JP2018039941A - (meth)acrylic block copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a (meth)acrylic block copolymer composition that provides a cured product, which is obtained by irradiation with active energy rays and the like, excellent in long-term stability of adhesive force.SOLUTION: A polymer composition contains a (meth)acrylic block copolymer (I) formed of a methacrylic polymer block (A) having an active energy ray curable group containing a partial structure (1) represented by general formula (1) and a (meth)acrylic polymer block (B) having no active energy ray curable group, and a (meth)acrylic block copolymer (II) formed of at least one polymer block (C) composed of a methacrylic acid ester unit and at least one polymer block (D) composed of an acrylic acid ester unit, and having no partial structure (1) represented by general formula (1). In formula (1), Rrepresents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a polymer composition having excellent adhesive properties that can be cured with active energy rays or the like.

  A display used for a flat-screen TV, a smartphone, a tablet terminal, and the like is a laminate of various components, and an acrylic adhesive is mainly used for bonding. As an acrylic adhesive, an adhesive obtained from an active energy ray-curable composition obtained by curing a mixture containing an active energy ray-curable oligomer and an active energy ray-curable monomer with active energy rays. Adhesives are known (see Patent Document 1). Adhesives obtained from active energy ray-curable compositions require high transparency, flexibility, adhesiveness, etc., but in recent years, due to the demand for thinner displays, particularly improved adhesiveness has been achieved. It has been demanded.

  As a means for improving the adhesive property of the adhesive, a method of adding a tackifier such as rosin is generally known. However, since such tackifiers may cause a so-called bleed-out phenomenon that floats on the surface of the cured product over time, they are suitable for optical adhesives that require long-term stability of adhesive strength such as display applications. Absent. Therefore, there has been a demand for an active energy ray-curable composition that has excellent long-term adhesion strength without causing a bleed-out phenomenon.

JP 2016-37574 A

“POLYMER HANDBOOK Forth Edition”, VII, Wiley Interscience, 1999, p. 675-714 Polymer Engineering and Science, 1974, Vol. 14, p. 147-154

  An object of the present invention is to provide a polymer composition containing a (meth) acrylic block copolymer from which an adhesive having excellent long-term stability of adhesive force without causing a bleed-out phenomenon can be obtained. .

According to the invention, the object is
[1] A methacrylic polymer block (A) having an active energy ray-curable group containing a partial structure (1) represented by the following general formula (1), and not having an active energy ray-curable group (meth) A (meth) acrylic block copolymer (I) comprising an acrylic polymer block (B), at least one polymer block (C) comprising a methacrylic acid ester unit, and at least a acrylic acid ester unit A (meth) acrylic block copolymer (II) comprising one polymer block (D) and not having the partial structure (1) represented by the general formula (1),
A polymer composition comprising:

(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
[2] In the (meth) acrylic block copolymer (I) and the (meth) acrylic block copolymer (II), the glass transition temperature of the polymer block (A) and the polymer block (C) is 90. The polymer composition according to [1], which is not lower than ° C. and the glass transition temperature of the polymer block (B) and the polymer block (D) is not higher than 30 ° C .;
[3] The solubility parameter (SP (B)) of the polymer block (B) in the (meth) acrylic block copolymer (I) and the polymer in the (meth) acrylic block copolymer (II) The polymer composition according to [1] or [2], wherein the difference from the solubility parameter (SP (D)) of the block (D) is −0.5 or more and 0.5 or less;
[4] The mass ratio (I) / (II) of the (meth) acrylic block copolymer (I) to the (meth) acrylic block copolymer (II) is 99.9 / 0.1. The polymer composition according to any one of claims 1 to 3, which is 50.0 / 50.0;
[5] An active energy ray-curable composition containing the polymer composition according to any one of [1] to [4];
[6] A cured product obtained by curing the polymer composition according to any one of [1] to [4] or the active energy ray-curable composition according to [5];
Is achieved by providing

  The polymer composition containing the (meth) acrylic block copolymer obtained in the present invention can be cured with active energy rays or the like, and the cured product obtained from this polymer composition causes a bleed-out phenomenon. Excellent long-term adhesive strength.

  Hereinafter, the present invention will be described in detail.

  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”. The “(meth) acrylate” described later means a generic name of “methacrylate” and “acrylate”.

  The (meth) acrylic block copolymer (I) is contained in the polymer composition of the present invention. The (meth) acrylic block copolymer (I) contains a methacrylic polymer block (A) and a (meth) acrylic polymer block (B), and the methacrylic polymer block (A) is a partial It has structure (1).

  The partial structure (1) exhibits polymerizability upon irradiation with active energy rays. As a result, the polymer composition containing the (meth) acrylic block copolymer (I) is cured by irradiation with active energy rays to become 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 viewpoint of curing speed, availability of an irradiation apparatus, price, and the like.

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

(In the formula (1), 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, sec- Butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl Group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, n-decyl group and other alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group, naphthyl Aryl groups such as groups; aralkyl groups such as benzyl groups and phenylethyl groups. Among these, from the viewpoint of active energy ray curability, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a methyl group is most preferable.

  The partial structure (1) in the methacrylic polymer block (A) is a part of the partial structure represented by the following general formula (2) (hereinafter referred to as “partial structure (2)”) from the viewpoint of curing speed. Preferably there is.

(In Formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and X represents O , S, or N (R ⁴ ) (R ⁴ 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 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 Alkyl groups such as n-pentyl group, 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 Aryl groups and the like. 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.

In the general formula (2), X represents O, S or N (R ⁴ ) (R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), and O is easy to control polymerization. Is preferred. When X is N (R ⁴ ), examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁴ 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 (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 (meth) acrylic block copolymer (I).

  The number of partial structures (1) contained in the (meth) acrylic block copolymer (I) is preferably 1 or more, more preferably 2 or more, and 3 or more. Further preferred.

  The content of the partial structure (1) with respect to all the monomer units constituting the methacrylic polymer block (A) is preferably in the range of 0.1 to 70 mol%, more preferably in the range of 1 to 50 mol%, The range of 5-40 mol% is more preferable.

  The partial structure (1) contained in the methacrylic polymer block (A) may be at the end of the methacrylic polymer block or at the side chain, but the partial structure (1) having a preferable content is introduced. From this point of view, it is preferably at least in the side chain.

  The methacrylic polymer block (A) includes a monomer unit derived from a monomer containing a methacrylic ester. Such methacrylic acid esters are roughly classified into monofunctional methacrylic acid esters having one methacryloyl group and polyfunctional methacrylic acid esters having two or more methacryloyl groups.

  Examples of the monofunctional methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate. , Methacrylates having no functional group such as isobornyl methacrylate, dodecyl methacrylate, 2-methoxyethyl methacrylate, phenyl methacrylate, naphthyl methacrylate; 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, methacryl Trimethoxysilylpropyl acid, 2-aminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2- (trimethylsilyl methacrylate) Oxy) ethyl, 3- (trimethylsilyloxy) propyl methacrylate, glycidyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of methacrylic acid, trifluoromethyl methyl methacrylate, 2-trifluoromethacrylate Methylethyl, 2-perfluoroethylethyl methacrylate, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, methacryl 2-perfluoromethyl-2-perfluoroethyl methyl acid, 2-perfluorohexyl ethyl methacrylate, 2-perfluorodecyl ethyl methacrylate, 2-perfluorohe methacrylate And methacrylates having a functional group such as xadecylethyl. Among these, methacrylic acid alkyl esters having an alkyl group having 1 to 5 carbon atoms, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate. Is preferred.

  The content of the monomer unit derived from the monofunctional methacrylate ester (for example, methyl methacrylate) with respect to all the monomer units of the methacrylic polymer block (A) is, from the viewpoint of active energy ray curability, It is preferably 30 mol% or more and 99.9 mol% or less, more preferably 50 mol% or more and 99 mol% or less, and further preferably 60 mol% or more and 95 mol% or less. Further, the content of the monomer unit derived from the monofunctional methacrylic acid ester is such that each of the methacrylic polymer blocks (A) is contained in the (meth) acrylic block copolymer (I), In each polymer block, it is preferably 30 mol% or more and 99.9 mol% or less, more preferably 50 mol% or more and 99 mol% or less, and further preferably 60 mol% or more and 95 mol% or less. preferable.

Further, when a bifunctional methacrylic acid ester represented by the following general formula (3) (hereinafter referred to as “dimethacrylate (3)”) is used as the polyfunctional methacrylic acid ester, living anionic polymerization is performed under the conditions described later. Thus, one methacryloyl group (a methacryloyl group to which “O (CH ₂ ) _n ” in the following general formula (3) is directly linked) is selectively polymerized to form a methacrylic polymer block having a partial structure (2) ( Since A) is obtained, it is preferable.

(In formula (3), R ² and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer of 1 to 20)
In the general formula (3), 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 (2). In the general formula (3), an integer of 1 to 20 represented by n is preferably 2 to 5 from the viewpoint of fluidity and curing rate of the (meth) acrylic block copolymer (I).

  Specific examples of the dimethacrylate (3) include, for example, 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 di Methacrylates, 1,1-diethylpentane-1,5-diol dimethacrylate, 1,1-diethylhexane-1,6-diol dimethacrylate, and the like. 1,1-dimethylpropane-1,3-diol dimethacrylate 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethyl Rupentane-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 are preferred, 1,1-dimethylpropane-1,3-diol Dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, and 1,1-dimethylhexane-1,6-diol dimethacrylate are more preferable.

  The monofunctional and polyfunctional methacrylates described above may be used alone or in combination of two or more.

  The content of the monomer unit derived from the polyfunctional methacrylic acid ester with respect to all the monomer units of the methacrylic polymer block (A) is preferably 70 mol% or less, and 50 mol% or less. Is more preferable, and it is further more preferable that it is 40 mol% or less. Moreover, when polyfunctional methacrylic acid ester contains dimethacrylate (3), content of the monomer unit derived from dimethacrylate (3) with respect to all monomer units of the methacrylic polymer block (A) is The range of 0.1 to 70 mol% is preferable, the range of 1 to 50 mol% is more preferable, and the range of 5 to 40 mol% is more preferable.

  When the methacrylic polymer block (A) is formed from a monomer containing a monofunctional methacrylate and a polyfunctional methacrylate, the content of the monomer unit derived from the monofunctional methacrylate is The total content of monomer units derived from the polyfunctional methacrylate is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. Preferably, it may be 100 mol%. Furthermore, when the methacrylic polymer block (A) is formed from a monomer containing methyl methacrylate and dimethacrylate (3), with respect to all monomer units of the methacrylic polymer block (A), The total amount of monomer units derived from methyl methacrylate and the content of monomer units derived from dimethacrylate (3) is based on the total monomer units of the methacrylic polymer block (A). 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 further preferable, and the range may be 100 mol%. In addition, when each methacrylic polymer block (A) is contained in the (meth) acrylic block copolymer (I), each content described above is preferably in the above preferred range, desirably Is a more preferable range.

  The methacrylic polymer block (A) may have a monomer unit derived 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, and 2-ethylhexyl acrylate. , Isobornyl acrylate, dodecyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl (meth) acrylate, trimethoxysilylpropyl acrylate, 2-aminoethyl acrylate, acrylic acid N , N-dimethylaminoethyl, N, N-diethylaminoethyl acrylate, phenyl acrylate, naphthyl acrylate, 2- (trimethylsilyloxy) ethyl acrylate, 3- (trimethylsilyloxy) propyl acrylate, glycidyl acrylate, -(Acryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl acrylate 2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acrylate, 2-perfluoroacrylate Acrylic esters such as fluorohexylethyl, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate; α-alkoxy amines such as methyl α-methoxyacrylate and methyl α-ethoxyacrylate Crylate ester; Crotonic acid ester such as methyl crotonate and ethyl crotonate; 3-alkoxy acrylate ester such as 3-methoxyacrylate; N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, 2 -Methyl bromomethyl acrylate, ethyl 2-bromomethyl acrylate, 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 is preferably 10 mol% or less with respect to all monomer units of the methacrylic polymer block (A), and preferably 5 mol%. The following is more preferable. In addition, when the content of the monomer unit formed by the other monomer is more than one methacrylic polymer block (A) in the (meth) acrylic block copolymer (I), In each of the polymer blocks, it is an embodiment that is preferably 10 mol% or less, more preferably 5 mol% or less.

  The glass transition temperature (Tg) of the polymer block (A) is preferably 90 ° C. or higher, more preferably 95 to 150 ° C., and further preferably 100 to 130 ° C. The glass transition temperature of the polymer block (A) can be controlled by the type of the monomer that forms the polymer block (A), the polymerization method, and the like. When Tg is in this range, the cohesive force is improved at the normal use temperature of the (meth) acrylic block copolymer composition, and excellent adhesive properties and durability are exhibited. The glass transition temperature in the present invention is the transition region of a polymer block observed in a curve obtained by DSC measurement of a polymer block or an acrylic block copolymer under a temperature rising condition of 10 ° C./min. Extrapolation start temperature (Tgi).

  The number average molecular weight (Mn) of the methacrylic polymer block (A) is preferably in the range of 500 to 100,000 from the viewpoints of handleability, fluidity, mechanical properties and the like of the resulting block copolymer. More preferably, it is in the range of 1,000 to 10,000. When a plurality of methacrylic polymer blocks (A) are contained in the (meth) acrylic block copolymer (I), the Mn of each polymer block is in the above preferred range, desirably in a more preferred range, This is a preferred embodiment. In the present specification, Mn, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) described later are calculated from standard polystyrene equivalent values obtained by gel permeation chromatography (GPC) measurement and the values thereof. Value.

  The content of the methacrylic polymer block (A) in the (meth) acrylic block copolymer (I) is preferably 1% by mass or more and 20% by mass or less, and preferably 2% by mass or more and 10% by mass or less. Is more preferable. When the content is 1% by mass or more, the curing rate when the polymer composition of the present invention is irradiated with active energy rays tends to be excellent, and when the content is 20% by mass or less, the polymer composition of the present invention. The cured product obtained by curing the resin tends to be excellent in flexibility.

  The (meth) acrylic block copolymer (I) contains a (meth) 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 (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyloxy group, 1,3-dienyl group, styryl group and other ethylenic double bonds ( In particular, a functional group having a general formula CH ₂ = CR— (wherein R is an alkyl group or a hydrogen atom)); an epoxy group, an oxetanyl group, a thiol group, a maleimide group, and the like.

  Examples of the (meth) acrylic acid ester that can form the (meth) acrylic polymer block (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth). Isopropyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid Dodecyl, trimethoxysilylpropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) Phenyl acrylate, (meth) acrylic acid naphthyl, (meth) acrylic acid 2- (trimethyl Rushiriruokishi) ethyl, and a monofunctional (meth) acrylic acid esters such as (meth) acrylic acid 3- (trimethylsilyloxy) propyl. Among these, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable from the viewpoint of glass transition temperature and adhesiveness. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  The content of the monomer unit formed by the (meth) acrylic ester in the (meth) acrylic polymer block (B) is the total monomer forming the (meth) acrylic polymer block (B). It is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol% with respect to the unit. In addition, the content of the monomer unit formed by the (meth) acrylic acid ester includes a plurality of (meth) acrylic polymer blocks (B) in the (meth) acrylic block copolymer (I). In that case, it is preferably 90 mol% or more, more preferably 95 mol% or more, and may be 100 mol% in each polymer block.

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

  The content of the monomer unit formed by the other monomer in the (meth) acrylic polymer block (B) is the total monomer forming the (meth) acrylic polymer block (B). The amount is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit. The content of the monomer unit formed by the other monomer is such that the (meth) acrylic polymer block (B) includes a plurality of (meth) acrylic block copolymers (I). In one mode, each polymer block is preferably 10 mol% or less, more preferably 5 mol% or less.

  The Tg of the polymer block (B) is preferably 30 ° C. or lower, more preferably −90 to 25 ° C., and further preferably −80 to 20 ° C. When Tg is in this range, when the polymer composition is used as an adhesive, it has an appropriate tack and adhesive strength.

  The Mn of the (meth) acrylic polymer block (B) is preferably in the range of 3,000 to 300,000, from the viewpoint of handleability, fluidity, mechanical properties, and the like of the resulting block copolymer, A range of 200,000 is more preferred. When a plurality of (meth) acrylic polymer blocks (B) are contained in the (meth) acrylic block copolymer (I), the Mn of each polymer block is in the above preferred range, desirably in a more preferred range. Is a preferred embodiment.

  The content of the (meth) acrylic polymer block (B) in the (meth) acrylic block copolymer (I) is preferably 80% by mass or more and 99% by mass or less, and 90% by mass or more and 98% by mass. The following is more preferable. When the content is 80% by mass or more, a cured product obtained by curing the polymer composition of the present invention tends to be excellent in flexibility, and when it is 99% by mass or less, the polymer composition of the present invention. It tends to be excellent in the curing rate when irradiated with active energy rays.

  The Mn of the (meth) acrylic block copolymer (I) is preferably 4,000 or more and 400,000 or less, and more preferably 7,000 or more and 200,000 or less. When Mn is in the above range, the cured product obtained from the polymer composition containing the block copolymer is excellent in handleability, fluidity, mechanical properties, etc., and the polymer composition is used as an adhesive. If it is, excellent long-term stability of adhesive strength.

  The molecular weight distribution of the (meth) acrylic block copolymer (I), that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), Mw / Mn is preferably 2.00 or less, 1.02-2 The range of 0.00 is more preferable, the range of 1.05-1.80 is more preferable, and the range of 1.10-1.50 is most preferable.

  The (meth) acrylic block copolymer (I) is a block copolymer having at least one methacrylic polymer block (A) and at least one (meth) acrylic polymer block (B). The number of each polymer block and the bonding order are not particularly limited, but from the viewpoint of active energy ray curability, the methacrylic polymer block (A) is at least one of the (meth) acrylic block copolymer (I). It is preferable to form a methacrylic block, from the viewpoint of ease of production of the (meth) acrylic block copolymer (I), more preferably a linear polymer. A diblock copolymer in which (A) and one (meth) acrylic polymer block (B) are bonded, or on both ends of one (meth) acrylic polymer block (B). Triblock copolymers each one acrylic polymer block (A) is bonded, respectively are more preferred.

  The method for producing the (meth) acrylic block copolymer (I) 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. An anionic polymerization method is more preferable.

  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, from the point that (meth) acrylic block copolymer (I) can be polymerized directly and efficiently, living anions are prepared using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound. A method of polymerization is preferred, and a method of living anion polymerization using an organolithium compound as a polymerization initiator in the presence of an organoaluminum compound and a Lewis base is more preferred.

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

  The amount of the organolithium compound used can be determined by the ratio to the amount of the monomer used depending on the number average molecular weight of the target block copolymer.

  As said organoaluminum compound, the organoaluminum compound shown by the following general formula (A-1) or (A-2) is mentioned.

AlR ⁵ (R ⁶ ) (R ⁷ ) (A-1)
Wherein R ⁵ represents a monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group, aryloxy group or N, N-disubstituted amino group, and R ⁶ and R ⁷ are each independently And R ⁶ and R ⁷ are bonded to each other to form an arylenedioxy group.)
AlR ⁸ (R ⁹ ) (R ¹⁰ ) (A-2)
(Wherein R ⁸ represents an aryloxy group, and R ⁹ and R ¹⁰ each independently represents 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 above general formulas (A-1) and (A-2), examples of the aryloxy group that R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent include a phenoxy group, a 2-methylphenoxy group, 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 arylenedioxy group formed by bonding R ⁶ and R ⁷ 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 atom and bromine atom.

In the above general formulas (A-1) and (A-2), examples of the monovalent saturated hydrocarbon group independently represented by R ⁵ , R ⁹ and R ¹⁰ 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 atom and bromine atom.

  Examples of the organoaluminum compound (A-1) include ethylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-t-butylphenoxy) aluminum, ethyl [2 , 2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-t) -Butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6-di-t-butylphenoxy) aluminum, n-octyl [2,2 ′ Methylenebis (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, Sopropoxy [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-methyl) Phenoxy) aluminum, di-n-octyl (2,6-di-t-butylphenoxy) aluminum and the like. These organoaluminum compounds may be used alone or in combination of two or more.

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

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

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

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

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

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

  The living anionic polymerization is preferably performed at -30 to 25 ° C. When it is lower than −30 ° C., the polymerization rate is lowered and the productivity tends to be lowered. On the other hand, when the temperature is higher than 25 ° C., it tends to be difficult to polymerize the monomer containing the dimethacrylate (3) with good living property.

  The living anionic polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium. Furthermore, it is preferable to carry out under sufficient stirring conditions so that the reaction system becomes 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; acetic acid or hydrochloric acid in methanol; a protic compound such as aqueous solution of acetic acid or hydrochloric acid to the reaction solution. The amount of the polymerization terminator used is usually preferably in the range of 1 to 1,000 mol per 1 mol of the organolithium compound used.

  As a method for separating and obtaining the block copolymer from the reaction solution after the living anionic polymerization is stopped, a known method can be adopted. Examples thereof include a method of pouring the reaction solution into a poor solvent of the block copolymer and precipitating, a method of distilling off the organic solvent from the reaction solution and obtaining a block copolymer.

  In addition, when the metal component derived from the organolithium compound and the organoaluminum compound remains in the block copolymer obtained separately, the physical properties of the block copolymer may be deteriorated, the transparency may be deteriorated, and the like. 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.

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

  A polymer block containing a hydroxyl group as a precursor structure is reacted with a compound having a partial structure (1) and a partial structure (carboxylic acid, ester, carbonyl halide, etc.) capable of reacting with a hydroxyl group, thereby allowing a methacrylic polymer block (A ) Can be formed. A polymer block containing a hydroxyl group protected by a protecting group as a precursor structure can form a methacrylic polymer block (A) in the same manner after removing the protecting group to form a hydroxyl group.

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

  A polymer block containing an isocyanate group as a precursor structure can form a methacrylic polymer block (A) by reacting with a compound having a partial structure (1) and a partial structure (such as a hydroxyl group) capable of reacting with an isocyanate group. .

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

  The polymer composition of the present invention further contains a (meth) acrylic block copolymer (II). The (meth) acrylic block copolymer (II) comprises at least one polymer block (C) composed of methacrylic acid ester units and at least one polymer block (D) composed of acrylate ester units. And it does not have the partial structure (1) represented by the general formula (1). In addition to the (meth) acrylic block copolymer (I), in addition to the (meth) acrylic block copolymer (II), the polymer composition not only has excellent heat resistance, Excellent adhesion to glass.

  The (meth) acrylic block copolymer (II) preferably does not have the above-described active energy ray-curable group.

  As the methacrylic acid ester that is a constituent unit of the polymer block (C), monofunctional methacrylic acid that becomes a monomer unit of the methacrylic polymer block (A) of the (meth) acrylic block copolymer (I). Examples of the acid ester include a methacrylic acid ester having no functional group and a methacrylic acid ester having a functional group.

  Among these, from the viewpoint of improving the heat resistance and durability of the obtained polymer composition, a methacrylic acid ester having no functional group is preferable, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylic acid. t-Butyl, cyclohexyl methacrylate, isobornyl methacrylate, and phenyl methacrylate are more preferable, the polymer block (C) has a glass transition temperature suitable for hot melt molding, and the polymer block (C) and the polymer Methyl methacrylate is more preferable from the point that the block (D) is phase-separated to increase the durability of the polymer composition. These methacrylic acid esters may be used alone or in combination of two or more.

  The proportion of methacrylic acid ester units contained in the polymer block (C) is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and 100 mol in the polymer block (C). %.

  The glass transition temperature (Tg) of the polymer block (C) is preferably 90 ° C. or higher, more preferably 95 to 150 ° C., and further preferably 100 to 130 ° C. The glass transition temperature of the polymer block (C) can be controlled by the type of the monomer that forms the polymer block (C), the polymerization method, and the like. When the Tg is in this range, the polymer block (C) acts as a physical pseudo-crosslinking point at the normal use temperature of the polymer composition, and a cohesive force is exhibited, and adhesion and durability are improved. Excellent heat resistance and excellent hot melt molding.

  The number average molecular weight (Mn) of the polymer block (C) is not particularly limited, but is preferably in the range of 1,000 to 80,000, more preferably in the range of 2,000 to 60,000, More preferably, it is in the range of 3,000 to 40,000. When the Mn of the polymer block (C) is smaller than this range, the cohesive force of the obtained (meth) acrylic block copolymer (II) may be insufficient. When the Mn of the polymer block (C) is larger than this range, the melt viscosity of the resulting (meth) acrylic block copolymer (II) becomes high, and the (meth) acrylic block copolymer ( It may be inferior to the productivity of II) and the hot melt moldability when producing the polymer composition of the present invention.

  Examples of the acrylic ester serving as the structural unit of the polymer block (D) include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid. sec-butyl, t-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, acrylic acid Acrylic acid ester having no functional group such as lauryl, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate; 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-aminoethyl acrylate, glyceryl acrylate Jill, 2-ethoxyethyl acrylate, acrylic acid 2- (diethylamino) ethyl, tetrahydrofurfuryl acrylate, acrylic acid esters having a functional group such as 2-phenoxyethyl acrylate.

  Among these, an acrylic ester having no functional group is used because the phase separation between the polymer block (C) and the polymer block (D) becomes clearer and the cohesive force of the resulting polymer composition increases. Preferably, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable. These acrylic acid esters may be used alone or in combination of two or more.

  The proportion of the acrylate unit contained in the polymer block (D) is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and 100 mol in the polymer block (D). %.

  When the (meth) acrylic block copolymer (II) contains two or more polymer blocks (D), the structures of the polymer blocks (D) are the same or different. Also good.

    The Tg of the polymer block (D) is preferably 30 ° C. or less, more preferably −90 to 25 ° C., and further preferably −80 to 20 ° C. When Tg is within this range, a composition that is flexible at the use temperature, has high adhesion, and is excellent in durability can be obtained.

  The polymer block (C) and the polymer block (D) may contain components of each other as long as the effects of the present invention are not impaired. Moreover, you may contain another monomer as needed. Examples of such other monomers include vinyl monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, and (meth) acrylamide; (meth) acrylonitrile Vinyl monomers having a functional group such as vinyl acetate, vinyl chloride, vinylidene chloride; aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene; butadiene, Examples thereof include conjugated diene monomers such as isoprene; olefin monomers such as ethylene, propylene, isobutene and octene; and lactone monomers such as ε-caprolactone and valerolactone. When these monomers are used, they are usually used in a small amount, but are preferably 40 mol% or less, more preferably 20 mol% or less, and more preferably 20 mol% or less, based on the total mass of monomers used in each polymer block. It is preferably used in an amount of 10 mol% or less.

  The content of the polymer block (C) in the (meth) acrylic block copolymer (II) used in the present invention is preferably 5 to 60% by mass, and the content of the polymer block (D) is 95. It is preferable that it is -40 mass%. The polymer block (C) is 6 in that the polymer composition has excellent adhesive properties and can be supplied in a form that is easy to handle (for example, pellets). ~ 50 mass% and polymer block (D) are preferably 94-50 mass%, polymer block (C) is 7-40 mass%, and polymer block (D) is 93-60 mass%. It is more preferable.

The (meth) acrylic block copolymer (II) has a general formula: when the polymer block (C) is “C”; and the polymer block (D) is “D”;
(CD) n
(CD) n-C
D- (C-D) n
(C−D) n−Z
(DC) nZ
(Wherein n represents an integer of 1 to 30 and Z represents a coupling site (a coupling site after a coupling agent reacts with a polymer terminal to form a chemical bond)). Is preferred. The value of n is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 4. Among the above structures, a linear block copolymer represented by (CD) n, (CD) n-C, D- (CD) n is preferable, and represented by CD. The linear diblock copolymer and the linear triblock copolymer represented by C-D-C are more preferable.

  The Mn of the (meth) acrylic block copolymer (II) increases the cohesive strength of the adhesive produced from the resulting polymer composition and suppresses the bleed-out phenomenon, resulting in long-term adhesion. From the point which is excellent in stability, 10,000-400,000 are preferable, 20,000-300,000 are more preferable, 30,000-200,000 are further more preferable.

  The molecular weight distribution Mw / Mn of the (meth) acrylic block copolymer (II) is preferably 1.0 to 1.5, and the bleed-out phenomenon is suppressed and the adhesive prepared from the polymer composition is used. From the viewpoint of high cohesive strength at high temperature, it is more preferably 1.0 to 1.4, and further preferably 1.0 to 1.3.

  The solubility parameter (SP (B)) of the polymer block (B) in the (meth) acrylic block copolymer (I) and the polymer block (D) in the (meth) acrylic block copolymer (II). The difference (SP (B) −SP (D)) from the solubility parameter (SP (D)) is preferably −0.5 or more and 0.5 or less. When (SP (B) -SP (D)) is not less than -0.5 and not more than 0.5, a transparent polymer composition having good compatibility can be obtained. From the viewpoint of the transparency of the polymer composition, (SP (B) -SP (D)) is more preferably from -0.2 to 0.2. The solubility parameter of each polymer block is a value obtained by the Fedors estimation method described in Non-Patent Document 1 (more specifically, Non-Patent Document 2). For the (meth) acrylic block copolymer in which the polymer block (B) is composed of two or more types of (meth) acrylic acid ester units, the mass ratio is the value of the solubility parameter of each (meth) acrylic acid ester unit. The solubility parameter (SP (B)) of the (meth) acrylic acid ester unit constituting the polymer block (B) in the (meth) acrylic block copolymer.

  The method for producing the (meth) acrylic block copolymer (II) is not particularly limited as long as a polymer satisfying the conditions of the present invention regarding the chemical structure is obtained, and a method according to a known method is adopted. can do. As this manufacturing method, the method similar to the manufacturing method of (meth) acrylic-type block copolymer (I) is mentioned. Among these production methods, the method of living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound results in high transparency of the resulting block copolymer, and less residual monomer and odor. In addition, when used as a polymer composition, generation of bubbles after bonding can be suppressed, which is preferable. Furthermore, the molecular structure of the methacrylic acid ester polymer block is highly syndiotactic, which has the effect of increasing the heat resistance of the hot melt adhesive composition, and can be used for living polymerization under relatively mild temperature conditions. In the production, the environmental load (mainly the electric power applied to the refrigerator for controlling the polymerization temperature) is also small.

  In the polymer composition of the present invention, the mass ratio (I) / (II) between the (meth) acrylic block copolymer (I) and the (meth) acrylic block copolymer (II) is 99. It is preferably 9 / 0.1 to 50.0 / 50.0, more preferably 95.0 / 5.0 to 45.0 / 55.0, and 85.0 / 15.0 to 45. More preferably, it is 0.0 / 55.0. When the mass ratio (I) / (II) is in the above range, not only the adhesive strength of glass or the like is excellent, but also the adhesive strength tends to be maintained after being held at a high temperature.

  The method for producing the polymer composition of the present invention is not particularly limited, and for example, each component is mixed using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer, and the like, for example, 100 to 250. It can be produced by mixing at a temperature in the range of ° C. Moreover, after dissolving each component in an organic solvent and mixing, you may manufacture by distilling off this organic solvent.

  The polymer composition of the present invention can be used as a material for an active energy ray-curable composition. The content of the (meth) acrylic block copolymers (I) and (II) in the active energy ray-curable composition is not particularly limited, but is preferably 5% by mass or more, and 10% by mass. More preferably, it is more preferably 20% by mass or more.

The active energy ray-curable composition 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) Carbonyl compounds such as -4-methoxybenzophenone, acrylated benzophenone), Michler ketones (for example, Michler ketone), and benzoins (for example, benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.); tetramethylthiuram monosulfide Sulfur compounds such as thioxanthones (eg, thioxanthone, 2-chlorothioxanthone, etc.); acylphosphine oxides (eg, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-) Phosphorus compounds such as trimethylbenzoyl) -phenylphosphine oxide, etc .; 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; azo compounds (for example, azobisisobutylnitrile and the like) and the like. Moreover, a photoinitiator may be used individually by 1 type, or may use 2 or more types together. Among these, acetophenones and benzophenones are preferable.

  When it contains a photopolymerization initiator, the content thereof is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic block copolymer (I) used in the present invention. 05-8 mass parts 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 said active energy ray curable composition may contain the sensitizer as needed. Examples of the sensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine, and diethylaminoethyl methacrylate. 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 has a reactive dilution that exhibits polymerizability by irradiation with active energy rays other than the (meth) acrylic block copolymer of the present invention, unless the effects of the present invention are impaired. An agent 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- Styrene derivatives such as t-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, isopropyl (meth) acrylate, n-butyl (meth) acrylate, amyl (meth) acrylate, (meth) Isobutyl acrylate, t-butyl (meth) acrylate, (meth) acrylic Pentyl, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Nonyl acid, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, (meth) acrylic Benzyl acid, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth ) 4-butylcyclohexyl acrylate, (meth) a 2-hydroxyethyl crylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic Butoxyethyl acid, ethoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol monoester (meth) acrylate, polypropylene glycol monoester (meth) acrylate, methoxyethylene glycol (meth) acrylate, ( (Meth) acrylic acid ethoxyethyl, (meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol, (meth) acrylic acid dimethylaminoethyl, (meth) acrylic acid die Ruaminoethyl, 7-amino-3,7-dimethyloctyl (meth) acrylate, 4- (meth) acryloylmorpholine, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyl dimethanol 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) Chryrate, bisphenol A diglycidyl ether end (meth) acrylic acid adduct, pentaerythritol tetra (meth) acrylate, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5 -Trisethanol tri (meth) acrylate, N, N'-bis [2-((meth) acryloyloxy) ethyl] -N "-(2-hydroxyethyl) -1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, tricyclodecanedimethanol di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, ethylene oxide of hydrogenated bisphenol A Or di (meth) a of diol which is adduct of propylene oxide Acrylate, epoxy (meth) acrylate with bisphenol A diglycidyl ether added with (meth) acrylate, and (meth) acrylic acid derivatives such as cyclohexanedimethanol di (meth) acrylate; bisphenol A type epoxy acrylate resin, phenol novolac Type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, etc .; carboxyl group-modified epoxy acrylate resin; polyol (polytetramethylene glycol, polyester diol of ethylene glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene Glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl group Hydroxyl-containing (meth) acrylates (hydroxyethyl (meta)) obtained from terminal polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) ) Urethane acrylate resins obtained by reaction with acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc .; (meth) acrylic groups introduced into the above polyols via ester bonds Polyester acrylate resin; Epoxy compounds such as epoxidized soybean oil and epoxy benzyl stearate. These reactive diluents may be used alone or in combination of two or more.

  The above active energy ray-curable composition does not impair the effects of the present invention, and does not significantly impair the curability, plasticizer, tackifier, softener, filler, stabilizer, pigment, Various additives that do not have an active energy ray-curable group such as a dye may be contained. These various additives may be used alone or in combination of two or more.

  As said plasticizer, the plasticizer contained in a polymer composition can be used, for example. When the plasticizer is contained in the active energy ray-curable composition, the content is 100 in total of the (meth) acrylic block copolymer (I) and the (meth) acrylic block copolymer (II). 5-150 mass parts is preferable with respect to 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 additive having no active energy ray-curable group may be an organic compound or an inorganic compound.

  The active energy ray used when the polymer composition of the present invention or the active energy ray-curable composition containing the polymer 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 10~20,000mJ / cm ^2, the range of 30~5,000mJ / cm ² is preferred. If it is less than 10 mJ / cm ^2, the curability of the (meth) acrylic block copolymer (I) tends to be insufficient, and if it exceeds 20,000 mJ / cm ² , the (meth) acrylic block copolymer ( I) and (II) may be deteriorated.

  The relative humidity when irradiating active energy rays to the polymer composition of the present invention or the active energy ray-curable composition containing the polymer composition is (meth) acrylic block copolymer (I ) And (II) from the viewpoint of suppressing decomposition, it is preferably 30% or less, and more preferably 10% or less.

  The polymer composition of the present invention or the active energy ray-curable composition containing the polymer composition is further heated during or after active energy ray irradiation to accelerate curing as necessary. You can also 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 adhesive comprising the polymer composition or active energy ray-curable composition of the present invention can be used for various applications. Moreover, the adhesive layer which consists of this adhesive composition can be used by itself as an adhesive sheet, and the laminated body containing this adhesive layer can also be applied to various uses. For example, for surface protection, masking, shoes, binding, packaging / packaging, office, labeling, decoration / display, bookbinding, bonding, dicing tape, sealing, anticorrosion / waterproof, medical・ For hygiene, glass scattering prevention, electrical insulation, electronic equipment holding and fixing, semiconductor manufacturing, optical display film, adhesive adhesive optical film, electromagnetic wave shield or electrical / electronic component sealing material An adhesive, an adhesive tape, a film, etc. are mentioned.

  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 synthesis examples, the raw material was dried and purified by a conventional method, degassed with nitrogen, and transferred and supplied under a nitrogen atmosphere.
[Monomer consumption rate]
In the following synthesis 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, mixing 0.1 mL from the mixture, ¹ H-NMR measurement was carried out under the following measurement conditions after dissolving in 0.5 mL of chloroform, and a peak derived from a proton directly connected to a carbon-carbon double bond of (meth) acrylic acid ester used as a monomer ( (Chemical shift value 5.79-6.37 ppm) and calculated from the change in the ratio of the integral value of the peak (chemical shift value 7.00-7.38 ppm) derived from the proton directly linked to the aromatic ring of toluene used as the solvent. .

⁽¹ H-NMR measurement conditions)
Equipment: Nuclear magnetic resonance equipment “JNM-ECX400” manufactured by JEOL Ltd.
Temperature: 25 ° C
[Number average molecular weight (Mn), molecular weight distribution (Mw / Mn)]
In the following synthesis examples, GPC (gel permeation chromatography) measurement of the obtained polymer is performed under the following measurement conditions, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) values in terms of standard polystyrene Asked.

(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)
[Synthesis Example 1]
(Process (1))
After 1,800 g of toluene was added to a 5 L flask which had been dried and purged with nitrogen, the solution in the flask was further stirred and 1.8 g of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine was added. And 36 g of a toluene solution containing 23% by mass of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum were sequentially added, and then cooled to −30 ° C. To this was added 5.0 g of a cyclohexane solution containing 9% by mass of sec-butyllithium, and then 5.0 g of 1,1-dimethylpropane-1,3-diol dimethacrylate (hereinafter abbreviated as DMA) as a monomer. And 9.2 g of a mixture of 4.2 g of methyl methacrylate (hereinafter abbreviated as MMA) were added all at once to initiate anionic polymerization. Subsequently, the reaction solution was stirred at −30 ° C. for 12 hours, and the reaction solution was sampled.

  The consumption rate of DMA and MMA in step (1) was 100%.

(Process (2))
Subsequently, while stirring the reaction solution at −30 ° C., 250 g of 2-methoxyethyl acrylate (hereinafter abbreviated as 2-MEA) and 250 g of 2-ethylhexyl acrylate (hereinafter abbreviated as 2-EHA) as monomers. Was added at a rate of 8 g / min. The reaction solution was sampled immediately after completion of the monomer addition.

  The consumption rate of 2-MEA and 2-EHA in the step (2) was 100%.

(Process (3))
Subsequently, 9.0 g of a mixture of 5.0 g of DMA and 4.0 g of MMA was added as a monomer while stirring the reaction solution at −30 ° C., and then the temperature was raised to 25 ° C. The reaction mixture was sampled 300 minutes after the addition of the mixture.

  The consumption rate of DMA and MMA in step (3) was 100%.

(Process (4))
Subsequently, while stirring the reaction solution at 25 ° C., 40 g of methanol was added to stop the anionic polymerization, and the methacrylic polymer block (A) -acrylic polymer block (B) -methacrylic polymer block (A). A solution containing (meth) acrylic block copolymer (I), which is a triblock copolymer bonded in the order of (ABA), was obtained. The Mn of the (meth) acrylic block copolymer (I) sampled from such a solution was 95,000 and Mw / Mn was 1.23.

(Process (5))
Next, the obtained solution was poured into 5,000 g of methanol to precipitate an oily precipitate. The oily precipitate was collected and then dried to obtain 410 g of a (meth) acrylic block copolymer (hereinafter referred to as “(meth) acrylic block copolymer (I-1)”). Table 1 shows the solubility parameter (SP (B)) of the polymer block (B) of the (meth) acrylic block copolymer (I-1).
[Synthesis Examples 2 and 3]
A (meth) acrylic block copolymer (I) was obtained by the same method as in Synthesis Example 1 except that the amount of reagent used was changed as shown in Table 1. Table 1 shows the number average molecular weight (Mn), molecular weight distribution (Mw / Mn), and solubility parameter (SP (B)) of the polymer block (B) of the polymers obtained in each synthesis example. The (meth) acrylic block copolymers obtained in Synthesis Examples 2 and 3 are (meth) acrylic block copolymers (I-2) and (meth) acrylic block copolymers (I-), respectively. 3).
[Synthesis Example 4]
(1) After replacing the inside of the 2 L three-necked flask with nitrogen, 870 g of toluene and 44 g of 1,2-dimethoxyethane were added while stirring at room temperature, followed by isobutylbis (2,6-di-t- 60 g of a toluene solution containing 23% by mass of butyl-4-methylphenoxy) aluminum was added, and 3.0 g of a cyclohexane solution of sec-butyllithium containing 9% by mass of sec-butyllithium was further added.
(2) Subsequently, 36 g of MMA was added thereto and stirred at room temperature for 60 minutes.
(3) Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., 240 g of n-butyl acrylate (hereinafter abbreviated as “nBA”) was added dropwise over 2 hours, and after completion of the addition, at −30 ° C. for 5 minutes. Stir.
(4) Furthermore, MMA36g was added to this, and it stirred at room temperature overnight.
(5) After adding 5 g of methanol to stop the polymerization reaction, the obtained reaction solution was poured into 1500 g of methanol to deposit a precipitate. Thereafter, the precipitate is collected and dried to obtain 310 g of (meth) acrylic block copolymer (II) (hereinafter referred to as “(meth) acrylic block copolymer (II-1)”). Obtained. As a result of performing GPC measurement and ¹ H-NMR measurement on the (meth) acrylic block copolymer (II-1), the number average molecular weight (Mn) was 67,900, and the molecular weight distribution (Mw / Mn) was 1. .13. The content ratio of each polymer block was 23 mass% for the PMMA block (polymer block (C)) and 77 mass% for the PnBA block (polymer block (D)).
[Synthesis Example 5]
Polymerization was carried out in the same manner as in Synthesis Example 4 except that the amount ratio of the monomers and the amount of the initiator were changed to obtain a (meth) acrylic block copolymer (II-2). The number average molecular weight (Mn) was 92,000, and the molecular weight distribution (Mw / Mn) was 1.20. The content ratio of each polymer block was 23 mass% for the PMMA block (polymer block (C)) and 77 mass% for the PnBA block (polymer block (D)).
[Synthesis Example 6]
Polymerization was carried out in the same manner as in Synthesis Example 4 except that the amount ratio of the monomers and the amount of the initiator were changed to obtain a (meth) acrylic block copolymer (II-3). The number average molecular weight (Mn) was 135,600, and the molecular weight distribution (Mw / Mn) was 1.14. Moreover, the content ratio of each polymer block was 16 mass% for the PMMA block (polymer block (C)) and 84 mass% for the PnBA block (polymer block (D)).
[Synthesis Example 7]
The interior of the 2 L three-necked flask was purged with nitrogen, then 870 g of toluene and 44 g of 1,2-dimethoxyethane were added at room temperature, followed by isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum 23 31 g of toluene solution containing mass% was added, and 3.0 g of a mixed solution of cyclohexane and n-hexane containing 9 mass% of sec-butyllithium was further added. Next, 22 g of MMA was added thereto and stirred at room temperature for 60 minutes. At this time, the polymerization conversion rate of MMA was 99.9% or more. Subsequently, the internal temperature of the polymerization liquid was cooled to −30 ° C., 288 g of nBA was added dropwise over 2 hours, and after completion of the addition, the mixture was stirred at −30 ° C. for 5 minutes, and then 5 g of methanol was added to stop the polymerization reaction. At this time, the polymerization conversion rate of nBA was 99.9% or more. The obtained reaction solution was poured into 1500 g of methanol to precipitate an oily precipitate. The oily precipitate was collected and dried to obtain 310 g of a diblock copolymer composed of PMMA-PnBA (hereinafter referred to as “(meth) acrylic block copolymer (II-4)”). As a result of GPC measurement and ¹ H-NMR measurement of the (meth) acrylic block copolymer (II-4), the number average molecular weight (Mn) was 55,400, and the molecular weight distribution (Mw / Mn) was 1. .21. The content ratio of each polymer block was 7 mass% for the PMMA block (polymer block (C)) and 93 mass% for the PnBA block (polymer block (D)).

Examples and comparative examples are described below.
[Preparation of cured sample]
The active energy ray-curable compositions prepared in the following Examples and Comparative Examples are placed on an alkali-free glass (OA-10G, 0.7 mmt), and a PET film (A4100, 125 μm) is placed thereon, and the entire glass is 100. The film was bonded using a roller so that the adhesive layer had a thickness of 100 μm while being heated to ° C. Using the UV irradiation device (GS Yuasa Co., Ltd., 12A12-A10-HD3A, lamp used: GS Yuasa Co., Ltd., MAK125AL-F metal halide lamp), the accumulated irradiating composition sample was 2,000 mJ. A cured product sample was obtained by UV irradiation so as to be / cm ² .
[Appearance evaluation]
The appearance of the cured product sample was visually evaluated.

○: Unevenness or white turbidity of the cured product ×: Unevenness or white turbidity of the cured product [180 ° peeling adhesive strength]
After the cured material sample was cut out to a width of 25 mm, the 180 ° peel adhesion was measured at a peel rate of 300 mm / min.
[180 ° peel adhesion after heat resistance test]
The same sample as that measured for the peel adhesive strength was put into a dryer at 85 ° C. for 500 hours, and the peel adhesive strength was measured in the same manner.
[Examples 1-10, Comparative Examples 1-2]
(1) (Meth) acrylic block copolymers (I-1) to (I-3) and (meth) acrylic block copolymers (II-1) to (II) produced in Synthesis Examples 1 to 7 above. II-4), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184) as a radical polymerization initiator, and rosin resin (manufactured by Harima Chemical Group Co., Ltd., Harrier Star TF) as a tackifier. The active energy ray-curable composition was dissolved in toluene at the mass ratios shown in Tables 3 and 4 below to prepare a toluene solution containing a polymer composition of 30% by mass, and the solvent was distilled off. Obtained.

  (2) For the cured product of the active energy ray-curable composition obtained in (1) above, the evaluation results of appearance, 180 ° peel adhesion, and 180 ° peel adhesion after the heat resistance test are shown in Table 3 and Table 3. 4 shows.

  As shown in Tables 3 and 4, the (meth) acrylic block copolymer (I) [(I-1) to (I-2)] and the (meth) acrylic block copolymer (II) [(II -1) to (II-4)] in an amount within the range specified in the present invention, the cured product obtained by curing the active energy ray-curable compositions of Examples 1 to 8 is (meta) Compared with the hardened | cured material of the comparative example 1 manufactured using the active energy ray hardening composition which consists only of acrylic type block copolymer (I), the glass adhesive force was improved. In addition, no significant decrease in glass adhesion was observed after the heat resistance test.

  On the other hand, as shown in Example 9, the solubility parameter (SP (B)) and (meth) acrylic of the polymer block (B) in the (meth) acrylic block copolymer (I) [(I-3)]. If the difference between the solubility parameter (SP (D)) of the polymer block (D) in the system block copolymer (II) [(II-1)] is not within the preferred range specified in the present invention, the compatibility is It was low and became cloudy when cured. As shown in Example 10, mass ratio of (meth) acrylic block copolymer (I) [(I-1)] and (meth) acrylic block copolymer (II) [(II-1)] When (I) / (II) is less than 50.0 / 50.0, the initial glass adhesive strength is improved, but the glass adhesive strength after the heat resistance test tends to be reduced. Moreover, as shown in Comparative Example 2, when a rosin resin was used instead of the (meth) acrylic block copolymer (II), a bleedout phenomenon occurred in the obtained cured product, and after the heat resistance test A significant decrease in glass adhesion was observed.

  The cured product of the polymer composition or active energy ray-curable composition of the present invention does not cause a bleed-out phenomenon and is excellent in long-term stability of adhesive force. For example, as an optical adhesive used in various displays Useful.

Claims (6)

A methacrylic polymer block (A) having an active energy ray-curable group containing a partial structure (1) represented by the following general formula (1), and a (meth) acrylic polymer having no active energy ray-curable group A (meth) acrylic block copolymer (I) comprising a combined block (B), at least one polymer block (C) comprising a methacrylic ester unit, and at least one polymer comprising an acrylic ester unit A (meth) acrylic block copolymer (II) comprising the polymer block (D) and not having the partial structure (1) represented by the general formula (1),
A polymer composition containing

(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)   In the (meth) acrylic block copolymer (I) and the (meth) acrylic block copolymer (II), the glass transition temperature of the polymer block (A) and the polymer block (C) is 90 ° C. or higher. The polymer composition according to claim 1, wherein the polymer block (B) and the polymer block (D) have a glass transition temperature of 30 ° C. or lower.   The solubility parameter (SP (B)) of the polymer block (B) in the (meth) acrylic block copolymer (I) and the polymer block (D) in the (meth) acrylic block copolymer (II) ) In the solubility parameter (SP (D)) is −0.5 or more and 0.5 or less, the polymer composition according to claim 1 or 2.   The mass ratio (I) / (II) between the (meth) acrylic block copolymer (I) and the (meth) acrylic block copolymer (II) is 99.9 / 0.1 to 50.0. The polymer composition according to any one of claims 1 to 3, which is /50.0.   An active energy ray-curable composition containing the polymer composition according to claim 1.   Hardened | cured material obtained by hardening | curing the polymer composition in any one of Claims 1-4, or the active energy ray-curable composition of Claim 5.