JP2016204610A - (meth)acrylic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a (meth)acrylic polymer composition with an excellent cure rate.SOLUTION: A (meth)acrylic polymer composition comprises: a (meth)acrylic polymer (A) having two or more active energy ray-curable groups in side chains; and a phosphorus-based compound (B) having two partial structures represented by the general formula (1) in the figure, where Rrepresents a C3-20 hydrocarbon group.SELECTED DRAWING: None

Description

  The present invention relates to a (meth) acrylic polymer composition having an improved curing rate when irradiated with active energy rays.

  Active energy ray-curable materials 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 agents, and optical modeling materials. ing.

Especially, the (meth) acrylic-type polymer which has an active energy ray hardening group can anticipate the usefulness to an optical use, and examination is advanced (refer patent document 1 and patent document 2).
These active energy ray-curable materials are required to increase the curing rate from the viewpoint of improving productivity.

International Publication No. 2013/141105 International Publication No. 2014/148251

  An object of this invention is to provide the (meth) acrylic-type polymer composition which is excellent in the cure rate at the time of irradiating an active energy ray.

  As a result of intensive studies to achieve the above-described object, the present inventors have added a specific phosphorus compound to a (meth) acrylic polymer having two or more active energy ray-curable groups in the side chain. It has been found that the curing rate is improved.

That is, the present invention
[1] A (meth) acrylic polymer (A) having two or more active energy ray-curable groups in the side chain, and a phosphorus compound (B) having two partial structures represented by the following general formula (1) (Meth) acrylic polymer composition comprising:
[2] The (meth) acrylic polymer according to the above [1], wherein the content of the phosphorus compound (B) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A). And [3] the (meth) acrylic polymer composition of [1] or [2] above, wherein R ^a in the general formula (1) represents an alkyl group having 3 to 20 carbon atoms. To do.

（式中、Ｒ^aは炭素数３〜２０の炭化水素基を表す）

(Wherein, R ^a represents a hydrocarbon group having 3 to 20 carbon atoms)

The (meth) acrylic polymer composition of the present invention is excellent in the curing rate when irradiated with active energy rays.
Such an effect is obtained when the phosphorus compound (B) dispersed in the vicinity of the active energy ray-curable group of the (meth) acrylic polymer (A) quickly traps the radicals generated by the photopolymerization initiator, It is presumed to be expressed by efficiently propagating to the energy ray curable group.

Hereinafter, the present invention will be described in detail.
The (meth) acrylic polymer composition of the present invention includes a (meth) acrylic polymer (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 polymer (A) contains an active energy ray-curable group as a side chain. Such an active energy ray-curable group exhibits polymerizability upon irradiation with an active energy ray. As a result, the (meth) acrylic polymer composition of the present invention is cured by irradiation with active energy rays.

  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 viewpoint of curing speed, availability of an irradiation apparatus, price, and the like.

The (meth) acrylic polymer (A) has two or more active energy ray-curable groups in the side chain. In the present specification, the active energy ray-curable group means a functional group that exhibits polymerizability upon irradiation with the active energy ray, for example, a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, an allyl group. , Vinyloxy groups, 1,3-dienyl groups, styryl groups, etc. (especially ethylenic double bonds represented by the general formula CH ₂ ═CR— (wherein R is an alkyl group or a hydrogen atom)) And a functional group having an epoxy group, such as an epoxy group, an oxetanyl group, a thiol group, and a maleimide group.

  The active energy ray-curable group is preferably an active energy ray-curable group containing a partial structure represented by the following general formula (2) (hereinafter referred to as “partial structure (2)”).

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表す）

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

In the general formula (2), 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.

  From the viewpoint of curing speed, the active energy ray-curable group containing the partial structure (2) in the (meth) acrylic polymer (A) is preferably represented by the following general formula (3). Hereinafter, the active energy ray-curable group represented by the following general formula (3) is referred to as “active energy ray-curable group (3)”.

（式中、Ｒ¹は水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ²およびＲ³はそれぞれ独立して水素原子または炭素数１〜６の炭化水素基を表し、ＸはＯ、Ｓ、またはＮ（Ｒ⁶）（Ｒ⁶は水素原子または炭素数１〜６の炭化水素基を表す）を表し、ｎは１〜２０の整数を表す）
一般式（３）中、Ｒ¹が表す炭素数１〜２０の炭化水素基の具体例および好適例としては、上記一般式（２）のＲ¹と同様の炭化水素基が挙げられる。

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and X represents O , S, or N (R ⁶ ) (R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and n represents an integer of 1 to 20)
Specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ in general formula (3) include the same hydrocarbon groups as R ^{1 in} general formula (2).

In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a monomer containing di (meth) acrylate (4) described later. From the viewpoint that it can be easily and directly introduced, a hydrocarbon group having 1 to 6 carbon atoms is preferred. Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and a 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 And alkyl groups such as 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; phenyl group and the like. Among these, from the viewpoint of curing speed, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

In the general formula (3), 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; phenyl group and the like.

In the general formula (3), the integer of 1 to 20 represented by n is preferably 2 to 5 from the viewpoint of the coating property and the curing rate of the (meth) acrylic polymer composition of the present invention.
In the (meth) acrylic polymer (A), the number of the active energy ray-curable groups is 2 or more, and is preferably 4 or more, and more preferably 8 or more from the viewpoint of the curing rate. More preferred.

  The content of the active energy ray-curable group in the (meth) acrylic polymer (A) is 0.1 to 20 with respect to all monomer units forming the (meth) acrylic polymer (A). The range is preferably in the range of mol%, more preferably in the range of 2 to 15 mol%, and still more preferably in the range of 3 to 10 mol%.

  The (meth) acrylic polymer (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 (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) Isopropyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic Dodecyl acid, trimethoxysilylpropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth ) Phenyl acrylate, (meth) acrylate naphthyl, (meth) acrylate 2- (trimethyl) Silyloxy) ethyl, and a mono (meth) acrylic acid esters such as (meth) acrylic acid 3- (trimethylsilyloxy) propyl.

  Above all, from the viewpoint of availability and the resulting (meth) acrylic polymer composition having excellent low hygroscopicity, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate And alkyl methacrylates having an alkyl group having 5 or less carbon atoms, such as t-butyl methacrylate, are preferred, and methyl methacrylate is most preferred. Moreover, the viewpoint which makes the (meth) acrylic-type polymer composition obtained more excellent in low moisture absorption, the softness | flexibility of the hardened | cured material obtained from this (meth) acrylic-type polymer composition, and adhesion | attachment with a base material From the viewpoint of safety, acrylic acid alkyl ester or alkyl 2-ethylhexyl methacrylate having an alkyl group having 4 or more carbon atoms such as n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc., methacrylic acid A methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms such as dodecyl is preferred. In addition, these monofunctional (meth) acrylic acid ester may be used individually by 1 type, or may use 2 or more types together.

Moreover, as polyfunctional (meth) acrylic acid ester which can form (meth) acrylic-type polymer (A), bifunctional (meth) acrylic acid ester (henceforth "di (meth)" shown by following General formula (4) is shown. (Referred to as “acrylate (4)”), by living anion polymerization under the conditions described later, one (meth) acryloyloxy group (“CH ₂ ═C (R ⁵ ) C” in the following general formula (4) (O) O "(meth) acryloyloxy group) is selectively polymerized, R ¹ is R ⁴ , R ² is R ^{2 '} , R ³ is R ^3' , X A (meth) acrylic polymer (A) having an active energy ray-curable group (3) in which is O is obtained.

（式中、Ｒ^2'およびＲ^3'はそれぞれ独立して炭素数１〜６の炭化水素基を表し、Ｒ⁴およびＲ⁵はそれぞれ独立して水素原子またはメチル基を表し、ｎは１〜２０の整数を表す）
一般式（４）中、Ｒ^2'およびＲ^3'が表す炭素数１〜６の炭化水素基の例としては上記一般式（４）のＲ²およびＲ³と同様の炭化水素基が挙げられる。

(Wherein R ^{2 ′} and R ^{3 ′} each independently represent a hydrocarbon group having 1 to 6 carbon atoms, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and n represents 1 to 1) Represents an integer of 20)
In the general formula (4), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ^{2 ′} and R ^{3 ′} include the same hydrocarbon groups as R ² and R ^{3 in} the general formula (4). .

From the viewpoint of increasing the selectivity of polymerization, R ⁴ is preferably a methyl group. From the viewpoint of productivity of di (meth) acrylate (4), 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 (4) 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 polyfunctional (meth) acrylic acid esters may be used alone or in combination of two or more.

  In the (meth) acrylic polymer (A), the content of the monomer unit formed from the methacrylic acid ester is preferably 2 to 100% by mass, more preferably 3 to 98% by mass. The content is more preferably 5 to 85% by mass, particularly preferably 7 to 80% by mass, and most preferably 10 to 75% by mass. In the (meth) acrylic polymer (A), the content of the monomer unit formed from the acrylate ester is preferably 0 to 98% by mass, and preferably 2 to 97% by mass. More preferably, it is more preferably 15 to 95% by mass, particularly preferably 20 to 93% by mass, and most preferably 25 to 90% by mass.

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

  The content of the monomer units formed from the other monomers in the (meth) acrylic polymer (A) is the total monomer units forming the (meth) acrylic polymer (A). On the other hand, it is preferably 10 mol% or less, and more preferably 5 mol% or less.

  The Mn of the (meth) acrylic polymer (A) is not particularly limited, but is preferably in the range of 4,000 to 3,000,000, and preferably 7,000 to 2 from the viewpoints of handleability, fluidity, mechanical properties, and the like. A range of 1,000,000 is more preferred.

The molecular weight distribution of the (meth) acrylic polymer (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, and in the range of 1.05 to 1.80. A range of 1.10 to 1.50 is more preferable.
In addition, in this specification, Mn and molecular weight distribution mean the standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

  As said (meth) acrylic-type polymer (A), (meth) acrylic-type polymer block (a) which has an active energy ray-curable group in a side chain, and no active energy ray-curable group (meth) A (meth) acrylic block copolymer having an acrylic polymer block (b) is a preferred embodiment. As the (meth) acrylic block copolymer, specifically, the (meth) acrylic polymer block (a) having an active energy ray-curable group containing the partial structure (2) in the side chain and the active A (meth) acrylic block copolymer (A1) having a (meth) acrylic polymer block (b) having no energy ray curable group is mentioned.

  The content of the partial structure (2) in the (meth) acrylic polymer block (a) is 0.2 to 100 mol based on 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 (2) contained in one (meth) acrylic polymer block (a) is preferably 2 or more, and more 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.

  Specific examples of the monofunctional (meth) acrylic acid ester that can form the (meth) acrylic polymer block (a) are the same as the monofunctional (meth) acrylic acid ester that can form the (meth) acrylic polymer (A). It is. From the viewpoint of availability and the resulting (meth) acrylic polymer composition having excellent low hygroscopicity, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid A methacrylic acid alkyl ester having an alkyl group having 5 or less carbon atoms such as t-butyl acid is preferred, and methyl methacrylate is most preferred.

Moreover, when the said di (meth) acrylate (4) is used as polyfunctional (meth) acrylic acid ester which can form a (meth) acrylic-type polymer block (a), it is by living anion polymerization on the conditions mentioned later. , One (meth) acryloyloxy group (a (meth) acryloyloxy group represented by “CH ₂ ═C (R ⁵ ) C (O) O” in the general formula (4)) is selectively polymerized, A (meth) acrylic polymer block having an active energy ray-curable group (3) in which R ¹ is R ⁴ , R ² is R ^{2 ′} , R ³ is R ^{3 ′} , and X is O (A) is obtained.

  Specific examples and preferred examples of the di (meth) acrylate (4) capable of forming the (meth) acrylic polymer block (a) include di (meth) acrylate (4) capable of forming the (meth) acrylic polymer (A). ). Di (meth) acrylate (4) may be used individually by 1 type, or may use 2 or more types together.

  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. Further, when the (meth) acrylic polymer block (a) contains a monomer unit formed from di (meth) acrylate (4), a single unit formed from di (meth) acrylate (4) 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. Further, when the (meth) acrylic polymer block (a) includes a monomer unit formed from methyl methacrylate and a monomer unit formed from di (meth) acrylate (4), this is required. The total content of monomer units formed from methyl methacrylate and monomer units formed from di (meth) acrylate (4) is the total monomer units formed from (meth) acrylate 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 the range may be 100 mol%.

  The (meth) acrylic polymer block (a) may have a monomer unit formed from a monomer other than the (meth) acrylic acid ester. The specific example of this other monomer is the same as that of other monomers other than the (meth) acrylic acid ester which can form a (meth) acrylic-type polymer (A). 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 Mn per one (meth) acrylic polymer block (a) is not particularly limited, but from the viewpoint of the handleability, fluidity and mechanical properties of the (meth) acrylic block copolymer (A1), 500 to The range of 1,000,000 is preferable, and the range of 1,000 to 300,000 is more preferable.

The (meth) acrylic block copolymer (A1) contains a (meth) acrylic polymer block (b) having no active energy ray-curable group.
The (meth) acrylic polymer block (b) is composed of monomer units formed by polymerizing a monomer containing a (meth) acrylic acid ester, and has the above-described active energy ray-curable group. It is a polymer block that does not have.

  Specific examples of the (meth) acrylic acid ester are the same as those of the monofunctional (meth) acrylic acid ester that can form the (meth) acrylic polymer (A). Among these, from the viewpoint of making the obtained (meth) acrylic polymer composition more excellent in low moisture absorption, flexibility of the cured product obtained from the (meth) acrylic polymer composition, and a substrate From the viewpoint of adhesiveness, an alkyl acrylate ester having an alkyl group having 4 or more carbon atoms such as n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc., or 2-ethylhexyl methacrylate, A methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms such as dodecyl methacrylate is preferred. In addition, these (meth) acrylic acid ester may be used individually by 1 type, or may use 2 or more types together.

  The content of the monomer unit formed by the (meth) acrylic ester in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b). It is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol% with respect to the unit.

  The (meth) acrylic polymer block (b) may have a monomer unit formed by a monomer other than the (meth) acrylic acid ester. The specific example of this other monomer is the same as that of other monomers other than the (meth) acrylic acid ester which can form a (meth) acrylic-type polymer (A). These other monomers may be used alone or in combination of two or more.

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

  Mn per one (meth) acrylic polymer block (b) is not particularly limited, but from the viewpoints of handleability, fluidity, mechanical properties and the like of the obtained (meth) acrylic block copolymer (A1), The range of 3,000 to 2,000,000 is preferable, and the range of 5,000 to 1,000,000 is more preferable.

  The (meth) acrylic block copolymer (A1) is a block in which at least one (meth) acrylic polymer block (a) and at least one (meth) acrylic polymer block (b) are bonded to each other. There are no particular restrictions on the number and order of bonding of each polymer block, but from the viewpoint of active energy ray curability, the (meth) acrylic polymer block (a) is a copolymer of (meth) acrylic blocks. It is preferable to form at least one terminal of the union (A1), and from the viewpoint of ease of production of the (meth) acrylic polymer (A), it is more preferably a linear polymer. A diblock copolymer in which a (meth) acrylic polymer block (a) and one (meth) acrylic polymer block (b) are combined, and one (meth) acrylic polymer block Both ends (meth) triblock copolymer each one acrylic polymer block (a) is bonded each (b) is more preferred.

  Ratio of mass of (meth) acrylic polymer block (a) and mass of (meth) acrylic polymer block (b) constituting (meth) acrylic block copolymer (A1) [(meth) acrylic The polymer block (a) :( meth) acrylic polymer block (b)] is not particularly limited, but is preferably 85:15 to 5:95, and 80:20 to 7:93. Is more preferable, and 75:25 to 10:90 is more preferable. The ratio of the mass of the (meth) acrylic polymer block (a) to the total mass of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) is 5% or more. And the curing rate tends to be excellent, and if it is 85% or less, the toughness of the cured product tends to increase.

  In the (meth) acrylic block copolymer (A1), the content of the monomer unit formed from the methacrylic acid ester is preferably 5 to 85% by mass, and 7 to 80% by mass. More preferably, it is more preferably 10 to 75% by mass. In the (meth) acrylic block copolymer (A1), 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 (meth) acrylic polymer (A) is obtained by polymerizing a monomer containing a (meth) acrylate having an active energy ray-curable group, for example, a monomer containing the above-mentioned di (meth) acrylate (4). Is obtained. The (meth) acrylic block copolymer (A1) can be obtained by forming the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) in a desired order.

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

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

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

  Examples of the organic lithium compound include methyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-pentyl lithium, 1-methylbutyl lithium, and 2-ethylpropyl lithium. , 1,1-dimethylpropyllithium, alkyllithium such as 1-methylpentyllithium; cycloalkyllithium such as cyclohexyllithium; diphenylmethyllithium, α-methylbenzyllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl Aralkyl lithium such as -3-methylpentyl lithium; α-lithioesters such as ethyl α-lithioisobutyrate, butyl α-lithioisobutyrate, methyl α-lithioisobutyrate; 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 usage-amount of an organolithium compound can be determined by the ratio with the usage-amount of the monomer to be used according to Mn of the target (meth) acrylic-type polymer (A).
As said organoaluminum compound, the organoaluminum compound shown by the following general formula (A-1) or (A-2) is mentioned.
AlR ⁷ (R ⁸ ) (R ⁹ ) (A-1)
Wherein R ⁷ represents a monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group, aryloxy group or N, N-disubstituted amino group, and R ⁸ and R ⁹ are each independently Or R ⁸ and R ⁹ are bonded to each other to form an aryleneoxy group)
AlR ¹⁰ (R ¹¹ ) (R ¹² ) (A-2)
(Wherein R ¹⁰ represents an aryloxy group, R ¹¹ and R ¹² each independently represent a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, or an N, N-disubstituted amino group. Represents a group)

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

In the above general formula (A-1), examples of the aryleneoxy group formed by bonding R ⁸ and R ⁹ to each other include 2,2′-biphenol, 2,2′-methylenebisphenol, 2,2 ′. -Methylenebis (4-methyl-6-tert-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2- 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 amount of the organoaluminum compound used can be appropriately selected in accordance with the type of solvent, other various polymerization conditions, etc., but is generally 1.0 to 10 with respect to 1 mol of the organic lithium compound from the viewpoint of the polymerization rate. It is preferably used in the range of 0.0 mol, more preferably in the range of 1.1 to 5.0 mol, and still more preferably in the range of 1.2 to 4.0 mol. If the amount of the organoaluminum compound used exceeds 10.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and if it is less than 1.0 mol, the polymerization initiation efficiency tends to decrease.

Examples of the Lewis base include compounds having an ether bond and / or a tertiary amine structure in the molecule.
Examples of the compound 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.

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

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

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

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

  The living anionic polymerization is preferably performed at -30 to 25 ° C. When it is lower than −30 ° C., the polymerization rate is lowered and the productivity tends to be lowered. On the other hand, when it is higher than 25 ° C., the polymerization of the di (meth) acrylate (4) tends to be difficult.

  The living anionic polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium. Moreover, it is preferable to carry out on stirring conditions so that a 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.

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

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

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

  As a method for introducing an active energy ray-curable group containing the partial structure (2) into the side chain in the production of the (meth) acrylic polymer (A), the di (meth) acrylate (4) described above is contained. In addition to the method for producing a (meth) acrylic polymer (A) by polymerizing monomers, a partial structure (hereinafter referred to as “precursor structure”) that is a precursor of the partial structure (2) is included. A method of converting the precursor structure into the partial structure (2) after forming a polymer having a side chain is also mentioned. A polymer having a side chain 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. The precursor structure includes a carboxyl group protected by a carboxyl group and a protecting group (silyloxy group, acyloxy group, alkoxy group, etc.), an amino group and an amino group protected by a protecting group, a thiol group and a protecting group. Examples include thiol groups and isocyanate groups.

  A polymer containing a carboxyl group as a precursor structure reacts with a partial structure (2) and a compound having a partial structure (such as an oxiranyl group, a carboxyl group, a hydroxyl group, an amino group, a vinyloxy group, or an acyloxy group) that can react with the carboxyl group. By doing so, the (meth) acrylic polymer (A) can be produced. In addition, a polymer containing a hydroxyl group protected by a protecting group as a precursor structure can be similarly produced from the (meth) acrylic polymer (A) after removing the protecting group to form a carboxyl group.

  A polymer containing an amino group as a precursor structure is a compound having a partial structure (2) and a partial structure capable of reacting with the amino group (carboxyl group, carboxylic anhydride, ester, carbonyl halide, aldehyde group, isocyanate group, etc.) By reacting with (meth) acrylic polymer (A), it can be produced. In addition, a polymer containing an amino group protected by a protecting group as a precursor structure can be similarly produced after removing the protecting group to form an amino group.

  The polymer containing a thiol group as a precursor structure includes a partial structure (2) and a partial structure capable of reacting with the thiol group (carboxyl group, carboxylic anhydride, ester, carbonyl halide, isocyanate group, carbon-carbon double bond, etc. The (meth) acrylic polymer (A) can be produced by reacting with a compound having). In addition, a polymer block containing a thiol group protected by a protective group as a precursor structure can produce a (meth) acrylic polymer (A) after removing the protective group to form a thiol group.

  A polymer containing an isocyanate group as a precursor structure is reacted with a compound having a partial structure (2) and a partial structure (hydroxyl group, amino group, etc.) capable of reacting with the isocyanate group, to form a (meth) acrylic polymer (A ) Can be manufactured.

  In the production of the (meth) acrylic polymer (A), a method of polymerizing a monomer containing di (meth) acrylate (4) from the viewpoint that an active energy ray-curable group can be easily introduced directly, typically For this, a method of living anion polymerization is preferred.

  The (meth) acrylic polymer composition of the present invention further contains a phosphorus compound (B). The phosphorus compound (B) has two partial structures represented by the following general formula (1). By including such a compound in the (meth) acrylic polymer composition, the curing rate when irradiated with active energy rays is significantly improved.

（式中、Ｒ^aは炭素数３〜２０の炭化水素基を表す）

(Wherein, R ^a represents a hydrocarbon group having 3 to 20 carbon atoms)

In the general formula (1), examples of the hydrocarbon group having 3 to 20 carbon atoms represented by ^Ra include, for example, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl. Group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group Alkyl groups such as 2-methylpentyl group, 3-methylpentyl group and n-decyl; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and naphthyl group; benzyl And aralkyl groups such as a phenylethyl group. Among these, from the viewpoint of improving the compatibility with the (meth) acrylic polymer (A), an alkyl group having 3 to 20 carbon atoms, specifically n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, Preferred are alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, n-decyl, etc., and n-alkyl group having 6 to 15 carbon atoms, specifically n-hexyl group. N-decyl and the like are more preferable.

  The phosphorus compound (B) is preferably a liquid at normal temperature (for example, 23 ° C.) from the viewpoint of improving handleability and chemical stability. Examples of the phosphorus compound (B) that is liquid at room temperature and can be easily obtained include 3,9-bis (isodecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro. [5.5] Undecane (for example, JPE-10 manufactured by Johoku Chemical Industry Co., Ltd.), bis (tridecyl) pentaerythritol diphosphite (for example, JPE-13R (manufactured by Johoku Chemical Industry Co., Ltd.)), bis ( Nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite (for example, JPP-2000PT (manufactured by Johoku Chemical Industry Co., Ltd.), PEP-8 (manufactured by ADEKA Corporation)), tetraalkyl (propane-2, 2-diylbis (4,1-phenylene) bis (phosphite) (for example, JA-805 (manufactured by Johoku Chemical Industry Co., Ltd.) (Manufactured by (Corporation) ADEKA) ADK STAB 1500), tetraphenyl dipropylene glycol diphosphite (manufactured by e.g. JPP-100 (Johoku Chemical Co.)) and the like.

  The content of the phosphorus compound (B) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic polymer (A). . If it is 0.01 part by mass or more, the curability of the (meth) acrylic polymer composition will be good, and if it is 10 parts by mass or less, deterioration with time of the resulting cured product tends to be suppressed. In addition, when using together 2 or more types of phosphorus compounds (B), the said content means the total amount.

The (meth) acrylic polymer 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, Sulfur compounds such as oxanthones (eg thioxanthone, 2-chlorothioxanthone); acyl phosphine 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 preferably 0.01 to 10 parts by mass, and 0.05 to 8 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic polymer (A). Is more preferable. If it is 0.01 part by mass or more, the curability of the (meth) acrylic polymer composition will be good, and if it is 10 parts by mass or less, deterioration with time of the resulting cured product tends to be suppressed. In addition, when using together 2 or more types of photoinitiators, the said content means the total amount.

  The (meth) acrylic polymer 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.

  Further, the (meth) acrylic polymer composition of the present invention may contain a reactive diluent that exhibits polymerizability by irradiation with active energy rays other than the (meth) acrylic polymer (A). Good. The reactive diluent is not particularly limited, but for example, styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene. Styrene derivatives such as 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, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Isoamyl acrylate, hexyl (meth) acrylate, (meth) acryl Heptyl acid, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) Undecyl acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, (meth) Tricyclodecanyl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) 2-Hydroxypropyl acrylate, (meth) a 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, (Meth) acrylic acid polyethylene glycol monoester, (meth) acrylic acid polypropylene glycol monoester, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid ethoxyethyl, (meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic Acid methoxypolypropylene glycol, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, 4- (meta ) Acryloylmorpholine, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate (Meth) acrylate, tricyclodecanediyldimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A jig Both terminal (meth) acrylic acid adducts of sidyl ether, pentaerythritol tetra (meth) acrylate, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanoltri ( (Meth) acrylate, N, N′-bis [2-((meth) acryloyloxy) ethyl] -N ″-(2-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, ethylene oxide or propylene oxide of hydrogenated bisphenol A Di (meth) acrylates of diols that are adducts, and cyclohexa (Meth) acrylic acid derivatives such as dimethanol di (meth) acrylate; epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin; carboxyl group-modified epoxy acrylate type resin; polyol (Polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl group-terminated hydrogenated polyisoprene, hydroxyl group-terminated polybutadiene, hydroxyl group-terminated polyisobutylene, etc.) and organic Isocyanates (tolylene diisocyanate, isophorone diisocyanate, dipheny Urethane resins obtained from methane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) are hydroxyl group-containing (meth) acrylates {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol tris Urethane acrylate resin obtained by reaction with acrylate, etc .; resin in which (meth) acrylic group is introduced into the above polyol via an ester bond; polyester (meth) acrylate resin; epoxidized soybean oil, epoxy benzyl stearate And epoxy compounds. These reactive diluents may be used alone or in combination of two or more.

  When the reactive diluent is contained in the (meth) acrylic polymer composition of the present invention, the content is determined by the fluidity of the (meth) acrylic polymer composition and the (meth) acrylic polymer composition. From the viewpoint of increasing the mechanical strength of the cured product obtained by irradiating the product with active energy rays, 10 to 90% by mass is preferable, and 20 to 80% by mass is more preferable. Moreover, it is preferable that it is 10-1000 mass parts with respect to 100 mass parts of (meth) acrylic-type polymers (A), and, as for this content, it is more preferable that it is 20-500 mass parts. In addition, when using together 2 or more types of reactive diluents, the said content means the total amount.

  The (meth) acrylic polymer composition of the present invention includes active energy rays such as plasticizers, tackifiers, softeners, fillers, stabilizers, pigments, dyes and the like within a range that does not significantly inhibit the curability thereof. Various additives having no curable group may be contained. These additives may be organic compounds or inorganic compounds.

  The purpose of including the plasticizer in the (meth) acrylic polymer composition of the present invention is, for example, adjustment of the viscosity of the (meth) acrylic polymer composition. 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 (meth) acrylic polymer composition of the present invention, the content is 5 to 150 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic polymer (A). Preferably, 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, the adhesion of the (meth) acrylic polymer composition to the base material is improved. .

  The molecular weight or number average molecular weight of these plasticizers is preferably 400 to 15000, more preferably 800 to 10000, and more preferably 1000 to 8000. Such a plasticizer may or may not have a functional group other than the active energy ray-curable group (for example, a hydroxyl group, a carboxyl group, a halogen group, etc.). When the molecular weight or Mn of the plasticizer is 400 or more, the surrounding contamination due to the outflow of the plasticizer from the cured product of the (meth) acrylic polymer composition is suppressed. Moreover, there exists a tendency for the handleability of a (meth) acrylic-type polymer composition to become favorable because the molecular weight or Mn of a plasticizer is 15000 or less.

  The purpose of including the tackifier in the (meth) acrylic polymer composition of the present invention is, for example, to impart tackiness to a cured product obtained from the (meth) acrylic polymer composition. 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 resin (polystyrene, poly-α-methylstyrene, etc.), polyhydric alcohol ester of rosin, hydrogenated rosin, hydrogenated wood rosin, ester of hydrogenated rosin and monoalcohol or polyhydric alcohol, turpentine tackifying resin And the like. Among these, aliphatic hydrocarbon resins, rosin polyhydric alcohol esters, hydrogenated rosins, hydrogenated wood rosins, hydrogenated rosins and monoalcohol or polyhydric alcohol esters are preferred.

  When the tackifier is contained in the (meth) acrylic polymer composition of the present invention, the content is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A), 10-120 mass parts is more preferable, and 20-100 mass parts is further more preferable. By setting it as 5 mass parts or more, the adhesiveness of hardened | cured material becomes remarkable, and the softness | flexibility of hardened | cured material tends to be excellent by setting it as 150 mass parts or less.

  The active energy rays used when the (meth) acrylic polymer composition of the present invention is cured can be irradiated using a known device. 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. If it is less than 10 mJ / cm ² , the curability of the (meth) acrylic polymer composition tends to be insufficient, and if it exceeds 20000 mJ / cm ² , the (meth) acrylic polymer composition may be deteriorated. .

  The (meth) acrylic polymer composition of the present invention may be further heated as necessary during or after irradiation of active energy rays 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.

  Applications of the (meth) acrylic polymer composition of the present invention include vehicle bodies, windows, lamps, batteries, window washer fluid units, air conditioner units, coolant units, brake oil units, electrical components, various interior and exterior products, oil Automotive applications such as filters; various recorders such as TVs, Blu-ray recorders, HDD recorders, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, fax recorders, photocopiers, telephones, door phones, rice cookers Oven, microwave oven, microwave oven, refrigerator, dishwasher, dish dryer, IH cooking heater, hot plate, vacuum cleaner, washing machine, charger, sewing machine, iron, dryer, air purifier, water purifier, electric toothbrush, lighting Appliance, air conditioner, air Acon's outdoor units, dehumidifiers, humidifiers and other household appliances; interior and exterior wall panels, windows, wallpaper and other architectural and civil engineering applications; liquid crystal display, plasma display, LED display device, organic EL display, field emission display, electronic paper , Flexible displays, 3D holograms, organic thin film transistor displays, head mounted displays, etc .; optical recording equipment applications such as pickup lenses; organic photorefractive elements, optical fibers, optical switches, lenses, optical waveguides, light emitting elements, photodiodes, light Applications for optical devices such as amplifying elements, optoelectronic integrated circuits, optical connectors, optical couplers, optical computing elements, photoelectric conversion devices, laser elements; lithium ion batteries, sodium / sulfur batteries, sodium molten salt batteries, nickel metal hydride batteries Curability used in battery applications such as nickel cadmium batteries, redox flow batteries, lithium sulfur batteries, air batteries, electrolytic capacitors, electric double layer capacitors, lithium ion capacitors, fuel cells, solar cells, dye-sensitized solar cells Resin, adhesive, tape, film, sheet, mat, sealing material, sealing material, coating material, potting material, ink, printing plate material, vibration isolator, foam, heat dissipation material, prepreg, gasket, packing, etc. Is mentioned. Particularly preferred for adhesives, tapes, sealing materials, paints, coating materials, potting materials, inks and the like.

  There is no restriction | limiting in particular in the material of a base material in the case of using the (meth) acrylic-type polymer composition of this invention hardened on a base material, For example, hot dip galvanized steel, aluminum zinc alloy plated steel, aluminum plated steel, stainless steel Metals such as steel, titanium, nickel, zinc, aluminum, copper, silver, gold; glass; wood; polyolefin (eg, polyethylene, polypropylene, ethylene-propylene copolymer, poly- (4-methylpentene-1), cyclic Polyolefin, modified polyolefin, etc.), polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide (eg nylon 6, nylon 66 etc.), polyimide, polyamideimide, polycarbonate, (meth) acrylic resin, acrylonitrile-conjugated diene-styrene copolymer Coalescence, acrylonitrile-styrene Polymer, conjugated diene-styrene copolymer, polyoxymethylene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyester (for example, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene) Naphthalate, polybutylene naphthalate, polycyclohexane terephthalate, various liquid crystal polyesters, etc.), polyether, polyether ketone, polyether ether ketone, polyether imide, polyacetal, polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, Polyphenylene sulfide, polyarylate, polyurethane, fluorine resin (for example, polytetrafluoroethylene, polyethylene Vinylidene fluoride, etc.), various thermoplastic elastomers (for example, styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluoro rubber, chlorinated polyethylene, Poly (meth) acrylates, etc.), epoxy resins, phenol resins, urea resins, melamine resins, silicone resins, and the like.

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

[Monomer consumption rate]
In the following Examples and Comparative Examples, the consumption rate of each monomer after polymerization was determined by collecting 0.5 ml of the reaction solution, mixing it in 0.5 ml of methanol, and then collecting 0.1 ml from the mixture solution. Then, ¹ H-NMR measurement was carried out under the following measurement conditions after dissolving in 0.5 ml of deuterated chloroform, and the proton directly connected to the carbon-carbon double bond of the (meth) acrylic acid ester used as the monomer was used. Of the integrated value of the peak derived from the proton (chemical shift value 6.08 to 6.10) and the peak derived directly from the aromatic ring of toluene used as the solvent (chemical shift value 7.00 to 7.38 ppm) Calculated from change.
⁽¹ H-NMR measurement conditions)
Apparatus: Nuclear magnetic resonance apparatus "JNM-ECX400" manufactured by JEOL Ltd.
Temperature: 25 ° C

[Number average molecular weight (Mn), molecular weight distribution (Mw / Mn)]
In the following examples and comparative examples, GPC (gel permeation chromatography) measurement of the obtained polymer was performed under the following measurement conditions, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of standard polystyrene ) Value.
(GPC measurement conditions)
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]
The Mn of the polymer actually obtained in the step (1) (referred to as Mn (R1)) and the Mn of the polymer obtained in the step (1) when the polymerization initiation efficiency is 100% (calculated value: Mn (I1)), the polymerization initiation efficiency (F1) in step (1) was calculated by the following equation.
F1 (%) = 100 × Mn (I1) / Mn (R1)

[Block efficiency from step (1) to step (2)]
Obtained in the above Mn (R1) and Mn (I1), the Mn of the polymer actually obtained in the step (2) (Mn (R2)), and the step (2) when the block efficiency is 100%. The block efficiency (F2) from the step (1) to the step (2) was calculated from the Mn (calculated value: Mn (I2)) of the polymer obtained by the following equation.
F2 (%) = 10000 · {Mn (I2) −Mn (I1)} / [F1 · {Mn (R2) −Mn (R1)}]

[Curing speed]
The curing rate of the (meth) acrylic polymer compositions obtained in the following examples and comparative examples was evaluated using a viscosity / viscoelasticity measuring apparatus (MARS III, manufactured by HAAKE).
On a parallel plate having a diameter of 20 mm, 1 g of a (meth) acrylic polymer composition was dropped to form a coating film. Using a high-speed OSC time-dependent measurement mode as the measurement mode, under the conditions of a measurement temperature of 25 ° C., a measurement gap of 0.15 mm, and a measurement frequency of 5 Hz, a UV lamp (manufactured by Lumen Dynamics, Omni Cure series 2000, irradiation intensity of 150 mW / cm ² ) The viscoelasticity was measured while irradiating with ultraviolet light.
The storage shear modulus (Pa) at the start of ultraviolet light irradiation is G ′ (0), and the storage shear modulus (Pa) after 4 seconds (after 600 mJ / cm ² irradiation) from the start of ultraviolet light irradiation is G ′ (4). The storage shear modulus (Pa) that reached a saturation value 40 seconds after the start of ultraviolet light irradiation (after 6000 mJ / cm ² irradiation) is G ′ (40), and the reaction rate R (%) obtained according to the following equation: ) As an index of curing speed.
Reaction rate (%) = {G ′ (4) −G ′ (0)} / {G ′ (40) −G ′ (0)} × 100

[Example 1]
(Process (1))
After 1.5L of toluene was added to a 3L flask which had been dried and purged with nitrogen, 1,1,4,7,10,10-hexamethyltriethylene was added as a Lewis base while stirring the solution in the flask. 3.7 ml (13.7 mmol) of tetramine, 33.2 ml (15.0 mmol) of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as an organoaluminum compound After adding sequentially, it cooled to -20 degreeC. To this was added 10 ml (13.0 mmol) of a 1.30 mol / L cyclohexane solution of sec-butyllithium as an organolithium compound, and 9.4 ml (39 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer. ) And 8.3 ml (78 mmol) of a mixture of methyl methacrylate were added all at once to initiate anionic polymerization. 160 minutes after completion of the addition of the mixture, the reaction solution changed from the original yellow color to colorless. After stirring for another 20 minutes, the reaction solution was sampled.

  The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (1) was 100%. Moreover, Mn (Mn (R1)) of the obtained polymer was 1,330 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., 20.2 ml of a 0.450 mol / L toluene solution of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum as an organoaluminum compound (9. 1 mmol), and 1 minute later, 575 ml (4.0 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 monomer addition.

  The consumption rate of n-butyl acrylate in the step (2) was 100%. Moreover, Mn (Mn (R2)) of the obtained polymer was 41,100, 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., 9.3 ml (38.7 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate and 8.2 ml (77.4 mmol) of methyl methacrylate were used as monomers. After 17.5 ml of the mixture was added all at once, the temperature was raised to 20 ° C. at a rate of 2 ° C./min. The reaction solution was sampled 120 minutes after the addition of the mixture.
The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step (3) was 100%.

(Process (4))
Subsequently, while the reaction solution was stirred at 20 ° C., anionic polymerization was stopped by adding 28.7 ml of 50 wt% aqueous acetic acid to obtain a solution containing the (meth) acrylic polymer (A). The Mn of the (meth) acrylic polymer (A) sampled from such a solution was 42,600, and Mw / Mn was 1.19.

(Process (5))
Subsequently, 3,9-bis (isodecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (manufactured by Johoku Chemical Co., Ltd.) was added to the resulting solution as the phosphorus compound (B). , JPE-10) was added, and the catalyst metal acetate was formed by heating for 90 minutes while stirring at 90 ° C. under nitrogen flow. After the reaction solution was cooled to 25 ° C., it was centrifuged for 30 minutes at a centrifugal force of 18,800 G using a centrifuge (manufactured by Hitachi Koki Co., Ltd., himacCR22GII) to precipitate acetate, and the supernatant was collected. . After removing the solvent from the collected supernatant liquid at 60 ° C. using an evaporator, it was further dried at 100 ° C. and 30 Pa to obtain 471 g of a (meth) acrylic polymer composition (1-1).

(Process (6))
Next, 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184) as a photopolymerization initiator is added to 100 parts by mass of the (meth) acrylic polymer composition (1-1). Then, the mixture was stirred and dissolved to obtain 476 g of (meth) acrylic polymer composition (1-2).

(Evaluation of curing speed)
According to the said method, the cure rate of the obtained (meth) acrylic-type polymer composition (1-2) was evaluated. The results are shown in Table 1.

[Example 2]
Except for changing the phosphorus compound (B) to tetraalkyl (propane-2,2-diylbis (4,1-phenylene)) bis (phosphite) (manufactured by ADEKA Corporation, ADK STAB 1500), the same as in Example 1. By the method, 465 g of (meth) acrylic polymer composition (2-2) was obtained. According to the said method, the cure rate of the obtained (meth) acrylic-type polymer composition (2-2) was evaluated. The results are shown in Table 1.

[Comparative Example 1]
The solution obtained in accordance with steps (1) to (4) of Example 1 was heated at 90 ° C. under a nitrogen flow while being heated for 90 minutes to form a catalyst metal acetate. After the reaction solution was cooled to 25 ° C., it was centrifuged for 30 minutes at a centrifugal force of 18,800 G using a centrifuge (manufactured by Hitachi Koki Co., Ltd., himacCR22GII) to precipitate acetate, and the supernatant was collected. . After removing the solvent from the recovered supernatant at 60 ° C. using an evaporator, the solvent was further dried at 100 ° C. and 30 Pa to obtain 466 g of a (meth) acrylic polymer. 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184) as a photopolymerization initiator is added to 100 parts by weight of the (meth) acrylic polymer, and stirred and dissolved to obtain 471 g. (Meth) acrylic polymer composition (1 ′) was obtained. The curing rate of the obtained (meth) acrylic polymer composition (1 ′) was evaluated. The results are shown in Table 1.

[Comparative Example 2]
Except for changing to 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane (manufactured by ADEKA, Adeka Stub 522A) instead of the phosphorus compound (B) In the same manner as in Example 1, 472 g of a (meth) acrylic polymer composition (2′-2) was obtained. According to the said method, the cure rate of the obtained (meth) acrylic-type polymer composition (2'-2) was evaluated. The results are shown in Table 1.

[Comparative Example 3]
466 g of (meth) acrylic polymer composition (3 ′) in the same manner as in Example 1 except that triisodecyl phosphite (manufactured by ADEKA, Adeka Stub 3010) was used instead of the phosphorus compound (B). -2) was obtained. According to the said method, the cure rate of the obtained (meth) acrylic-type polymer composition (3'-2) was evaluated. The results are shown in Table 1.

表１から分かるように、本発明の（メタ）アクリル系重合体組成物は、硬化速度が高い。

As can be seen from Table 1, the (meth) acrylic polymer composition of the present invention has a high curing rate.

Claims (3)

A (meth) acrylic polymer (A) having two or more active energy ray-curable groups in the side chain, and a phosphorus compound (B) having two partial structures represented by the following general formula (1) ( (Meth) acrylic polymer composition.

(Wherein, R ^a represents a hydrocarbon group having 3 to 20 carbon atoms)   The (meth) acrylic polymer composition according to claim 1, wherein the content of the phosphorus compound (B) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A). . The (meth) acrylic polymer composition according to claim 1 or 2, wherein ^Ra in the general formula (1) represents an alkyl group having 3 to 20 carbon atoms.