilyloxy) ethyl methacrylate, methacrylate 3- (trimethylsilyloxy) propyl phosphate, glycidyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of methacrylic acid, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, methacrylic acid 2-perfluoroethylethyl acid, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-permethacrylate Fluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, etc. I can get lost. Among these, methacrylic acid alkyl esters having an alkyl group having 5 or less carbon atoms such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate are preferable.

In addition, when a dimethacrylate represented by the following general formula (4) (hereinafter referred to as “dimethacrylate (4)”) is used as a polyfunctional methacrylic acid ester capable of forming a methacrylic polymer (B), conditions described later Under the living anion polymerization, one methacryloyloxy group (in the general formula (4) below, methacryloyloxy group not directly bonded to “C (R ² ) (R ³ )”) is selectively polymerized. The methacrylic polymer (B) having an active energy ray-curable group represented by the general formula (2) is preferably obtained.

（式中、Ｒ²およびＲ³はそれぞれ独立して炭素数１〜６の炭化水素基を表し、ｎは１〜２０の整数を表す）

(Wherein R ² and R ³ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 20)

In the general formula (4) showing the dimethacrylate (4) capable of forming the methacrylic polymer (B), specific examples and preferred examples of R ² and R ³ are the (meth) acrylic polymer block (a) described above. This is the same as in the case of R ² and R ^{3 in} the general formula (3) showing the di (meth) acrylate (3) capable of forming

  Examples of the dimethacrylate (4) include 1,1-dimethylpropane-1,3-diol dimethacrylate, 1,1-dimethylbutane-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, 1,1-diethylhexane-1,6-diol dimethacrylate and the like can be mentioned, and 1,1-dimethylpropane-1,3-diol dimethacrylate, , 1-Dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethyl Pentane-1,5-diol dimethacrylate, and 1,1-dimethyl hexane-1,6-diol dimethacrylate is preferred. These dimethacrylates (4) may be used alone or in combination of two or more.

  Content of the monomer unit formed from the methacrylic acid ester in the methacrylic polymer (B) is in the range of 90 to 100 mol% with respect to all the monomer units forming the methacrylic polymer (B). Is preferable, the range of 95-100 mol% is more preferable, and 100 mol% may be sufficient. When the methacrylic polymer (B) includes a monomer unit formed from dimethacrylate (4), the content of the monomer unit formed from dimethacrylate (4) is methacrylic. The range of 0.2 to 100 mol% is preferable, the range of 10 to 90 mol% is more preferable, and the range of 25 to 80 mol% is more preferable with respect to all monomer units forming the polymer (B). Furthermore, the sum of the content of monomer units formed from methyl methacrylate and the content of monomer units formed from dimethacrylate (4) is the monomer unit formed from all methacrylate esters. The range of 80 to 100 mol% is preferable, the range of 90 to 100 mol% is more preferable, the range of 95 to 100 mol% is more preferable, and 100 mol% may be used.

  The methacrylic polymer (B) may have a monomer unit formed from another monomer other than the methacrylic acid ester. Examples of the other monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, Isobornyl acrylate, lauryl acrylate, dodecyl acrylate, trimethoxysilylpropyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, 2-methoxyethyl acrylate, phenyl acrylate, acrylic Acrylic acid esters such as naphthyl acid, 2- (trimethylsilyloxy) ethyl acrylate, 3- (trimethylsilyloxy) propyl acrylate; α-alkoxy acrylates such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate Crotonic acid esters such as methyl crotonate and ethyl crotonate; 3-alkoxy acrylate esters such as 3-methoxy acrylate; N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide Acrylamide such as N, N-diethylacrylamide; methacrylamide such as N-isopropylmethacrylamide, Nt-butylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide; 2-phenylacrylic acid Methyl, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, methyl 2-bromomethylacrylate, ethyl 2-bromomethylacrylate, methyl vinyl ketone, ethyl vinyl ketone, methyl isopropeni Ketones, such as ethyl isopropenyl ketone. These other monomers may be used alone or in combination of two or more.

  The content of the monomer unit formed from the other monomer in the methacrylic polymer (B) is 10 mol% or less with respect to the total monomer units forming the methacrylic polymer (B). It is preferable that it is 5 mol% or less.

Although there is no restriction | limiting in particular in Mn of a methacrylic polymer (B), From viewpoints of a handleability, fluidity | liquidity, a mechanical characteristic, etc., it is preferable that it is the range of 500-1,000,000, 1,000-300, More preferably, it is in the range of 000.
The molecular weight distribution (Mw / Mn) of the methacrylic polymer (B) is preferably in the range of 1.02 to 2.00, more preferably in the range of 1.05 to 1.80, and in the range of 1.10 to 1.50. Is more preferable.

  The content of the active energy ray-curable group containing the partial structure (1) in the methacrylic polymer (B) is 0.2 to 100 with respect to all monomer units forming the methacrylic polymer (B). The range of mol% is preferable, the range of 10 to 90 mol% is more preferable, and the range of 25 to 80 mol% is more preferable.

  The number of active energy ray-curable groups contained in the methacrylic polymer (B) is preferably 2 or more, more preferably 4 or more, per polymer molecule from the viewpoint of curing speed.

  Since the methacrylic polymer (B) has a structure similar to the methacrylic polymer block (a) of the (meth) acrylic block copolymer (A), compared with a general reactive diluent ( An active energy ray-curable composition having high compatibility with the (meth) acrylic block copolymer (A) and excellent transparency and mechanical properties of the cured product can be obtained.

  The method for producing the methacrylic polymer (B) in the present invention is not particularly limited, but an anionic polymerization method or a radical polymerization method is preferred, a living anion polymerization method or a living radical polymerization method is more preferred from the viewpoint of polymerization control, and a living anion polymerization method is preferred. Legal is more preferred. About the specific example of a living radical polymerization method and a living anion polymer, and a suitable example, the method similar to a (meth) acrylic-type block copolymer (A) is mentioned.

  As a method for producing a methacrylic polymer (B), an active energy ray-curable group represented by the general formula (2) can be easily and directly introduced, and a monomer containing dimethacrylate (4) is used. A preferred method is a polymerization method, typically a living anion polymerization method.

  As a method for introducing the active energy ray-curable group containing the partial structure (1) in the production of the methacrylic polymer (B), in addition to the method for polymerizing the monomer containing the dimethacrylate (4) described above. A method of converting the precursor structure into the partial structure (1) after producing a polymer containing the precursor structure is also included. The definition of the precursor structure, the preferred example, the method for producing the polymer containing the precursor structure, and the method for converting the precursor structure into the partial structure (1) are the same as those described above for the (meth) acrylic block copolymer (A). This is the same as described in the method for introducing the partial structure (1) in the production.

  In the polymerization of the (meth) acrylic block copolymer (A), the methacrylic polymer (B) can be obtained by inactivating the polymerization active terminal at the stage of forming the methacrylic polymer block (a). it can. If a (meth) acrylic block copolymer (A) is produced from a polymerization active terminal that is not deactivated by partially deactivating such polymerization active terminal, a (meth) acrylic block copolymer (A ) And a methacrylic polymer (B), and the active energy ray-curable composition of the present invention can be efficiently produced by controlling the ratio of such deactivation. Examples of the method for deactivating the polymerization active terminal include a method of adding an appropriate amount of a known terminator (alcohol or the like), and a method of stirring for a predetermined time in a state where the monomers in the polymerization system are exhausted.

  In the polymerization of a (meth) acrylic block copolymer containing a precursor structure, after the formation of a methacrylic polymer block containing the precursor structure, the polymerization active terminal is deactivated, and then the precursor structure is partially structured The methacrylic polymer (B) can also be obtained by the method of converting to (1). If a precursor of a (meth) acrylic block copolymer (A) containing a precursor structure is produced from a polymerization active terminal that has not been deactivated by partially deactivating such a polymerization active terminal, (meth) A mixture of the precursor of the acrylic block copolymer (A) and the precursor of the methacrylic polymer (B) can be obtained, and the active energy ray curability of the present invention is controlled by controlling the ratio of such deactivation. A composition can be produced efficiently. As a method for deactivating the polymerization active terminal, the polymerization active terminal is deactivated at the stage of forming the methacrylic polymer block (a) in the polymerization of the (meth) acrylic block copolymer (A). However, this is the same as in the case of obtaining the methacrylic polymer (B).

  Ratio m (A) of the content mass m (A) of the (meth) acrylic polymer (A) and the content mass m (B) of the methacrylic polymer (B) in the active energy ray-curable composition of the present invention. ) / M (B) is not particularly limited, but the viewpoint of the viscosity and curing rate of the active energy ray-curable composition and the flexibility and transparency of the cured product obtained by curing the active energy ray-curable composition. To 99.999 / 0.001 to 60/40, more preferably 99.99 / 0.01 to 65/35, and 99.9 / 0.1 to 70/30. It is more preferable that the ratio is 99/1 to 80/20.

  In the active energy ray-curable composition of the present invention, the Mn (Mn (A)) of the (meth) acrylic block copolymer (A) and the Mn (Mn (B)) of the methacrylic polymer (B). The ratio Mn (A) / Mn (B) is preferably 1.5 or more and 1000 or less, more preferably 1.8 or more and 900 or less, and more preferably 2 or more and 800 or less from the viewpoint of compatibility between the two. More preferably.

The active energy ray-curable composition of the present invention may further contain a photopolymerization initiator. 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 (eg, thioxanthone, 2-chlorothioxanthone, etc.); 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). Among these, acetophenones and benzophenones are preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  When it contains a photopolymerization initiator, the content is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic block copolymer (A) and the methacrylic polymer (B). Is preferable, and 0.05 to 8 parts by mass is more preferable. When the amount is 0.01 parts by mass or more, the curability of the active energy ray-curable composition becomes good, and when the amount is 10 parts by mass or less, the resulting cured product tends to have good heat resistance.

Moreover, the active energy ray-curable composition 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. Among 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.

  In addition, the active energy ray-curable composition of the present invention has reactivity other than the (meth) acrylic block copolymer (A) and the methacrylic polymer (B) that exhibits polymerizability upon irradiation with active energy rays. A diluent may be included. The reactive diluent is not particularly limited as long as it is a compound that exhibits polymerizability upon irradiation with active energy rays. For example, styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert -Styrene derivatives such as butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, divinylbenzene; fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic T-butyl acid, pentyl (meth) acrylate, (meth) a Isoamyl crylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth ) Decyl acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate, Lauryl (meth) acrylate, Stearyl (meth) acrylate, Isostearyl (meth) acrylate, (Meta ) Benzyl acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (Meth) acrylic acid 4-butylcyclohexyl, ( 2) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meta ) Butoxyethyl acrylate, (meth) acrylic acid ethoxydiethylene glycol, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid polyethylene glycol monoester, (meth) acrylic acid polypropylene glycol monoester, (meth) acrylic acid methoxyethylene glycol , Ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic Diethylaminoethyl acid, 7-amino-3,7-dimethyloctyl (meth) acrylate, 4- (meth) acryloylmorpholine, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (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, tris (2-hydroxyethyl) isocyanurate tri (meta) ) Acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, Di (meth) acrylate of diol, which is an adduct of hydrogenated bisphenol A with ethylene oxide or propylene oxide, and (meth) acrylate with diglycidyl ether of bisphenol A Epoxy (meth) acrylate added and (meth) acrylic acid derivatives such as cyclohexanedimethanol di (meth) acrylate; epoxy such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin Acrylate resin; COOH group-modified epoxy acrylate resin; polyol (polytetramethylene glycol, polyester glycol 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 isocyanate (tolylene) Urethane resin obtained from diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) (hydroxy) -containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) Urethane acrylate resin obtained by reacting acrylate, pentaerythritol triacrylate, etc.]; a resin in which a (meth) acryl group is introduced through an ester bond to the polyol; a polyester (meth) acrylate resin; Examples include soybean oil and epoxy compounds such as epoxy benzyl stearate. 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 composition of the present invention, the content is determined by the flowability of the active energy ray-curable composition and the active energy ray-curable composition. From the viewpoint of increasing the mechanical strength of the cured product obtained by irradiation, 10 to 90% by mass is preferable, and 20 to 80% by mass is more preferable.

  The active energy ray-curable composition of the present invention has an active energy ray-curable property such as a plasticizer, a tackifier, a softener, a filler, a stabilizer, a pigment, and a dye as long as the curability is not significantly inhibited. Various additives having no group may be contained.

  The purpose of including the plasticizer in the active energy ray-curable composition of the present invention is, for example, the adjustment of the viscosity of the active energy ray-curable composition, or the cured product obtained by curing the active energy ray-curable composition. It is adjustment of mechanical strength. 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.

  When the plasticizer is contained in the active energy ray-curable composition of the present invention, the content thereof is (meth) acrylic triblock copolymer (A) and (meth) acrylic diblock copolymer (B). 5-150 mass parts is preferable with respect to the total amount of 100 mass parts, 10-120 mass parts is more preferable, and 20-100 mass parts is further more preferable. By adjusting the amount to 5 parts by mass or more, effects such as physical property adjustment and property adjustment become remarkable, and by setting the amount to 150 parts by mass or less, a cured product obtained by curing the active energy ray-curable composition tends to have excellent mechanical strength. .

  The molecular weight or Mn (number average molecular weight) of these plasticizers is preferably 400 to 15,000, more preferably 800 to 10,000, and more preferably 1,000 to 8,000. 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 cured product of the active energy ray-curable composition with time, and 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 composition tends to be improved.

  The purpose of including the tackifier in the active energy ray-curable composition of the present invention is to impart tackiness to a cured product obtained from the active energy ray-curable composition, for example. Examples of the tackifier include coumarone / indene resin, phenol resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin (terpene resin, etc.) , Styrene resins (polystyrene, poly-α-methylstyrene, etc.), polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, esters of hydrogenated rosin and monoalcohol or polyhydric alcohol, terpine tackifying resin And the like. Among these, aliphatic hydrocarbon resins (terpene resins and the like), polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, esters of hydrogenated rosin and monoalcohol or polyhydric alcohol are preferable.

  The additive having no active energy ray-curable group may be an organic compound or an inorganic compound.

  The active energy ray used when the active energy ray-curable composition is cured can be irradiated using a known apparatus. In the case of an electron beam (EB), an acceleration voltage of 0.1 to 10 MeV and an irradiation dose of 1 to 500 kGy are appropriate.

For the ultraviolet irradiation, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED, or the like that emits light having a wavelength range of 150 to 450 nm can be used. Integrated light quantity of active energy rays, usually in the range of 10~20000mJ / cm ^2, the range of 30~5000mJ / cm ² is preferred. When the amount is less than 10 mJ / cm ^{2, the} curability of the active energy ray-curable composition tends to be insufficient, and when it exceeds 20000 mJ / cm ² , the active energy ray-curable composition may be deteriorated.

  From the viewpoint of suppressing the decomposition of the active energy ray-curable composition, the relative humidity when irradiating the active energy ray-curable composition with the active energy ray is preferably 30% or less, and 10% or less. More preferably.

  The active energy ray-curable composition may be further heated as necessary during or after irradiation with the active energy ray 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.

  The active energy ray-curable composition is applied to a base material such as an adhesive or a coating material, and then cured. From this point of view, it can be easily separated and separated by suitably applying the wet pyrolysis method.

The wet heat decomposition temperature is preferably 100 to 250 ° C, more preferably 130 to 220 ° C.
In addition, 10-100% is preferable and the wet heat decomposition relative humidity is more preferably 30-100%. The wet heat decomposition time is preferably 1 minute to 24 hours, more preferably 1 minute to 5 hours, and further preferably 1 minute to 2 hours.

  Applications of the active energy ray-curable composition of the present invention include curable resins and adhesives used in fields such as automobiles, home appliances, architecture, civil engineering, sports, displays, optical recording equipment, optical equipment, semiconductors, batteries, and printing. Adhesives, tapes, films, sheets, mats, sealing materials, sealing materials, coating materials, potting materials, inks, printing plate materials, anti-vibration materials, foams, heat dissipation materials, prepregs, gaskets, packing, etc. .

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more 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]
The consumption rate of each monomer after polymerization was calculated by the following method. That is, 0.5 ml of a polymerization reaction solution collected from the polymerization system was put into 0.5 ml of methanol to prepare 1.0 ml of a mixed solution, and 0.1 ml of the obtained mixed solution was dissolved in 0.5 ml of deuterated chloroform. ¹ H-NMR measurement was performed, and a peak (chemical shift value: 6.08 to 6.10) derived from a proton directly connected to a carbon-carbon double bond of (meth) acrylic acid ester used as a monomer and a solvent It calculated from the change of the ratio of the integral value of the peak (chemical shift value 7.00-7.38 ppm) derived from the proton directly connected to the aromatic ring of toluene used.
¹ H-NMR measurement condition apparatus: JEOL Ltd. nuclear magnetic resonance apparatus “JNM-ECX400”
Solvent: Deuterated chloroform Temperature: 25 ° C

[Number average molecular weight (Mn), molecular weight distribution (Mw / Mn)]
The obtained polymer was subjected to GPC (gel permeation chromatography) measurement, and the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) in terms of standard polystyrene were determined.
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 (used by connecting two in series)
Eluent: Tetrahydrofuran eluent Flow rate: 0.35 ml / min Column temperature: 40 ° C
Detection method: differential refractive index (RI)

[Initiation efficiency of polymerization]
When Mn of the polymer obtained in the following step (1) is Mn (R1) and the polymerization initiation efficiency is 100%, the Mn (calculated value) of the polymer obtained in step (1) is Mn (I1). Then, the polymerization initiation efficiency (F1) in the step (1) is calculated from the following equation.
F1 (%) = 100 × Mn (I1) / Mn (R1)

[Block efficiency from step (1) to step (2)]
The block copolymer obtained in step (2) when Mn of the diblock copolymer obtained in the following step (2) is Mn (R2) and the block efficiency from step 1 to step 2 is 100%. Assuming that Mn (calculated value) is 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)}]

[Reference 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-hexamethyltriethylenetetramine 7 as a Lewis base was added while stirring the flask. .4 ml (27.3 mmol), 63.6 ml (28.6 mmol) of 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the organoaluminum compound was added sequentially. Then, it cooled to -20 degreeC. To this was added 20.0 ml (26.0 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 17.0 ml (78.0 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate as a monomer. And 33.6 ml of a mixture of 16.6 ml (156 mmol) of methyl methacrylate was added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization 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 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate in step (1) was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 1,300, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) in the step (1) was 98%.

(Process (2))
Subsequently, while stirring the reaction solution at −20 ° C., 31.8 ml of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as an organoaluminum compound (14. 3 mmol), and 1 minute later, 504 ml (3.5 mol) of n-butyl acrylate was added as a monomer at a rate of 10 ml / min. The reaction solution was sampled immediately after 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 (diblock copolymer) was 21,300, and Mw / Mn was 1.18. Furthermore, the block efficiency (F2) from the step (1) to the step (2) was 100%.

(Process (3))
Subsequently, while stirring the reaction solution at −20 ° C., 29.2 ml of a mixture of 14.8 ml (67.8 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate and 14.4 ml (136 mmol) of methyl methacrylate was used as a monomer. After the addition, the temperature was raised to 20 ° C. at a rate of 2 ° C./min. The reaction solution was sampled 60 minutes after the addition of the monomer.
The consumption rate of 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate in step (3) was 100%. Moreover, Mn of the obtained polymer (triblock copolymer) was 22,800, and Mw / Mn was 1.17.

(Process (4))
Subsequently, 100 ml of methanol was added while stirring the obtained reaction liquid at 20 ° C. to stop anionic polymerization.

(Process (5))
Next, 22 ml (267 mmol) of dichloroacetic acid was added to the obtained reaction solution, and the mixture was stirred at room temperature for 30 minutes. Subsequently, the obtained solution was poured into 10 L of methanol, and the produced polymer was precipitated, recovered by filtration, and dried at 100 ° C. and 30 Pa to recover 467 g of the polymer.

(Process (6))
Furthermore, 1.5 L of the obtained polymer and toluene were added and dissolved in a 3 L flask, and 97 ml (696 mmol) of triethylamine was added, followed by cooling with an ice water bath. To this, 67 ml (692 mmol) of methacryloyl chloride was added dropwise and stirred for 2 hours. When sampled and subjected to ¹ H-NMR measurement, the reaction rate was 95%. Thereafter, 50 ml of methanol was added to stop the reaction.

In order to remove the amine salt precipitated from the solution after the reaction, suction filtration was performed, and then toluene was distilled off from the filtrate. After adding 1.5 L of chloroform, washing was performed with an aqueous sodium hydrogen carbonate solution, and the chloroform layer was removed. Suction filtered. Next, the chloroform layer was washed 3 times with a saturated saline solution, and magnesium sulfate was added to the chloroform layer to remove water. At 70 ° C., chloroform, triethylamine and methacrylic acid were distilled off, and 415 g of the desired (meth) acrylic type was obtained. A block copolymer (A) (hereinafter referred to as “(meth) acrylic block copolymer (A1)”) was obtained.
Mn of the obtained (meth) acrylic block copolymer (A1) was 23,100, and Mw / Mn was 1.19.

[Reference Example 2]
(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. 7.4 ml (27.3 mmol) of tetramine and 63.6 ml (28.6 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 20.0 ml (26.0 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 18.7 ml of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. (78 mmol) and 35.3 ml of a mixture of 16.6 ml (156 mmol) of methyl methacrylate were added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization 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 polymer obtained at the process (1) was 1,340, and Mw / Mn was 1.16. Furthermore, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Process (2))
Subsequently, while stirring the reaction solution at −20 ° C., 31.8 ml of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as an organoaluminum compound (14. 3 mmol), and 1 minute later, 504 ml (3.5 mol) of n-butyl acrylate was added as a monomer at a rate of 10 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 (diblock copolymer) was 21,300, and Mw / Mn was 1.18. Furthermore, the block efficiency (F2) from the step (1) to the step (2) was 100%.

(Process (3))
Subsequently, while stirring the reaction solution at −20 ° C., a mixture of 16.3 ml (67.8 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as the monomer and 14.4 ml (136 mmol) of methyl methacrylate. After 30.7 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 60 minutes after the addition of the monomer.
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 the anionic polymerization. The obtained solution was poured into 10 L of methanol, and the produced polymer was precipitated, collected by filtration, dried at 100 ° C. and 30 Pa, and 471 g of the desired (meth) acrylic block copolymer (A) ( Hereinafter, “(meth) acrylic block copolymer (A2)”) was obtained.
Mn of the obtained (meth) acrylic block copolymer (A2) was 22,600, and Mw / Mn was 1.19.

[Reference Example 3]
(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. 3.7 ml (13.7 mmol) of tetramine, 36.1 ml (16.2 mmol) of 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 10.0 ml (13 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as the organic lithium compound, and 18.7 ml (78 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as the monomer. And 22.8 ml of a mixture of 4.1 ml (39 mmol) of methyl methacrylate were added all at once to initiate anionic polymerization. After 280 minutes from the end of the monomer addition, the polymerization 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 polymer obtained at the process (1) was 1,780, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) in the step (1) was 98%.

(Process (2))
Subsequently, the reaction solution was stirred at −20 ° C., and 15.9 ml (7. 7) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as the organoaluminum compound. 2 mmol), and 1 minute later, 501 ml (3.48 mol) of n-butyl acrylate was added as a monomer at a rate of 5 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 (diblock copolymer) was 44,600, and Mw / Mn was 1.18. Furthermore, the block efficiency (F2) from the step (1) to the step (2) was 100%.

(Process (3))
Subsequently, while stirring the reaction solution at −20 ° C., 16.1 ml (67.1 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and 3.6 ml (33.6 mmol) of methyl methacrylate were used. After 19.7 ml of the mixture was added all at once, the temperature was raised to 10 ° C. at a rate of 2 ° C./min. The reaction solution was sampled 300 minutes after the addition of the monomer.
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, and the produced polymer was precipitated, recovered by filtration, dried at 100 ° C. and 30 Pa, and 487 g of the desired (meth) acrylic block copolymer (A) ( Hereinafter, “(meth) acrylic block copolymer (A3)”) was obtained.
Mn of the obtained (meth) acrylic block copolymer (A3) was 46,300, and Mw / Mn was 1.23.

[Reference Example 4]
(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. 7.4 ml (27.3 mmol) of tetramine, 63.6 ml (28.6 mmol) of a 4.50 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 20.0 ml (26.0 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as the organolithium compound, and 17.0 ml (78.0 mmol) of 2- (trimethylsilyloxy) ethyl methacrylate as the monomer. And 33.6 ml of a mixture of 16.6 ml (156 mmol) of methyl methacrylate was added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization reaction solution changed from the original yellow color to colorless. After stirring for another 20 minutes, anionic polymerization was stopped by adding 100.0 ml of methanol.

  The consumption rate of 2- (trimethylsilyloxy) ethyl methacrylate and methyl methacrylate was 100%. Moreover, Mn of the obtained polymer was 1,340 and Mw / Mn was 1.16. Furthermore, the polymerization initiation efficiency (F1) calculated in the same manner as in Step (1) of Reference Example 1 was 99%.

(Process (2))
To the resulting reaction solution, 22 ml (267 mmol) of dichloroacetic acid was added and stirred at room temperature for 30 minutes. Subsequently, the obtained solution was poured into 10 L of methanol, and the produced polymer was precipitated, recovered by filtration, and dried at 100 ° C. and 30 Pa to recover 29 g of the polymer.

(Process (3))
Further, the obtained copolymer and 1.5 L of toluene were added and dissolved in a 3 L flask, 97 ml (696 mmol) of triethylamine was added, and the mixture was cooled in an ice water bath. To this, 67 ml (692 mmol) of methacryloyl chloride was added dropwise and stirred for 2 hours. When the reaction solution was sampled and ¹ H-NMR measurement was performed, the reaction rate was 98%.
Thereafter, 50 ml of methanol was added to stop the reaction.

In order to remove the amine salt precipitated from the solution after the reaction, suction filtration was performed, and then toluene was distilled off from the filtrate. After adding 1.5 L of chloroform, washing was performed with an aqueous sodium hydrogen carbonate solution, and the chloroform layer was removed. Suction filtered. Next, the chloroform layer was washed three times with saturated saline, magnesium sulfate was added to the chloroform layer to remove water, chloroform, triethylamine and methacrylic acid were distilled off at 70 ° C., and 26 g of the desired methacrylic polymer ( B) (hereinafter referred to as “methacrylic polymer (B1)”) was obtained.
Mn of the obtained methacrylic polymer (B1) was 1490, and Mw / Mn was 1.17.

[Reference Example 5]
Anionic polymerization was carried out in the same manner as in step (1) of Reference Example 2, and 100 minutes after the completion of the addition of the monomer, 100 ml of methanol was added to stop the anionic polymerization. The obtained solution was poured into 10 L of methanol, the produced polymer was precipitated, recovered by filtration, dried at 100 ° C. and 30 Pa, and 33 g of the desired methacrylic polymer (B) (hereinafter “methacrylic heavy”). Combined (B2) ”) was obtained.

  The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate was 100%. Moreover, Mn of the obtained methacrylic polymer (B2) was 1,380, and Mw / Mn was 1.18. Furthermore, the polymerization initiation efficiency (F1) calculated in the same manner as in Step (1) of Reference Example 2 was 99%.

[Reference Example 6]
Anionic polymerization was carried out in the same manner as in step (1) of Reference Example 3, and anionic polymerization was stopped by adding 100 ml of methanol 300 minutes after the completion of addition of the monomer. The obtained solution was poured into 10 liters of methanol, and the produced polymer was precipitated, collected by filtration, dried at 100 ° C. and 30 Pa, and 21 g of the desired methacrylic polymer (B) (hereinafter “methacrylic”). Polymer (B3) ") was obtained.

  The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate was 100%. Moreover, Mn of the obtained methacrylic polymer (B3) was 1,790, and Mw / Mn was 1.15. Further, the polymerization initiation efficiency (F1) calculated in the same manner as in Step (1) of Reference Example 3 was 98%.

[Reference Example 7]
(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. 7.4 ml (27.3 mmol) of tetramine and 63.6 ml (28.6 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 20 ml (26.0 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 18.7 ml (78 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. ) And 16.3 ml (156 mmol) of a mixture of methyl methacrylate were added all at once to initiate anionic polymerization. After 80 minutes from the end of the monomer addition, the polymerization 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 polymer obtained at the process (1) was 1,360, and Mw / Mn was 1.15. Furthermore, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Process (2))
Subsequently, after the reaction solution was stirred at −20 ° C. for 200 minutes, 31.8 ml of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as an organoaluminum compound ( 14.3 mmol), and 1 minute later, 504 ml (3.5 mol) of n-butyl acrylate was added as a monomer at a rate of 10 ml / min. Immediately after the addition of n-butyl acrylate, the reaction solution in step (2) was sampled.
The consumption rate of n-butyl acrylate in the step (2) was 100%. Moreover, Mn (Mn (R2)) of the obtained polymer was 21,300 and Mw / Mn was 1.18. Furthermore, the block efficiency (F2) from the step (1) to the step (2) was 55%.

(Process (3))
Subsequently, while the reaction solution was stirred at −20 ° C., a mixture of 16.3 ml (67.8 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and 14.4 ml (136 mmol) of methyl methacrylate was used. After 30.7 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 60 minutes after the addition of the monomer.
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 produced polymer was precipitated, recovered by filtration, dried at 100 ° C. and 30 Pa, and 492 g of the desired polymer composition (hereinafter “polymer composition (C1 ) ”).
Mn of the obtained polymer composition (C1) was 23,800, and Mw / Mn was 1.52.

  Moreover, about the composition which mixed the (meth) acrylic block copolymer (A2) and the methacrylic polymer (B2) in a specific ratio, GPC (gel permeation chromatography, HLC-8220 GPC (manufactured by Tosoh Corp.), column) : TSK-gel SuperMultipore HZ-M (manufactured by Tosoh Corporation) (column diameter = 4.6 mm, column length = 15 cm), measurement conditions: flow rate = 0.35 ml / min, temperature = 40 ° C., eluent = tetrahydrofuran) A calibration curve showing the relationship between the mixing ratio (mass ratio) of the (meth) acrylic block copolymer (A2) and the methacrylic polymer (B2) and the peak area ratio of GPC was prepared, and the obtained polymer composition The (meth) acrylic block copolymer (C1) in the polymer composition (C1) from the area ratio obtained by GPC measurement of the product (C1) When the ratio of the content mass m (A) of A) to the content mass m (B) of the methacrylic polymer (B) was determined, m (A) / m (B) = 96.4 / 3.6. there were.

Example 1
95 parts by mass of the (meth) acrylic block copolymer (A1) obtained in Reference Example 1 as the (meth) acrylic block copolymer (A), and obtained in Reference Example 4 as the methacrylic polymer (B). 100 parts by mass of a polymer component consisting of 5 parts by mass of the resulting methacrylic polymer (B1), 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and 100 parts by mass of toluene as a solvent were mixed to obtain a solution. Produced. After removing most of the toluene from the obtained solution at 20 ° C. and normal pressure, the toluene was further completely removed at 70 ° C. and 30 Pa under reduced pressure to obtain an active energy ray-curable composition. The curing rate of the obtained active energy ray-curable composition, the transparency of the cured product, and the elastic modulus were evaluated by the following methods. The evaluation results are shown in Table 1.

[Curing speed]
The curing rate of the active energy ray-curable composition was evaluated using MARS III manufactured by HAAKE. A high-speed OSC time-dependent measurement mode is used as a measurement mode. An active energy ray-curable composition is applied on a φ20 mm parallel plate at a thickness of 50 μm, a measurement temperature is 25 ° C., a measurement gap is 0.15 mm, and a measurement frequency is 5 Hz. Under the conditions, viscoelasticity measurement was performed while irradiating a UV lamp (Omni Cure series 2000, irradiation intensity 150 mW / cm ² , manufactured by Lumen Dynamics), and the storage shear modulus (G ′) and loss shear modulus (G ″) were The time for crossover was measured and used as an index of curing speed.

[transparency]
Transparency of the cured product of the active energy ray-curable composition is determined by setting a 1 mm thick spacer along the four sides of the release PET film (K1504, manufactured by Toyobo) and curing the active energy ray on the release PET film. After pouring the adhesive composition and placing the release PET film on the release PET film so as not to contain air bubbles, an ultraviolet irradiation device HTE-3000B INTEGRATOR 814M (manufactured by HI-TECH) is used on one of the release PET films. The film was prepared by curing the active energy ray-curable composition by irradiating ultraviolet rays at 5000 mJ / cm ² , and visually evaluated according to the following indices.
○: Good △: Slightly inferior ×: Inferior

[Flexibility] Elasticity of cured product The flexibility of the cured product of the active energy ray-curable composition was determined by using a dynamic viscoelasticity measuring device (“Rheogel E-4000 manufactured by UBM Co., Ltd.). )) In a temperature-dependent (tensile) mode (frequency: 11 Hz), the temperature increase rate was 3 ° C./min, the temperature was increased from −100 ° C. to 180 ° C., the storage elastic modulus was measured, and 25 ° C. The storage elastic modulus E ′ (Pa) in was used as an index of flexibility.

(Examples 2 to 4)
Example except that the type and amount of the (meth) acrylic block copolymer (A) and the type and amount of the (meth) acrylic block copolymer (B) are changed as shown in Table 1. The active energy ray-curable composition was prepared in the same manner as in Example 1, and the curing rate, the transparency of the cured product, and the elastic modulus were evaluated. The evaluation results are shown in Table 1.

(Example 5)
An active energy ray-curable composition is prepared in the same manner as in Example 1 except that 100 parts by mass of the polymer component is changed to 100 parts by mass of the polymer composition (C1), and the curing speed, transparency of the cured product, and elasticity are obtained. Rate was evaluated. The evaluation results are shown in Table 1.

(Comparative Examples 1-3)
An active energy ray-curable composition was prepared in the same manner as in Example 1 except that the polymer component was changed to the (meth) acrylic block copolymer (A) shown in Table 2, and the curing rate and cured product were obtained. The transparency and elastic modulus were evaluated. The evaluation results are shown in Table 2.

As shown in Table 1, it can be seen that the active energy ray-curable compositions of the present invention obtained in the Examples are all cured to obtain a cured product having excellent transparency and flexibility.
Further, as shown in Table 1 and Table 2, when Example 1 and Comparative Example 1, Examples 2 and 3 were compared with Comparative Example 2, and Example 4 and Comparative Example 3 were respectively compared, It can be seen that the active energy ray-curable composition of the invention has a faster curing rate than the active energy ray-curable composition not containing the methacrylic polymer (B).

Claims (3)

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 an acrylic polymer block (b) having no active energy ray-curable group (Meth) acrylic block copolymer (A) consisting of
An active energy ray-curable composition containing a methacrylic polymer (B) having an active energy ray-curable group containing a partial structure represented by the following general formula (1).

(Wherein R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms)   The active energy ray-curable composition according to claim 1, further comprising a photopolymerization initiator. The active energy ray-curable group of the (meth) acrylic block copolymer (A) and the methacrylic polymer (B) includes a partial structure represented by the following general formula (2). The active energy ray-curable composition described.

(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 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)