TW201734068A - (meth)acrylic block copolymer - Google Patents

Abstract

Provided is a highly curable (meth)acrylic block copolymer, of which the cured product, obtained by irradiation with an actinic energy ray, has excellent stretchability and lacks tackiness. This (meth)acrylic block copolymer contains: a methacrylic polymer block (A) having an actinic energy ray-curable group including a partial structure (1) represented by general formula (1) below; and a (meth)acrylic polymer block (B) which does not have any actinic energy ray-curable groups, wherein the content of the partial structure (1) is 0.3-5.0 mole% with respect to the entirety of the monomer units constituting the (meth)acrylic block copolymer, the content of the methacrylic polymer block (A) in the (meth)acrylic block copolymer is 30-60 mass%, and the number average molecular weight of the (meth)acrylic block copolymer is 40,000 or greater. (In formula (1), R1 represents a hydrogen atom or a hydrocarbon group having 1-20 carbon atoms).

Description

(meth)acrylic block copolymer

The present invention relates to a (meth)acrylic block copolymer which is obtained by irradiating an active energy ray with a cured product which is excellent in stretchability and has no adhesive feeling.

Conventionally, an active energy ray-curable material which is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam has been known, and has been used for an adhesive, an adhesive, a paint, an ink, a coated material, a light-formed material, and a shadow. Use of materials, lining materials, etc.

Among them, the active energy ray-curable composition containing a (meth)acrylic block copolymer having an active energy ray-curable group is excellent in adhesiveness, moldability, weather resistance, etc., and can be expected by utilizing these characteristics. The usefulness of the use of adhesives, adhesives, inks, coating materials, masking materials, lining materials, various molding materials, and the like has been discussed.

For example, an active energy ray-curable composition containing a (meth)acrylic block copolymer which is obtained by polymerizing n-butyl acrylate is known by the following: After forming the acrylic polymer block, methyl methacrylate and 2-hydroxyethyl methacrylate are copolymerized to form a hydroxyl group-containing methacrylic polymer block, so that the obtained block copolymer has The hydroxy group is reacted with a chlorinated propylene group to introduce an acrylonitrile group which is an active energy ray-curable group (see Patent Document 1).

Further, an active energy ray-curable composition containing a (meth)acrylic block copolymer obtained by using methyl methacrylate is known. After copolymerizing with 1,1-dimethylpropane-1,3-diol dimethacrylate to form a methacrylic polymer block into which a methacrylic acid group which is an active energy ray-curable group is introduced, An acrylic polymer block is formed by polymerizing n-butyl acrylate (see Patent Document 2).

However, the conventional active energy ray-curable composition is difficult to obtain a toughened hardened material system in a technical field requiring high toughness and toughness. In particular, a material for forming a film such as an ink or a paint is expected to have an elongation and a toughness, and it is not necessary to have a feeling of adhesion (see Patent Document 3).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2011-184678

Patent Document 2 International Publication No. 2014/148251

Patent Document 3 Japanese Patent Laid-Open Publication No. 2015-81294

The present invention has an object of providing a (meth)acrylic block copolymer having excellent curability, and the cured product obtained by irradiating an active energy ray is an active energy ray hardening which is excellent in extensibility and has no adhesive feeling. Sexual composition.

According to the present invention, the above object can be attained by providing the following: [1] A (meth)acrylic block copolymer comprising: a partial structure comprising the following formula (1) (1) (active) energy ray-curable group methacrylic polymer block (A) and (meth)acrylic polymer block (B) without active energy ray-curable group (meth)acrylic acid a block copolymer in which the content of the partial structure (1) is 0.3 mol% or more and 5.0 mol% or less, based on the all monomer unit constituting the (meth)acrylic block copolymer, (meth)acrylic acid The content of the methacrylic polymer block (A) in the block copolymer is 30% by mass or more and 60% by mass or less, and the number average molecular weight of the (meth)acrylic block copolymer is 40,000 or more;

(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms).

[2] An active energy ray-curable composition containing the (meth)acrylic block copolymer of [1]; [3] A cured product obtained by curing the (meth)acrylic block copolymer of [1] or the active energy ray-curable composition of [2].

The (meth)acrylic block copolymer of the present invention is excellent in curability, and the active energy ray-curable composition containing the (meth)acrylic block copolymer is irradiated with an active energy ray. Excellent extensibility and no stickiness.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

In addition, in the present specification, "(meth)acrylic acid" means a general term for "methacrylic acid" and "acrylic acid", and "(meth)acrylic acid group" which will be described later means "methacrylic acid" and " The term "acryloyl acrylate" is a generic term for "methacrylate" and "acrylate".

The (meth)acrylic block copolymer of the present invention contains a methacrylic polymer block (A) and a (meth)acrylic polymer block (B), and the methacrylic polymer is embedded. Segment (A) has a partial configuration (1).

Part of the structure (1) exhibits polymerizability by irradiation with active energy rays. As a result, the active energy ray-curable composition containing the (meth)acrylic block copolymer of the present invention is cured to be a cured product by irradiation with an active energy ray. Moreover, in the present specification, active energy ray means light, electromagnetic waves, particle beams, and combinations thereof. As light, ultraviolet rays, ultraviolet rays (UV), and near ultraviolet rays can be cited. Examples of the electromagnetic wave include X-rays and γ-rays, and examples of the particle beam include an electron beam (EB), a proton beam (α-ray), and a neutron beam. From the viewpoints of the curing speed, the availability of the irradiation device, the price, and the like, among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable.

Part of the structure (1) is represented by the following formula (1).

(In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms).

In the above formula (1), the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. Second butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 3-ethylbutyl, 2,2-dimethylbutyl, 2, An alkyl group such as 3-dimethylbutyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, n-decyl or the like; cyclopropyl, cyclobutyl, cyclo a cycloalkyl group such as a pentyl group or a cyclohexyl group; an aryl group such as a phenyl group or a naphthyl group; or an aralkyl group such as a benzyl group or a phenylethyl group. Among them, a hydrogen atom, a methyl group, and an ethyl group are preferred from the viewpoint of active energy ray curability, and a methyl group is preferred.

The partial structure (1) in the methacrylic polymer block (A) of the present invention is a partial structure represented by the following general formula (2) from the viewpoint of the curing rate (hereinafter referred to as "partial structure (2)" One part is preferred.

(In the formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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).

In the above formula (2), specific examples and preferred examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include the same hydrocarbon groups as those of R ^{1 of the} above formula (1).

In the above formula (2), the hydrocarbon group having 1 to 6 carbon atoms independently represented by R ² and R ³ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. Isobutyl, second butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 3-ethylbutyl, 2,2-dimethylbutyl Alkyl group, 2,3-dimethylbutyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, etc.; cyclopropyl, cyclobutyl, ring a cycloalkyl group such as a pentyl group or a cyclohexyl group; an aryl group such as a phenyl group; and the like. Among them, a methyl group and an ethyl group are preferred from the viewpoint of active energy ray hardenability, and a methyl group is most preferable.

In the above 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 the ease of polymerization control, and O is preferred. In the case where 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, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , second butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 3-ethylbutyl, 2,2-dimethylbutyl, 2 , an alkyl group such as 3-dimethylbutyl, n-pentyl, neopentyl, n-hexyl, 2-methylpentyl or 3-methylpentyl; cyclopropyl, cyclobutyl, cyclopentyl, a cycloalkyl group such as a cyclohexyl group; a phenyl group or the like.

In the above formula (2), the integer of 1 to 20 represented by n is preferably 2 to 5 from the viewpoints of fluidity and curing rate of the (meth)acrylic block copolymer.

The content of the partial structure (1) is 0.3 mol% or more and 5.0 mol% or less based on the all monomer unit constituting the (meth)acrylic block copolymer of the present invention. When the content of the partial structure (1) is in the above range, the obtained cured product is excellent in stretchability and does not have an adhesive feeling. The obtained cured product tends to have more excellent elongation and less adhesiveness, and the content of the partial structure (1) is preferably 0.4 mol% or more and 4.5 mol% or less, and 0.5 mol% or more and 4.0 mol. It is more preferable that the ear% or less is less than 0.5 mol% or more and 3.5 mol% or less.

The partial structure (1) contained in the methacrylic polymer block (A) may be at the end of the methacrylic polymer block or in the side chain, but may be formed by introducing a portion having a preferred content (1) The point of view, at least in the side chain is preferred.

The methacrylic polymer block (A) contains a monomer unit derived from a monomer containing a methacrylate. The methacrylate type can be roughly classified into a monofunctional methacrylate having one methacryl fluorenyl group and a polyfunctional methacrylate having two or more methacryl fluorenyl groups.

Examples of the above monofunctional methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methyl group. Tert-butyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, 2-methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, trimethoxydecyl propyl methacrylate, 2-aminoethyl methacrylate, N,N-dimethylamine methacrylate Ethyl ethyl ester, N,N-diethylaminoethyl methacrylate, phenyl methacrylate, naphthyl methacrylate, 2-(trimethyldecyloxy)ethyl methacrylate, methyl 3-(Trimethyldecyloxy)propyl acrylate, glycidyl methacrylate, γ-(methacryloyloxypropyl)trimethoxydecane, ethylene oxide addition of methacrylic acid , trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-Perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, methacrylic acid 2-Perfluoromethyl-2-perfluoroethyl methyl ester, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecyl methacrylate Ethyl ester and the like. Among these, there are carbon number such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and butyl methacrylate. The alkyl methacrylate of 1 to 5 alkyl groups is preferred.

From the above monofunctional methacrylate (for example, methacrylic) relative to the all monomer unit of the methacrylic polymer block (A) The content of the monomer unit of the acid methyl ester is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint that the cured product does not have a feeling of adhesion. Moreover, the content of the monomer unit derived from the monofunctional methacrylate is a case where the methacrylic polymer block (A) is contained in a plurality of (meth)acrylic block copolymers, and Each of the polymer blocks is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.

In addition, when the bifunctional methacrylate represented by the following formula (3) (hereinafter referred to as "dimethacrylate (3)")) is used as the polyfunctional methacrylate, the conditions described later are used. By selective polymerization with a methacryl oxime group (methacryl fluorenyl group directly bonded to "O(CH ₂ ) _n " in the following general formula (3)) by living anionic polymerization, The methacrylic polymer block (A) having a partial structure (2) is preferred.

(In the 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), the hydrocarbon group R of Example ² and carbon atoms represented by R ³ of 1-6, R & lt include the general formula (2) ² and R ³ of the same hydrocarbon. In the above formula (3), the 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.

Specific examples of the dimethacrylate (3) include, for example, 1,1-dimethylpropane-1,3-diol dimethacrylate and 1,1-dimethylbutane-1. , 4-diol dimethacrylate, 1,1-dimethylpentane-1,5-diol dimethacrylate, 1,1-dimethylhexane-1,6-diol II Methacrylate, 1,1-diethylpropane-1,3-diol dimethacrylate, 1,1-diethylbutane-1,4-diol dimethacrylate, 1, 1-diethylpentane-1,5-diol dimethacrylate, 1,1-diethylhexane-1,6-diol dimethacrylate, etc., 1,1-dimethyl Propane-1,3-diol dimethacrylate, 1,1-dimethylbutane-1,4-diol dimethacrylate, 1,1-dimethylpentane-1,5- Diol dimethacrylate, 1,1-dimethylhexane-1,6-diol dimethacrylate, 1,1-diethylpropane-1,3-diol dimethacrylate 1,1-diethylbutane-1,4-diol dimethacrylate, 1,1-diethylpentane-1,5-diol dimethacrylate, and 1,1- Diethyl hexane-1,6-diol dimethacrylate is 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 is more preferred.

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

The content of the monomer unit derived from the polyfunctional methacrylate is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total monomer units of the methacrylic polymer block (A). The mass % or more is further preferable. Further, a monomer derived from a polyfunctional methacrylate relative to all monomer units of the methacrylic polymer block (A) The content of the unit is preferably 0.5% by mass or more, more preferably 5% by mass or more, and still more preferably 45% by mass or more. Further, in the case where the polyfunctional methacrylate has a dimethacrylate (3), it is derived from dimethacrylate (3) with respect to all the monomer units of the methacrylic polymer block (A). The content of the monomer unit is preferably in the range of 0.1 to 40% by mass, more preferably in the range of 1 to 30% by mass, even more preferably in the range of 2 to 20% by mass. Further, the polyfunctional methacrylate is in the case of containing the dimethacrylate (3), and is derived from the dimethacrylate (3) with respect to all the monomer units of the methacrylic polymer block (A). The content of the monomer unit is preferably in the range of 0.5 to 70% by mass, more preferably in the range of 5 to 65% by mass, and still more preferably in the range of 45 to 60% by mass.

The methacrylic polymer block (A) is formed from a monomer containing a monofunctional methacrylate and a polyfunctional methacrylate, and the content of the monomer unit derived from the monofunctional methacrylate is derived from The total content of the monomer units of the polyfunctional methacrylate is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, and may be 100% by mass. Further, the methacrylic polymer block (A) is formed of a monomer containing methyl methacrylate and dimethacrylate (3), relative to a methacrylic polymer block ( The total amount of monomer units of A), the content of monomer units derived from methyl methacrylate and the content of monomer units derived from dimethacrylate (3), is embedded with respect to the methacrylic polymer All of the monomer units of the segment (A) are preferably in the range of 80 to 100% by mass, more preferably in the range of 90 to 100% by mass, and further in the range of 95 to 100% by mass. Good, can be 100% by mass. Further, in the case where the (meth)acrylic block copolymer contains a plurality of methacrylic polymer blocks (A), each of the polymer blocks has the above preferred range, and preferably more A good range is one of the preferred aspects.

The methacrylic polymer block (A) may have a monomer unit derived from a monomer other than the above methacrylate. As the other monomer, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tributyl acrylate, cyclohexyl acrylate, acrylic acid 2- Ethylhexyl ester, isodecyl acrylate, dodecyl acrylate, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl (meth) acrylate, trimethoxy decyl acrylate Propyl ester, 2-aminoethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, phenyl acrylate, naphthalene acrylate, acrylic acid 2-(three Methyl decyloxy)ethyl ester, 3-(trimethyldecyloxy)propyl acrylate, glycidyl acrylate, γ-(acrylenyloxypropyl)trimethoxynonane, ring of acrylic acid Oxyethane adduct, trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl acrylate Ester, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl acrylate Acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecyl acrylate, etc.; α-methoxy acrylate, α-ethoxy Alpha-alkoxy acrylate such as methyl acrylate; butenoate such as methyl crotonate or ethyl crotonate; 3-alkoxy acrylate such as 3-methoxy acrylate; Isopropyl (meth) propylene oxime Amine, n-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc. (methyl) Acrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, methyl 2-bromomethyl acrylate, ethyl 2-bromomethacrylate, methyl vinyl Ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone, and the like. These other single systems 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% by mass or less, and more preferably 5% by mass or less based on the total monomer unit of the methacrylic polymer block (A). Further, the content of the monomer unit formed by the other monomer described above is in the case where the methacrylic polymer block (A) is contained in a plurality of (meth)acrylic block copolymers, respectively. Each of the polymer blocks is preferably 10% by mass or less, and more preferably 5% by mass or less.

The number average molecular weight (Mn _A ) of the methacrylic polymer block (A) is preferably in the range of 12,000 to 120,000 from the viewpoints of handleability, fluidity, and mechanical properties of the obtained block copolymer. It is better in the range of 15,000 to 60,000. In the case where the methacrylic polymer block (A) is a plurality of (meth)acrylic block copolymers, the number average molecular weight of each polymer block is in the above preferred range, and preferably in a better range. It is a better aspect. Moreover, in the present specification, the number average molecular weight and the molecular weight distribution described later are values measured by a colloidal permeation chromatography (GPC) method (standard polystyrene conversion).

The content of the methacrylic polymer block (A) in the (meth)acrylic block copolymer of the present invention is 30% by mass or more and 60% by mass or less. By obtaining the content of the polymer block (A) in the above range, The cured product has excellent extensibility and becomes non-sticky. The obtained cured product tends to have excellent elongation and a less adhesive feeling, and the content of the polymer block (A) is preferably 32.5 mass% or more and 57.5 mass% or less, and preferably 35 mass% or more and 55 mass% or less. For better.

The (meth)acrylic block copolymer of the present invention contains a (meth)acrylic polymer block (B) having no active energy ray-curable group.

Further, in the present specification, the active energy ray-curable group means a functional group which exhibits polymerizability by irradiation with the above-mentioned active energy ray. Examples of the active energy ray-curable group include (meth)acryl fluorenyl group, (meth)acryl fluorenyloxy group, vinyl group, allyl group, vinyloxy group, and 1,3-dienyl group. a functional group having an ethylenic double bond (especially an ethylenic double bond represented by the formula CH ₂ =CR- (wherein R is an alkyl group or a hydrogen atom); an epoxy group or an oxygen ring; Oxetanyl, thiol, maleimine, and the like.

Examples of the (meth) acrylate which can form the (meth)acrylic polymer block (B) include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. N-propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, isodecyl (meth)acrylate, dodecyl (meth)acrylate, trimethoxydecylpropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate Ester, N,N-diethylaminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (A) 2-(trimethyldecyloxy)ethyl acrylate, (meth)acrylic acid A monofunctional (meth) acrylate such as 3-(trimethyldecyloxy)propyl ester. Among them, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferred, and n-butyl acrylate is more preferred. These (meth) acrylates may be used alone or in combination of two or more.

The content of the monomer unit formed by the (meth) acrylate in the (meth)acrylic polymer block (B) is relative to the total amount of the (meth)acrylic polymer block (B) formed. The monomer unit is preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass. In addition, when the (meth)acrylic polymer block (B) is contained in a plurality of (meth)acrylic block copolymers, the content of the monomer unit formed of the (meth) acrylate is plural. Each of the polymer blocks is preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass.

The (meth)acrylic polymer block (B) may be a monomer unit having a monomer other than (meth) acrylate. Examples of the other monomer include α-alkoxy acrylate such as α-methoxy acrylate or α-ethoxy acrylate; methyl crotonate, ethyl crotonate, and the like. Butenoate; 3-alkoxy acrylate such as 3-methoxy acrylate; N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N,N-dimethyl(meth)acrylamide, (meth)acrylamide such as N,N-diethyl(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 above other monomer in the (meth)acrylic polymer block (B) is relative to all the monomers forming the (meth)acrylic polymer block (B) Body unit, 10% by mass Preferably, it is more preferably 5% by mass or less. Further, in the case where the (meth)acrylic polymer block (B) is contained in a plurality of (meth)acrylic block copolymers, the content of the monomer unit formed by the other monomer is Each of the polymer blocks is preferably 10% by mass or less, more preferably 5% by mass or less.

The number average molecular weight (MnB) of the (meth)acrylic polymer block (B) is from 16,000 to 140,000 from the viewpoints of workability, fluidity, and mechanical properties of the obtained (meth)acrylic block copolymer. The range is preferably in the range of 20,000 to 70,000. When the (meth)acrylic polymer block (B) is contained in a plurality of (meth)acrylic block copolymers, the number average molecular weight of each polymer block is preferably in the above preferred range, and is preferably better. The range is a better aspect.

The content of the (meth)acrylic polymer block (B) in the (meth)acrylic block copolymer of the present invention is preferably 40% by mass or more and 70% by mass or less, and more preferably 42.5% by mass or more and 67.55% by mass. More preferably, it is more preferably 45 mass% or more and 65 mass% or less.

The (meth)acrylic block copolymer of the present invention has a number average molecular weight (Mn) of 40,000 or more. When the Mn is 40,000 or more, the cured product obtained from the block copolymer is excellent in elongation. The Mn is preferably 40,000 or more and 200,000 or less, and more preferably 45,000 or more and 100,000 or less, from the viewpoints of workability, fluidity, and mechanical properties of the obtained (meth)acrylic block copolymer.

The molecular weight distribution of the (meth)acrylic block copolymer of the present invention, that is, the weight average molecular weight/number average molecular weight is preferably 2.00 or less, and the range of 1.02 to 2.00 is more preferable, and the range of 1.05 to 1.80. Further preferably, the range of 1.05 to 1.50 is optimal, and may range from 1.10 to 1.50.

The (meth)acrylic block copolymer of the present invention has at least one methacrylic polymer block (A) and at least one (meth)acrylic polymer block (B). The block copolymer, the number of each polymer block, and the order of bonding are not particularly limited, but from the viewpoint of active energy ray hardenability, the methacrylic polymer block (A) forms a (meth)acrylic type. At least one terminal of the segment copolymer is preferred, and from the viewpoint of easiness of production of the (meth)acrylic block copolymer, a linear polymer is more preferable, and one methacrylic polymer is preferred. Two-block copolymer of block (A) combined with one (meth)acrylic polymer block (B), or both ends of one (meth)acrylic polymer block (B) Further, a triblock copolymer in which one methacrylic polymer block (A) is bonded is further preferred.

The method for producing the (meth)acrylic block copolymer in the present invention is not particularly limited, but an anionic polymerization method or a radical polymerization method is preferred, and from the viewpoint of controlling polymerization, living anionic polymerization or living radical polymerization The method is more preferred, and the living anionic polymerization method is further preferred.

The living radical polymerization method includes a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, and a polymerization method using a nitroxide radical (refer to International Publication No. 2004/ (No. 014926), a polymerization method using a high-period hetero-element compound such as an organic ruthenium compound (refer to Japanese Patent No. 3839829), and a reversible addition elimination chain transfer polymerization method (RAFT) (refer to Japanese Patent No. 3639859 ), atomic mobile radical polymerization (ATRP) According to Japanese Patent No. 3040172, International Publication No. 2004/013192, etc. Among these living radical polymerization methods, an atomic mobile radical polymerization method is preferred; an organohalide or a halogenated sulfonyl compound is used as a starter, and at least one selected from the group consisting of Fe, Ru, Ni, and Cu is used. An atomic mobile radical polymerization method in which a metal dislocation as a central metal is used as a catalyst is more preferable.

In the living anionic polymerization method, a method of livingly polymerizing an organic rare earth metal complex as a polymerization initiator is described (refer to Japanese Laid-Open Patent Publication No. Hei 06-93060), and an organic alkali metal compound is used as a polymerization initiator. A method for living anionic polymerization in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt (refer to Japanese Patent Publication No. Hei 05-507737), using an organic alkali metal compound as a polymerization initiation in the presence of an organoaluminum compound A method of active anionic polymerization is used (see Japanese Laid-Open Patent Publication No. Hei 11-335432, International Publication No. 2013/141105). Among these living anionic polymerization methods, the organic alkali metal compound is polymerized in the presence of an organoaluminum compound from the point where the (meth)acrylic block copolymer of the present invention can be directly and efficiently polymerized. A method of performing living anionic polymerization as a starting agent is preferred; and a method of living anionic polymerization using an organolithium compound as a polymerization initiator in the presence of an organoaluminum compound and a Lewis base is more preferable.

The above organolithium compound may, for example, be a third butyllithium, a 1,1-dimethylpropyllithium, a 1,1-diphenylhexyllithium or a 1,1-diphenyl-3-methyl group. Lithyl lithium, ethyl alpha-lithium isobutyrate, butyl alpha-lithium isobutyrate, methyl alpha-lithium isobutyrate, isopropyl lithium, second butyl lithium, 1- Methyl butyl lithium, 2-ethyl propyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, α-methylbenzyl lithium, methyl lithium, n-propyl lithium , n-butyl lithium, n-pentyl lithium, and the like. Among them, from the viewpoints of easiness of obtaining and anionic polymerization initiating ability, lithium isopropylate, second butyllithium, 1-methylbutyllithium, 1-methylpentyllithium, cyclohexyllithium, diphenyl An organolithium compound having 3 to 40 carbon atoms having a chemical structure of a secondary carbon atom as an anion center such as methyllithium or α-methylbenzyllithium is preferred, and second 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 is the number average molecular weight of the block copolymer according to the purpose, and can be determined depending on the ratio of the amount of the monomer used.

The organoaluminum compound represented by the following formula (A-1) or (A-2) is exemplified.

AlR ⁵ (R ⁶ )(R ⁷ ) (A-1)

(wherein R ⁵ represents a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, an aryloxy group or an N,N-disubstituted amine group, and R ⁶ and R ⁷ each independently represent an aryloxy group, Or R ⁶ and R ⁷ are bonded to each other to form a perylene dioxy group.

AlR ⁸ (R ⁹ )(R ¹⁰ ) (A-2)

(wherein R ⁸ represents an aryloxy group, and R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group or an N,N-disubstituted amine group).

In the above formulae (A-1) and (A-2), examples of the aryloxy group in which R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently represent a phenoxy group or a 2-methyl group. Phenoxy, 4-methylphenoxy, 2,6-dimethylphenoxy, 2,4-di-t-butylphenoxy, 2,6-di-t-butylphenoxy 2,6-di-t-butyl-4-methylphenoxy, 2,6-di-t-butyl-4-ethylphenoxy, 2,6-diphenylphenoxy, 1-naphthyloxy, 2-naphthyloxy, 9-phenanthryloxy, 1-decyloxy, 7-methoxy-2-naphthyloxy and the like.

In the above formula (A-1), examples of the exoardioxy group formed by bonding R ⁶ and R ^{7 to} each other include, for example, 2,2'-biphenol and 2,2'-methylene bisphenol. , 2,2'-methylenebis(4-methyl-6-tert-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-( -) A functional group for removing a hydrogen atom of the two phenolic hydroxyl groups in a compound having two phenolic hydroxyl groups such as -1,1'-bi-2-naphthol.

In addition, one or more hydrogen atoms contained in the above-mentioned aryloxy group and arylenedioxy group may be substituted by a substituent, and examples of the substituent include a methoxy group and an ethoxy group. An alkoxy group such as an isopropoxy group or a tert-butoxy group; a halogen atom such as a chlorine atom or a bromine atom; and the like.

In the above formulae (A-1) and (A-2), R ⁵ , R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group, and examples thereof include a methyl group, an ethyl group, and a positive C-propyl group. Alkanes such as isopropyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, n-octyl, 2-ethylhexyl Examples of the monovalent aromatic hydrocarbon group include an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and the like; and examples of the alkoxy group include an alkoxy group. For example, a methoxy group, an ethoxy group, an isopropoxy group, a third butoxy group, etc.; as the N,N-disubstituted amine group, for example, a dimethylamino group, a diethylamino group, a diiso group a dialkylamino group such as a propylamino group, a bis(trimethyldecyl)amino group or 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 amine group may be substituted by a substituent, and the substituent may be substituted. Examples thereof include alkoxy groups such as a methoxy group, an ethoxy group, an isopropoxy group, and a third butoxy group; and a halogen atom such as a chlorine atom or a bromine atom.

The above organoaluminum compound (A-1) may, for example, be ethylbis(2,6-di-tert-butyl-4-methylphenoxy)aluminum or ethylbis(2,6-di). -T-butylphenoxy)aluminum, ethyl[2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, isobutyl bis (2,6 -di-tert-butyl-4-methylphenoxy)aluminum, isobutylbis(2,6-di-t-butylphenoxy)aluminum, isobutyl [2,2'-sub-armor Bis(4-methyl-6-t-butylphenoxy)]aluminum, n-octylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, n-octyl Bis(2,6-di-t-butylphenoxy)aluminum, n-octyl[2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, Methoxybis(2,6-di-tert-butyl-4-methylphenoxy)aluminum, methoxybis(2,6-di-t-butylphenoxy)aluminum, methoxy [2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, ethoxybis(2,6-di-t-butyl-4-methylbenzene Oxy) aluminum, ethoxybis(2,6-di-t-butylphenoxy)aluminum, ethoxy[2,2'-methylenebis(4-methyl-6-tributyl) Phenyloxy)]aluminum, isopropoxy bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum, isopropoxy bis (2 ,6-di-t-butylphenoxy)aluminum, isopropoxy[2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, third Butoxy bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum, tert-butoxybis(2,6-di-t-butylphenoxy)aluminum, Tributoxy[2,2'-methylenebis(4-methyl-6-t-butylphenoxy)]aluminum, ginseng (2,6-di-t-butyl-4-methyl) Phenoxy)aluminum, ginseng (2,6-diphenylphenoxy) Base) aluminum and the like. Among them, isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, from the viewpoints of polymerization initiation efficiency, activity of polymerization terminal anion, ease of obtaining and handling, and the like, Isobutylbis(2,6-di-t-butylphenoxy)aluminum, isobutyl [2,2'-methylenebis(4-methyl-6-t-butylphenoxy) Aluminum or the like is preferred.

The above organoaluminum compound (A-2) may, for example, be diethyl (2,6-di-tert-butyl-4-methylphenoxy)aluminum or diethyl (2,6-di). -T-butylphenoxy)aluminum, diisobutyl(2,6-di-tert-butyl-4-methylphenoxy)aluminum, diisobutyl (2,6-di-third Butylphenoxy)aluminum, di-n-octyl (2,6-di-t-butyl-4-methylphenoxy)aluminum, di-n-octyl (2,6-di-third) Phenoxy group) aluminum or the like. These organoaluminum compounds may be used alone or in combination of two or more.

The amount of the organoaluminum compound to be used may be selected in accordance with the kind of the solvent, various other polymerization conditions, etc., but from the viewpoint of the polymerization rate, it is usually in the range of 1.0 to 10.0 mol with respect to the organolithium compound 1 mol. Preferably, the user is preferably in the range of 1.1 to 7.5 moles, and further preferably in the range of 1.2 to 5.0 moles. When the amount of the organoaluminum compound used is more than 10.0 mol per mol of the organolithium compound, the economical tendency tends to be unfavorable, and when it is less than 1.0 mol, the polymerization initiation efficiency tends to be lowered.

The Lewis base is exemplified by a compound 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 above Lewis base include an ether. With respect to the above ether, from the viewpoint of the height of the polymerization initiation efficiency and the activity of the polymerization terminal anion, the molecule has A cyclic ether having two or more ether bonds or an acyclic ether having one or more ether bonds in the molecule 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 groups such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole. Monoether; 1,2-dimethoxyethane, 1,2-diethoxyethane, 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 , 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane, 1,4-diisopropoxybutane, 1,4-two Acyclic diethers such as butoxybutane and 1,4-diphenoxybutane; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutyl glycol dimethyl ether, and Ethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutyl glycol diethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributyl glycol dimethyl ether, three Ethylene glycol diethyl ether, tripropylene glycol diethyl ether Tributyl glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, tetrabutyl glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, Acyclic polyether such as tetrabutyl glycol diethyl ether. Among them, from the viewpoints of suppression of side reactions, ease of availability, and the like, an acyclic ether having 1 or 2 ether bonds in the molecule is preferred, and diethyl ether or 1,2-dimethoxyethane is preferred. Better.

As the compound having a tertiary amine structure in the molecule used as the above Lewis base, a tertiary polyamine can be mentioned. The tertiary polyamine system means a compound having two or more tertiary amine structures in the molecule. As the tertiary polyamine, for example, N,N,N',N'-tetramethylethylidene diamine, N,N,N',N'-tetraethylethylenediamine, N may be mentioned. ,N,N',N",N"-pentamethyldiethylideneamine, 1,1,4,7,10,10-hexamethyltriethyltetramine, ginseng [2-(two a chain polyamine such as methylamino)ethyl]amine; 1,3,5-trimethylhexahydro-1,3,5-tri 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13, a non-aromatic heterocyclic compound such as 16-hexazacyclooctadecane; aromaticity such as 2,2'-bipyridyl, 2,2':6',2"-terpyridine (terpyridine) Heterocyclic compounds and the like.

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

These Lewis bases may be used alone or in combination of two or more.

The use amount of the Lewis base is preferably in the range of 0.1 to 6.0 moles, and the range of 0.2 to 4.0 moles is from the viewpoint of the polymerization initiation efficiency, the stability of the polymerization terminal anion, and the like, with respect to the organolithium compound 1 molar. More preferably, the range of 0.3 to 2.0 moles is further preferred. When the amount of the Lewis base is less than 6.0 mol with respect to the organic lithium compound, the economical tendency tends to be unfavorable, and when it is less than 0.1 mol, the polymerization initiation efficiency tends to be lowered.

Further, the amount of Lewis base used is preferably in the range of 0.1 to 0.6 mol with respect to the organoaluminum compound 1 mol, and more preferably in the range of 0.2 to 0.5 mol.

From the viewpoint of temperature control and homogenization in the system to carry out the smooth progress of the polymerization, it is preferred that the living anionic polymerization be carried out in the presence of an organic solvent. The organic solvent is toluene, xylene, cyclohexane, methylcyclohexane from the viewpoints of safety, separation from water in water washing of the reaction liquid after polymerization, recovery, ease of use, and the like. A hydrocarbon such as chloroform, dichloromethane or carbon tetrachloride; an ester such as dimethyl phthalate or the like is preferred. These organic solvents may be used alone or in combination of two or more. Moreover, it is preferable that the organic solvent is degassed in advance in the presence of an inert gas from the viewpoint of allowing the polymerization to proceed smoothly.

Further, in the above living anionic polymerization, other additives may be present in the reaction system as necessary. Examples of the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxylate and potassium t-butoxide; and tetraethylammonium chloride; Tetraethylphosphonium bromide and the like.

The living anionic polymerization is preferably carried out at -30 to 25 °C. When the temperature 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 activity of the monomer containing the above-mentioned dimethacrylate (3) tends to be difficult to carry out.

The living anionic polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen, argon or helium. Further, it is preferred to carry out the reaction under a sufficient stirring condition in such a manner that the reaction system is uniform.

In the above living anionic polymerization, an organolithium compound, an organoaluminum compound, a Lewis base, and a monomer are added to the reaction system. In the method, it is preferred that the Lewis base is added in contact with the organoaluminum compound before contact with the organolithium compound. Further, the organoaluminum compound may be added to the reaction system prior to the monomer, or may be added at the same time. When the organoaluminum compound and the monomer are simultaneously added to the reaction system, the organoaluminum compound may be additionally mixed with the monomer and added.

The living anionic polymerization system may be carried out by adding a polymerization stopper such as methanol, a methanol solution of acetic acid or hydrochloric acid, or a proton compound such as an aqueous solution of acetic acid or hydrochloric acid to the reaction liquid. The amount of the polymerization stopper used is usually in the range of 1 to 1,000 moles per mole of the organolithium compound used.

As a method of separating the block copolymer from the reaction liquid after the completion of the living anionic polymerization, a well-known method can be employed. For example, a method of injecting a reaction solution into a poor solvent of a block copolymer to precipitate it, a method of distilling off an organic solvent from a reaction liquid, and a method of obtaining a block copolymer may be mentioned.

In addition, when the metal component derived from the organolithium compound and the organoaluminum compound remains in the block copolymer obtained by the separation, the physical properties of the block copolymer may be lowered, and the transparency may be poor. Therefore, it is preferred to remove the metal component derived from the organolithium compound and the organoaluminum compound after termination of the anionic polymerization. As a method of removing the metal component, it is effective to use a cleaning treatment of an acidic aqueous solution, an adsorption treatment using an adsorbent such as an ion exchange resin, diatomaceous earth or activated carbon. Here, as the acidic aqueous solution, for example, hydrochloric acid, an aqueous sulfuric acid solution, an aqueous solution of nitric acid, an aqueous solution of acetic acid, an aqueous solution of propionic acid, an aqueous solution of citric acid or the like can be used.

In the production of the (meth)acrylic block copolymer of the present invention, the method of introducing the above partial structure (1) is carried out by polymerizing a monomer containing the above-mentioned dimethacrylate (3). In addition to the method of the methacrylic polymer block (A), a partial structure including a partial structure (1) which is an active energy ray-curable group (hereinafter referred to as "precursor structure" may be mentioned. After the polymer block, the precursor structure is converted into a partial structure (1). The polymer block system including the precursor structure can be obtained by polymerizing a monomer containing a polymerizable functional group and a precursor structure (hereinafter referred to as "polymerizable precursor"). The polymerizable functional group may, for example, be a styryl group, a 1,3-dienyl group, a vinyloxy group or a (meth)acrylonyl group, and a (meth)acrylonitrile group is preferred. Examples of the precursor structure include a hydroxyl group protected by a hydroxyl group and a protecting group (nonyloxy group, a nonyloxy group, an alkoxy group or the like), an amine group, and an amine group protected by a protective group. A thiol group and a thiol group protected by a protecting group, an isocyanate group or the like.

A polymer block system having a hydroxyl group as a precursor structure can form a methyl group by reacting a compound having a partial structure (carboxylic acid, ester, carbonyl halide, etc.) which reacts with a partial structure (1) and a hydroxyl group. Acrylic polymer block (A). Further, a polymer block having a hydroxyl group protected by a protecting group as a precursor structure is removed, and after the protective group is removed to form a hydroxyl group, the methacrylic polymer block (A) can be formed in the same manner.

A polymer block having an amine group as a precursor structure by a partial structure (carboxylic acid, carboxylic acid anhydride, ester, carbonyl halide, aldehyde group, isocyanate) having a partial structure (1) and an amine group reaction The compound of the group or the like is reacted to form a methacrylic polymer block (A). Further, a polymer block having an amine 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 an amine group.

A polymer block having a thiol group as a precursor can be constructed by reacting with a moiety having a reactivity with a partial structure (1) and a thiol group (carboxylic acid, an anhydride of an carboxylic acid, an ester, a carbonyl halide) A compound of an isocyanate group or a carbon-carbon double bond is reacted to form a methacrylic polymer block (A). Further, a polymer block having a thiol group protected by a protecting group as a precursor structure can be similarly formed into a methacrylic polymer block (A) after removing the protecting group to form a thiol group.

The polymer block structure having an isocyanate group as a precursor structure can be formed by reacting with a compound having a partial structure (hydroxy group or the like) capable of reacting with a partial structure (1) and an isocyanate group to form a methacrylic polymer block. (A).

In the production of the (meth)acrylic block copolymer of the present invention, the method of forming the methacrylic polymer block (A) is based on the viewpoint that the partial structure (1) can be easily introduced directly. A method of polymerizing a monomer containing dimethacrylate (3), typically a method of living anionic polymerization, is preferred.

The (meth)acrylic block copolymer of the present invention can be used as a material of an active energy ray-curable composition. In the active energy ray-curable composition, the content of the (meth)acrylic block copolymer of the present invention is not particularly limited, but preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass. The above is further preferred.

The active energy ray-curable composition may further contain a photopolymerization initiator. The photopolymerization initiator may, for example, be an acetophenone (for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1- Ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-1-butanone, etc., benzophenones (eg, benzophenone, benzhydrylbenzoic acid, hydroxybenzophenone, 3,3'-dimethyl-4- Methoxybenzophenone, propylene benzophenone, etc.), mischoketones (for example, mazinone, etc.) and benzoin (for example, benzoin, benzoin methyl ether, a carbonyl compound such as benzoin isopropyl ether or the like; a sulfur compound such as tetramethylthiuram monosulfide or thioxanthone (for example, thioxanthone or 2-chlorothioxanthone); Phosphine oxides (for example, 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc.) Phosphorus compound; ferrocene (for example, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)- a titanium compound such as phenyl)titanium or the like; an azo compound (for example, azobisisobutylnitrile or the like) or the like. Further, the photopolymerization initiator may be used singly or in combination of two or more. Among these, acetophenones and benzophenones are preferred.

In the case where the photopolymerization initiator is contained, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, per 100 parts by mass of the (meth)acrylic block copolymer of the invention. When the amount is 0.01 parts by mass or more, the curability of the active energy ray-curable composition is good, and the heat resistance of the cured product obtained at 10 parts by mass or less tends to be good.

Further, the active energy ray-curable composition may contain a sensitizer as necessary. As the sensitizer, there may be mentioned n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine, diethylaminoethyl methacrylate. Wait. Among these, diethylaminoethyl methacrylate and triethylamine are particularly preferable.

In the case where a photopolymerization initiator is used in combination with a sensitizer, the mass ratio of the photopolymerization initiator to the sensitizer is preferably in the range of 10:90 to 90:10, and 20:80 to 80:20. The range is better.

In addition, the active energy ray-curable composition may contain a polymerizable reaction by irradiation with an active energy ray, in addition to the (meth)acrylic block copolymer of the present invention, as long as the effects of the present invention are not impaired. Thinner. The reactive diluent is not particularly limited as long as it exhibits polymerizability by irradiation with an active energy ray, and examples thereof include styrene, hydrazine, p-methylstyrene, and α-. Styrene derivatives of methylstyrene, p-methoxystyrene, p-t-butoxystyrene, p-chloromethylstyrene, p-ethoxylated styrene, divinylbenzene, etc. ; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl benzoate, vinyl querceate, etc.; methyl (meth) acrylate, (meth) acrylate Ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Tert-butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (methyl) ) isooctyl acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, isodecyl (meth)acrylate , undecyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, (methyl) Isodecyl acrylate, decyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ( 4-butylcyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid 4-hydroxybutyl ester, tetrahydrofuran methyl (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 ester, (meth)acrylic acid Methoxy polyethylene glycol, methoxypolypropylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylic acid 7-Amino-3,7-dimethyloctyl ester, 4-(methyl)acrylonitrile Porphyrin, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tris(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate , triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecane diyl 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(methyl) Two-terminal (meth)acrylic acid adduct of acrylate, bisphenol A diglycidyl ether, pentaerythritol tetra(meth)acrylate, 2,4,6-trisethoxy hexahydro-1,3,5 -three -1,3,5-ethanol tris(meth)acrylate, N,N'-bis[2-((methyl)propenyloxy)ethyl]-N"-(2-hydroxyethyl )-1,3,5-three a diol of -2,4,6(1H,3H,5H)-trione, tricyclodecane dimethanol di(meth) acrylate, bisphenol A ethylene oxide or propylene oxide adduct a di(meth)acrylate of a diol of a di(meth)acrylate, an ethylene oxide or a propylene oxide adduct of hydrogenated bisphenol A, and a diglycidyl ether of bisphenol A. a (meth) acrylate epoxy (meth) acrylate, and a (meth) acryl derivative such as cyclohexane dimethanol di (meth) acrylate; a bisphenol A epoxy acrylate resin; An epoxy acrylate resin such as a phenol novolak type epoxy acrylate resin or a cresol novolak type epoxy acrylate resin; a carboxyl group-modified epoxy acrylate resin; and a polytetramethylene glycol (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 end Polybutadiene, hydroxyl terminated polyisobutylene, etc.) with organic isocyanate (toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate) A urethane resin obtained by hexamethylene diisocyanate, benzodimethyl diisocyanate or the like and a (meth) acrylate having a hydroxyl group (hydroxyethyl (meth) acrylate, hydroxy propyl (a) a urethane acrylate resin obtained by a reaction of an acrylate, a hydroxybutyl (meth) acrylate, a pentaerythritol triacrylate, or the like; and a (meth) propylene introduced into the above polyol via an ester bond A sulfhydryl resin; a polyester acrylate resin; an epoxy compound such as epoxidized soybean oil or phenylethyl stearyl stearate. These reactive diluents may be used alone or in combination of two or more.

The active energy ray-curable composition may contain a plasticizer, a tackifier, or a soft layer within a range that does not significantly inhibit the curability thereof. Various additives which do not have an active energy ray-curable group, such as a chemical agent, a filler, a stabilizer, a pigment, and a dye.

The purpose of including the plasticizer in the active energy ray-curable composition is, for example, adjustment of the viscosity of the active energy ray-curable composition, and mechanical strength of the cured product obtained by curing the active energy ray-curable composition. Adjustment. Examples of the above plasticizer include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, and butyl benzyl phthalate. Non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.; butyl oleate, An aliphatic ester of acetaminophen phthalic acid methyl ester or the like; an ester of a polyalkylene glycol such as diethylene glycol dibenzoate, triethylene glycol dibenzoate or pentaerythritol ester; Phosphate ester of ester, tributyl phosphate, etc.; trimellitate; polybutadiene, butadiene-acrylonitrile copolymer, polydichlorobutadiene, etc. Alkene; polyisobutylene; chlorinated paraffin; alkyl diphenyl, partially hydrogenated terphenyl, etc.; hydrocarbon; operating oil; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. a polyether in which an alcohol and a hydroxyl group of the polyether polyol are converted into a derivative such as an ester group or an ether group; a diproton acid such as azelaic acid, adipic acid, sebacic acid or phthalic acid; , A polyester obtained by a divalent alcohol such as diethylene glycol, triethylene glycol, propylene glycol or dipropylene glycol. Further, the (co)polymer is a generic term for a single polymer and a copolymer. These plasticizers may be used alone or in combination of two or more.

In terms of the molecular weight or the number average molecular weight of the plasticizer, 400 to 15,000 is preferred, and 800 to 10,000 is more preferred, 1,000 to 8,000. For better. Further, the plasticizer may have a functional group other than the active energy ray-curable group (for example, a hydroxyl group, a carboxyl group, a halogen group, or the like), or may not. When the molecular weight or the number average molecular weight of the plasticizer is 400 or more, the plasticizer does not flow out from the hardening of the active energy ray-curable composition with time, and the initial physical properties can be maintained over a long period of time. In addition, the molecular weight of the plasticizer or the number average molecular weight is 15,000 or less, and the workability of the active energy ray-curable composition tends to be improved.

In the case where the active energy ray-curable composition contains a plasticizer, the content thereof is preferably from 5 to 150 parts by mass, based on 100 parts by mass of the (meth)acrylic block copolymer of the present invention, and 10~ 120 parts by mass is more preferable, and 20 to 100 parts by mass is further preferable. When the amount is 5 parts by mass or more, the effect of the adjustment of the physical properties and the adjustment of the properties is remarkable, and the cured product obtained by curing the active energy ray-curable composition tends to have excellent mechanical strength by being made into 150 parts by mass or less.

Further, 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 (meth)acrylic block copolymer of the present invention or the active energy ray-curable composition containing the (meth)acrylic block copolymer is cured can be used. The device is illuminated. The acceleration voltage in the case of the electron beam (EB) is 0.1 to 10 MeV, and the range of 1 to 500 kGy is appropriate in terms of the amount of irradiation.

In the ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an LED, or the like which emits light in a wavelength region of 150 to 450 nm can be used. The integrated light amount of the active energy ray is usually in the range of 10 to 20,000 mJ/cm ² , and preferably in the range of 30 to 5,000 mJ/cm ² . When the amount is less than 10 mJ/cm ² , the curability of the (meth)acrylic block copolymer tends to be insufficient, and when it is more than 20,000 mJ/cm ² , the (meth)acrylic block copolymer is deteriorated. may.

The relative humidity in the case where the (meth)acrylic block copolymer of the present invention or the active energy ray-curable composition containing the (meth)acrylic block copolymer is irradiated with an active energy ray is suppressed (A) From the viewpoint of decomposition of the acrylic block copolymer, 30% or less is preferable, and 10% or less is more preferable.

The (meth)acrylic block copolymer of the present invention or the active energy ray-curable composition containing the (meth)acrylic block copolymer may be further subjected to active energy ray irradiation or after irradiation. Heating is required to promote hardening. The heating temperature is preferably in the range of 40 to 130 ° C, and more preferably in the range of 50 to 100 ° C.

The method of using the active energy ray-curable composition is not particularly limited, and the cured product applied to the substrate and cured can be used as an ink, a paint, a coating material, a masking material, and a lining material. Examples of the effects that can be expected include information imparting, surface protection, corrosion resistance, insulation, and abrasion resistance. In addition, it can be used for further coating on plating or lining, self-coating materials, and piping provided.

Examples of the substrate include polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene naphthalate, polyethylene terephthalate, etc.), and polyamine (polyamide). -6, nylon-66, etc.), polystyrene, ethyl vinyl alcohol, polyvinyl chloride, polyimine, polyvinyl alcohol, poly Carbonate, polyether oxime, cellulose acylate (triethyl fluorenyl cellulose, diethyl hydrazine cellulose, etc.), polymethyl methacrylate resin, glass, iron, stainless steel, etc., coated plating Film or lining film, etc.

The cured product obtained by curing the active energy ray-curable composition may be used in water or an acidic aqueous solution, an alkaline aqueous solution, or hypochlorous acid water. The use temperature is not particularly limited.

The cured product obtained by curing the active energy ray-curable composition is excellent in elongation and mechanical strength, and can be prevented from being corroded, and the duration of the insulating function is prolonged or extended.

The cured product obtained by curing the active energy ray-curable composition may be peeled off using an organic solvent when it is not necessary. Examples of the organic solvent include n-hexane, n-heptane, n-octane, isooctane, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl ether, tetrahydrofuran, dichloromethane, chloroform, and Ethyl chloride, 1,1-dichloromethane, 1,2-dichloromethane, 1,1,1-trichloroethane, acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone , methyl isobutyl ketone, diisobutyl ketone, toluene, cyclohexanone, diacetone alcohol, and the like. Further, the organic solvent may be used singly or in combination of two or more.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the invention is not limited to the examples.

In the following examples and comparative examples, the raw materials were dried and purified by a usual method, and nitrogen was used as a degassing agent, and the transfer and supply were carried out under a nitrogen atmosphere.

[Monomer consumption rate]

In the following examples and comparative examples, the consumption rate of each monomer after polymerization was 0.5 mL of methanol in 0.5 mL of the reaction liquid, and 0.1 mL of the mixture was taken, and dissolved in deuterated chloroform 0.5 mL. ¹ H-NMR measurement was carried out under the following measurement conditions, and a peak (chemical shift value 5.79 to 6.37 ppm) derived from a proton directly bonded to a carbon-carbon double bond of a (meth) acrylate used as a monomer The ratio of the integral value of the peak (chemical shift value of 7.00 to 7.38 ppm) of the proton directly bonded to the aromatic ring used as the solvent was calculated.

( ¹ H-NMR measurement conditions)

Device: Nuclear Magnetic Resonance Device "JNM-ECX400" manufactured by Nippon Electronics Co., Ltd.

Temperature: 25 ° C

[Quantitative average molecular weight (Mn), molecular weight distribution (Mw/Mn)]

In the following examples and comparative examples, GPC (colloidal permeation chromatography) of the obtained polymer was measured under the following measurement conditions, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) in terms of standard polystyrene were determined. The value of ).

(GPC measurement conditions)

Device: GPC device "HLC-8220GPC" manufactured by TOSOH Co., Ltd.

Separation column: "TSKgel SuperMultiporeHZ-M (column diameter = 4.6 mm, column length = 15 cm) manufactured by TOSOH Co., Ltd." (two tubes are connected in series)

Dissolution: tetrahydrofuran

Dissolution flow: 0.35 mL / min

Column temperature: 40 ° C

Detection method: differential refractive index (RI)

[Polymerization efficiency]

Mn of the polymer obtained by the step (1) of the Mn (as Mn(R1)) of the polymer obtained in the step (1) and the polymerization initiation efficiency of 100% (calculated value: as Mn ( I1)), the polymerization initiation efficiency (F1) in the step (1) is calculated by the following formula.

F1 (%) = 100 × Mn (I1) / Mn (R1)

[Block efficiency from step (1) to step (2)]

Obtained by the above Mn(R1) and Mn(I1), Mn (as Mn(R2)) of the polymer obtained in the step (2), and the step (2) in the case where the block efficiency is 100% The Mn of the polymer (calculated value: Mn (I2)), the block efficiency (F2) from the step (1) to the step (2) was calculated by the following formula.

F2 (%) = 10000 × {Mn (I2) - Mn (I1)} / [F1 × {Mn (R2) - Mn (R1)}]

[Content of each monomer unit forming a (meth)acrylic block copolymer]

The content of each monomer unit of the (meth)acrylic block copolymer obtained in the following examples and comparative examples was calculated by the following method.

0.01 g of the obtained (meth)acrylic block copolymer was dissolved in 0.5 mL of deuterated chloroform to carry out ¹ H-NMR measurement, and was directly bonded to 1,1-dimethylpropane-1,3- The peak of the proton of the carbon-carbon double bond of the methacryloyl group (-C(=O)-C(=CH ₂ )-CH ₃ ) of the diol dimethacrylate unit (near 6.0 ppm), from A The proton peak (near 3.6 ppm) of the methoxy group (-O-CH ₃ ) of the methyl acrylate unit, derived from n-butoxy (-O-CH ₂ -CH ₂ - directly bonded to the n-butyl acrylate unit) Proton peak of methylene group of oxygen atom of CH ₂ -CH ₃ ) (near 4.0 ppm), from 2-ethylhexyloxy group (-O-CH ₂ - directly bonded to 2-ethylhexyl acrylate unit) The proton peak of the methylene group of the oxygen atom of CH(-CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₃ ) (near 3.9 ppm), 2 from the 2-methoxyethyl acrylate unit The ratio of the integral value of the proton peak (near 3.3 ppm) of the methoxy group of the methoxyethoxy group (-O-CH ₂ -CH ₂ -O-CH ₃ ) was calculated.

( ¹ H-NMR measurement conditions)

Device: Nuclear Magnetic Resonance Device "JNM-ECX400" manufactured by Nippon Electronics Co., Ltd.

Temperature: 25 ° C

[Evaluation of elongation at break of hardened material]

When the (meth)acrylic block copolymer obtained in the examples and the comparative examples was a solid at 25 ° C, 100 parts by mass of the (meth)acrylic block copolymer and 154 mass of methyl ethyl ketone. 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, IRGACURE (registered trademark) 184) as a radical polymerization initiator was stirred and mixed to obtain a solution. The obtained solution was poured into a box-shaped container made of a release-treated PET film (K1504, manufactured by Toyobo Co., Ltd.), and dried at room temperature for 24 hours to prepare an active energy ray-curable composition having a thickness of 150 μm. A UV irradiation apparatus (manufactured by GS YUASA, 12A12-A10-HD3A, using a lamp: GS YUASA, HAK 125AL-F) was irradiated with UV at 600 mJ/cm ² in the atmosphere to harden the curable composition. The obtained cured product was cut into a rectangular shape having a length of 40 mm and a width of 5 mm, and the test piece was placed in a tensile tester (manufactured by Instron Japan, model 5566), and the fracture was determined at 25 ° C and a tensile speed of 60 mm/min. Elongation.

The (meth)acrylic block copolymer obtained in the examples and the comparative examples was liquid at 25 ° C, except that 100 parts by mass of the (meth)acrylic block copolymer was used as a radical polymerization initiation. 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, IRGACURE (registered trademark) 184), stirred and mixed to obtain a solution, and the (meth)acrylic block copolymer was solid. The active energy ray-curable composition was produced in the same manner to determine the elongation at break.

[Evaluation of adhesion of hardened materials]

The surface of the cured product of the (meth)acrylic block copolymer obtained in the examples and the comparative examples was touched with a finger at room temperature, and the presence or absence of the adhesive feeling was examined. Also, it is considered that there is a feeling of adhesion when there is a little adhesion.

[Example 1] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene as a Lewis base was further added thereto while stirring. 2.3 g (10.1 mmol) of tetraamine and 37.8 g of a toluene solution containing 25.9% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound ( 18.7 mmol) and cooled to -20 °C. Adding it as there is 6.16 g (9.60 mmol) of a lithium pentoxide solution of 9.98 mass% of a lithium hydride compound, followed by the addition of 1,1-dimethylpropane-1,3-diol dimethyl as a monomer A mixture of 6.34 g (26.4 mmol) of acrylate and 118 g (1.13 mol) of methyl methacrylate was 118.34 g, and anionic polymerization was started. After 390 minutes from the end of the addition of the mixture, the reaction liquid became colorless from the original yellow color. After further stirring for 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 12,500 and Mw/Mn of 1.10. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), and after 1 minute, 257 g (2.01 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 41,600 and Mw/Mn of 1.08. Further, the block efficiency (F2) from the step (1) to the step (2) was 93%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 1.61 g (23.2 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate were added in one portion. Mix of 98.9g (988mmol) After the compound was 104.46 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 120 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction solution was stirred at 20 ° C while anion polymerization was stopped by adding 51.2 g of 50% by mass of acetic acid water to obtain a block containing the methacrylic polymer block (A)-(meth)acrylic polymer. A solution of the (meth)acrylic block copolymer of the triblock copolymer in which the segment (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,800 and a Mw/Mn of 1.23.

(Step (5))

Next, the obtained solution was stirred under nitrogen flow at 90 ° C while forming an acetate of the catalyst metal by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped into 5 times of hexane to reprecipitate, and further dried at 80 ° C and 30 Pa to obtain 450 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (1)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (1) are shown in Table 1.

[Embodiment 2] (step 1))

After adding 867 g of toluene to a 2 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene tetraamine as a Lewis base was further added thereto while stirring. 1.03 g (4.48 mmol), and a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 32.6 g (16.4 mmol) ) and cooled to -20 ° C. 2.70 g (4.27 mmol) of a cyclohexane solution containing 10.1% by mass of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. - 76.06 g of a mixture of 3.06 g (12.7 mmol) of diol dimethacrylate and 73.0 g (730 mmol) of methyl methacrylate, and anionic polymerization was initiated. After 340 minutes from the end of the addition of the mixture, the reaction liquid became colorless from the original yellow color. Further, after stirring for 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 18,000 and Mw/Mn of 1.10. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Then, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound of 26.4% by mass. 4.65 g (2.35 mmol), after which one minute, 174 g (1.35 mol) of n-butyl acrylate as a monomer was added at a rate of 3 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 59,800 and Mw/Mn of 1.20. Further, the block efficiency (F2) from the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 2.71 g (11.3 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate were added in one portion. After a mixture of 64.8 g (647 mmol) of 67.51 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 120 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 33.0 g of 50% by mass acetic acid water to obtain a block containing the methacrylic polymer block (A)-(meth)acrylic polymer. A solution of the (meth)acrylic block copolymer of the triblock copolymer in which the segment (B)-methacrylic polymer block (A) (ABA) is bonded in sequence. The (meth)acrylic block copolymer sampled from the solution had an Mn of 71,600 and a Mw/Mn of 1.27.

(Step (5))

Next, the obtained solution was stirred under nitrogen flow at 90 ° C while the acetate metal of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane and reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 294 g of a (meth)acrylic block copolymer (hereinafter referred to as "(methyl)). Acrylic block copolymer (2)"). will The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (2) are shown in Table 1.

[Example 3] (step 1))

After adding 1.47 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.36 g (10.1 mmol) of an amine and 47.4 g of a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound (23.9 g (23.9 g) Mmmol), cooled to -20 °C. 6.16 g (9.76 mmol) of a cyclohexane solution containing 10.1% by mass of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. - 129.44 g of a mixture of 3.44 g (14.3 mmol) of diol dimethacrylate and 126 g (1.26 mol) of methyl methacrylate, and initial anionic polymerization. After the end of the addition of the mixture for 220 minutes, the reaction solution turned from the original yellow color to colorless. After further stirring for 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 13,300 and Mw/Mn of 1.09. Further, the polymerization initiation efficiency (F1) in the step (1) was 100%.

(Step (2))

The reaction solution was then stirred at -20 ° C while adding isobutyl bis(2,6-di-t-butyl-4-methyl) as an organoaluminum compound. 10.6 g (5.37 mmol) of a 26.4 mass% toluene solution of phenoxy)aluminum, and after that, 282 g (2.20 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 43,600 and Mw/Mn of 1.06. Further, the block efficiency (F2) of the step (1) to the step (2) was 96%.

(Step (3))

Next, the reaction liquid was stirred at -20 ° C while adding 1,5 g (12.7 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. After a mixture of 111 g (1.11 mol) of 114.05 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 120 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 50.3% by mass of 50% by mass of acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 51,700 and an Mw/Mn of 1.11.

(Step (5))

Next, the obtained solution was stirred under nitrogen flow at 90 ° C while making the acetate metal of the catalyst metal by heating for 90 minutes. to make. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to be reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 500 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (3)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (3) are shown in Table 1.

[Example 4] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.32 g (10.1 mmol) of an amine, and a toluene solution containing 45.9 mass% of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 47.5 g (23.5) Mmmol) and cooled to -20 °C. 6.16 g (9.60 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. A mixture of 15.9 g (66.1 mmol) of diol dimethacrylate and 102 g (1.01 mol) of methyl methacrylate was added and anion polymerization was initiated. The reaction solution changed from the original yellow color to colorless after 220 minutes from the end of the addition of the mixture. After further stirring for 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 12,400 and Mw/Mn of 1.09. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), which was added to 266 g (2.08 mol) of n-butyl acrylate as a monomer at a rate of 5 g/min after 1 minute. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 41,000 and Mw/Mn of 1.06. Further, the block efficiency (F2) from the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 14.0 g (58.3 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer was added in one go with methyl methacrylate. After 103.5 g of a mixture of 89.5 g (894 mmol), the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 120 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C, and anionic polymerization was stopped by adding 57.3 g of 50% by mass of acetic acid water to obtain a block (A)-(meth)acrylic polymer containing a methacrylic polymer. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (A-B-A) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,400 and an Mw/Mn of 1.23.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate metal acetate was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to be reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 480 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (4)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (4) are shown in Table 1.

[Example 5] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.32 g (10.1 mmol) of an amine, and a toluene solution containing 55.9 % by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 50.4 g (25.0) Mmmol) and cooled to -20 °C. A cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound is added thereto 6.16 g (9.60 mmol), followed by adding 20.0 g (83.3 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and 112 g of methyl methacrylate (in one part) A mixture of 1.11 mol) was 132.0 g and anion polymerization was initiated. After 260 minutes from the end of the addition of the mixture, the reaction liquid turned from the original yellow color to colorless. After further stirring for 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 14,200 and Mw/Mn of 1.10. Further, the polymerization initiation efficiency (F1) in the step (1) was 97%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), after 1 minute, 240 g (1.88 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 40,800 and Mw/Mn of 1.07. Further, the block efficiency (F2) of the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 17.1 g (73.4 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate were added in one portion. After a mixture of 99.3 g (982 mmol) of 115.9 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 140 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 59.1 g of 50% by mass aqueous acetic acid to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,300 and a Mw/Mn of 1.23.

(Step (5)

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to be reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 480 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (5)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (5) are shown in Table 1.

[Embodiment 6] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.32 g (10.1 mmol) of an amine, and a toluene solution containing 25.9% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 37.8 g (18.7) Mmmol) and cooled to -20 °C. 6.16 g (9.60 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. - 89.03 g of a mixture of 6.53 g (27.2 mmol) of diol dimethacrylate and 82.5 g (824 mmol) of methyl methacrylate, and anionic polymerization was initiated. After the end of the addition of the mixture for 200 minutes, the reaction liquid became colorless from the original yellow color. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 9,400 and Mw/Mn of 1.10. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), and after 1 minute, 315 g (2.46 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 43,000 and Mw/Mn of 1.07. Further, the block efficiency (F2) of the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C while adding 1.76 g (24.0 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. After 72.7 g (726 mmol) of a mixture of 78.46 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 100 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 51.2 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,400 and a Mw/Mn of 1.18.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to reprecipitate, and further dried at 80 ° C and 30 Pa to obtain 470 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Acrylic block copolymer (6)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (6) are shown in Table 1.

[Embodiment 7] (step 1))

After adding 1.21 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.03 g (8.82 mmol) of an amine, and a toluene solution containing 45.9% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 44.1 g (21.8) Mmmol) and cooled to -20 °C. 5.39 g (8.40 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. - 124.71 g of a mixture of 5.71 g (23.8 mmol) of diol dimethacrylate and 119 g (1.19 mol) of methyl methacrylate, and anionic polymerization was initiated. After the end of the addition of the mixture for 220 minutes, the reaction solution turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 15,000 and Mw/Mn of 1.11. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

The reaction solution was then stirred at -20 ° C while adding isobutyl bis(2,6-di-t-butyl-4-methyl) as an organoaluminum compound. 9.33 g (4.62 mmol) of a toluene solution of phenoxy)aluminum (25.9 mass%) was added, and after that, 192 g (1.50 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 38,300 and Mw/Mn of 1.08. Further, the block efficiency (F2) of the step (1) to the step (2) was 100%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 5.01 g (21.0 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer was added in one portion with methyl methacrylate. After a mixture of 105 g (1.05 mol) of 110.04 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 140 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 51.7 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,100 and an Mw/Mn of 1.16.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate metal acetate was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to reprecipitate, and further dried at 80 ° C and 30 Pa to obtain 420 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (7)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (7) are shown in Table 1.

[Embodiment 8] (step 1))

After adding 867 g of toluene to a 2 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene tetraamine as a Lewis base was further added thereto while stirring. 1.39 g (6.05 mmol) and a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 27.9 g (14.1 mmol) ) and cooled to -20 ° C. 3.70 g (5.76 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. - 72.17 g of a mixture of 1.87 g (7.77 mmol) of diol dimethacrylate and 70.3 g (703 mmol) of methyl methacrylate, and initial anionic polymerization. After 260 minutes from the end of the addition of the mixture, the reaction liquid turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 12,700 and Mw/Mn of 1.07. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Then, the reaction liquid was stirred at -20 ° C while adding a toluene solution of 6.64% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (3.17 mmol), after 1 minute, 154 g (833 mmol) of 2-ethylhexyl acrylate as a monomer was added at a rate of 3 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of 2-ethylhexyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 40,100 and Mw/Mn of 1.04. Further, the block efficiency (F2) of the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 1.71 g (6.94 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer was added in one go with methyl methacrylate. After 62.67 g of a mixture of 61.0 g (609 mmol), the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 60 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction solution was stirred at 20 ° C while anion polymerization was stopped by adding 34.4 g of 50% by mass acetic acid water to obtain a content. Triblock copolymer bonded in the order of methacrylic polymer block (A)-(meth)acrylic polymer block (B)-methacrylic polymer block (A) (ABA) A solution of the (meth)acrylic block copolymer. The (meth)acrylic block copolymer sampled from the solution had an Mn of 49,800 and a Mw/Mn of 1.05.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate metal of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to be reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 280 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (8)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (8) are shown in Table 1.

[Embodiment 9] (step 1))

After adding 919 g of toluene to a 2 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene tetraamine as a Lewis base was further added thereto while stirring. 1.51 g (6.56 mmol), and a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 30.3 g (15.3 mmol) ) and cooled to -20 ° C. Adding it as a 3.85 g (6.25 mmol) of a cyclohexane solution of an organic lithium compound of 10.4% by mass in a cyclohexane solution, and thereafter, 1,1-dimethylpropane-1,3-diol dimethyl group as a monomer was added in one portion. A mixture of 2.09 g (8.70 mmol) of acrylate and 78.8 g (787 mmol) of methyl methacrylate was 80.89 g, and anion polymerization was initiated. After the end of the addition of the mixture for 300 minutes, the reaction liquid became colorless from the original yellow color. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 13,000 and Mw/Mn of 1.09. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 6.84% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (3.44 mmol), and after 1 minute, 173 g (1.33 mol) of 2-methoxyethyl acrylate as a monomer was added at a rate of 3 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of 2-methoxyethyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 42,000 and Mw/Mn of 1.07. Further, the block efficiency (F2) of the step (1) to the step (2) was 96%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C while adding 1.87 g (7.80 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. Mix of 68.5g (684mmol) After 114.05 g of the compound, the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 80 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 37.3 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 47,800 and a Mw/Mn of 1.09.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate metal of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., it was centrifuged at a centrifugal force of 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Kogyo Co., Ltd.) to precipitate an acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to be reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 320 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (9)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (9) are shown in Table 1.

[Comparative Example 1] (step 1))

After adding 1.30 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.83 g (12.3 mmol) of an amine and 60.2 g of a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound (30.4) Mmmol) and cooled to -20 °C. 6.93 g (11.7 mmol) of a cyclohexane solution containing 10.8% by mass of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. A mixture of 17.5 g (72.9 mmol) of diol dimethacrylate and 98.4 g (983 mmol) of methyl methacrylate was 115.9 g, and anion polymerization was initiated. After 240 minutes from the end of the addition of the mixture, the reaction liquid turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 10,000 and Mw/Mn of 1.10. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (6.44 mmol), and after 1 minute, 211 g (1.64 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 28,400 and Mw/Mn of 1.09. Further, the block efficiency (F2) of the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C while adding 1,1 g (64.2 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. After 102.1 g of a mixture of 86.7 g (866 mmol), the temperature was raised to 20 ° C at a rate of 2 ° C/min. After 150 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C, and anionic polymerization was stopped by adding 72.1 g of 50% by mass of acetic acid water to obtain a block containing the methacrylic polymer block (A)-(meth)acrylic polymer. A solution of the (meth)acrylic block copolymer of the triblock copolymer in which the segment (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 36,300 and an Mw/Mn of 1.23.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., a centrifugal separator (manac CR22GII, manufactured by Hitachi Kogyo Co., Ltd.) was used, and centrifugation was carried out for 30 minutes at a centrifugal force of 18,800 G to precipitate an acetate, and the supernatant was collected. will The recovered supernatant was subjected to reprecipitation by dropping to 5 times the amount of hexane, and further dried at 80 ° C and 30 Pa to obtain 410 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(methyl) ) acrylic block copolymer (10)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (10) are shown in Table 1.

[Comparative Example 2] (step 1))

After adding 1.21 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 9.44 g (41.0 mmol) of an amine, and a toluene solution containing 86.4% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 85.0 g (42.9) Mmmol) and cooled to -20 °C. 23.1 g (39.0 mmol) of a cyclohexane solution containing 10.8% by mass of a second butyl lithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. A mixture of 27.9 g (116 mmol) of diol dimethacrylate and 23.3 g (232 mmol) of methyl methacrylate was added and anion polymerization was initiated. After 80 minutes from the end of the addition of the mixture, the reaction liquid turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 1,320 and Mw/Mn of 1.16. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 46.4% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (21.5 mmol), and after 1 minute, 345 g (2.69 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 11,300 and Mw/Mn of 1.18. Further, the block efficiency (F2) of the step (1) to the step (2) was 89%.

(Step (3))

Next, the reaction liquid was stirred at -20 ° C while adding 1,1 -1 - dimethyl diol - 1,3-diol dimethacrylate as a monomer, 24.3 g (101 mmol) and methyl methacrylate 20.2. After 44.5 g of a mixture of g (202 mmol), the temperature was raised to 20 ° C at a rate of 2 ° C / min. The reaction solution was sampled after 100 minutes from the addition of the above mixture.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 166 g of 50% by mass of acetic acid water to obtain a block containing the methacrylic polymer block (A)-(meth)acrylic polymer. A solution of the (meth)acrylic block copolymer of the triblock copolymer in which the segment (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 13,400 and an Mw/Mn of 1.19.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was subjected to removal of the solvent at 60 ° C using an evaporator, and then dried at 100 ° C and 30 Pa to obtain 430 g of a (meth)acrylic block copolymer (hereinafter referred to as "(methyl)). Acrylic block copolymer (11)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (11) are shown in Table 1.

[Comparative Example 3] (step 1))

After adding 1.21 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 5.66 g (24.6 mmol) of an amine, and a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 51.0 g (25.7) Mmmol) and cooled to -20 °C. 13.9 g (23.4 mmol) of a cyclohexane solution containing 10.8% by mass of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. a mixture of 16.7 g (69.7 mmol) of diol dimethacrylate and 14.0 g (139 mmol) of methyl methacrylate, and started Anionic polymerization. After the addition of the mixture was completed, the reaction liquid became colorless from the original yellow after 80 minutes. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 1,340 and Mw/Mn of 1.16. Further, the polymerization initiation efficiency (F1) in the step (1) was 98%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 26.4% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (12.9 mmol), and after 1 minute, 401 g (3.13 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 21,300 and Mw/Mn of 1.18. Further, the block efficiency (F2) of the step (1) to the step (2) was 88%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C while adding 1,1 g (60.6 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. After 12.7 g of a mixture of 12.1 g (121 mmol), the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 60 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Next, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 99.8 g of 50% by mass aqueous acetic acid to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 22,600 and an Mw/Mn of 1.19.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., a centrifugal separator (manac CR22GII, manufactured by Hitachi Kogyo Co., Ltd.) was used, and centrifugation was carried out for 30 minutes at a centrifugal force of 18,800 G to precipitate an acetate, and the supernatant was collected. The supernatant recovered from the evaporator was removed at 60 ° C, and then dried at 100 ° C and 30 Pa to obtain 450 g of a (meth)acrylic block copolymer (hereinafter referred to as "(meth)acrylic acid). Block copolymer (12)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (12) are shown in Table 1.

[Comparative Example 4] (step 1))

After adding 1.30 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the mixture was further added as a Lewis base while stirring. 1,1,4,7,10,10-hexamethyltriethylamine 4 g (13.7 mmol), and isobutyl bis(2,6-di-third butyl) as an organoaluminum compound 29.6 g (15.0 mmol) of a 26.4% by mass solution of toluene of 4-methylphenoxy)aluminum and cooled to -20 °C. 7.9 g (13.0 mmol) of a cyclohexane solution containing 10.5 mass% of a second butyl lithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. A mixture of 9.4 g (39 mmol) of diol dimethacrylate and 7.8 g (78 mmol) of methyl methacrylate was 17.2 g, and anion polymerization was initiated. After the end of the addition of the mixture for 160 minutes, the reaction liquid turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 1,330 and Mw/Mn of 1.16. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 14.8% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (9.1 mmol), after which one minute, 446 g (3.48 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 41,200 and Mw/Mn of 1.18. Further, the block efficiency (F2) of the step (1) to the step (2) was 87%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 8.1 g (33.6 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate were added in one portion. After a mixture of 6.7 g (67.3 mmol) of 14.8 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 120 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 50. mass% of acetic acid water to 29.4 g, thereby obtaining a (meth)acrylic polymer block (A)-(meth)acrylic polymer. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 42,600 and a Mw/Mn of 1.19.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The supernatant recovered from the evaporator was removed at 60 ° C, and then dried at 100 ° C and 30 Pa to obtain 460 g of a (meth)acrylic block copolymer (hereinafter referred to as "(methyl)). Acrylic block copolymer (13)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (13) are shown in Table 1.

[Comparative Example 5] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.32 g (10.1 mmol) of an amine, and a toluene solution containing 25.9% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 37.8 g (18.7) Mmmol) and cooled to -20 °C. 6.16 g (9.60 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 117 g (1.17 mol) of methyl methacrylate as a monomer was added in one portion, and Initial anionic polymerization. After 80 minutes from the end of the addition of the mixture, the reaction liquid turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The methyl methacrylate consumption rate in the step (1) is 100%. Further, the obtained polymer had Mn (Mn(R1)) of 12,400 and Mw/Mn of 1.07. Further, the polymerization initiation efficiency (F1) in the step (1) was 98%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), which was added to 266 g (2.08 mol) of n-butyl acrylate as a monomer at a rate of 5 g/min after 1 minute. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 40,900 and Mw/Mn of 1.07. Further, the block efficiency (F2) of the step (1) to the step (2) was 100%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and while 103 g (1.03 mol) of methyl methacrylate as a monomer was added in one portion, the temperature was raised to 20 ° C at a rate of 2 ° C / min. After the addition of the above mixture for 100 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 51.2 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,300 and a Mw/Mn of 1.12.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant is dropped to 5 times the amount of hexane to reprecipitate One step was dried at 80 ° C and 30 Pa to obtain 480 g of a (meth)acrylic block copolymer (hereinafter referred to as "(meth)acrylic block copolymer (14)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (14) are shown in Table 1.

[Comparative Example 6] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the mixture was further added as a 1,1,4,7,10,10-hexamethyltriethyl group as a Lewis base while stirring. 2.32 g (10.1 mmol) of tetraamine and 37.8 g of a toluene solution containing 25.9% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound ( 18.7 mmol) and cooled to -20 °C. 6.16 g (9.60 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. A mixture of 26.6 g (111 mmol) of diol dimethacrylate and 83.4 g (833 mmol) of methyl methacrylate was 110.0 g, and anion polymerization was initiated. After 280 minutes from the end of the addition of the mixture, the reaction liquid turned from the original yellow color to colorless. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 11,600 and Mw/Mn of 1.12. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), after 1 minute, 255 g (2.00 mol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 38,900 and Mw/Mn of 1.10. Further, the block efficiency (F2) of the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C, and 2,3.4 g (97.4 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer was added in one go with methyl methacrylate. After 96.9 g of a mixture of 73.5 g (734 mmol), the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 150 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 51.2 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 47,400 and a Mw/Mn of 1.22.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to be reprecipitated, and further dried at 80 ° C and 30 Pa to obtain 450 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (15)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (15) are shown in Table 1.

[Comparative Example 7] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. 2.32 g (10.1 mmol) of an amine and 37.8 g (15.0 g) of a toluene solution containing 25.9 mass% of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound Mmmol) and cooled to -20 °C. 6.16 g (9.60 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. 63.63g of a mixture of 6.53g (27.2mmol) of diol dimethacrylate and 57.1g (571mmol) of methyl methacrylate Initial anionic polymerization. After the end of the addition of the mixture for 140 minutes, the reaction liquid became colorless from the original yellow color. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 6,700 and Mw/Mn of 1.10. Further, the polymerization initiation efficiency (F1) in the step (1) was 99%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing 10.58% by mass of isobutyl bis(2,6-di-tert-butyl-4-methylphenoxy)aluminum as an organoaluminum compound. g (5.28 mmol), which was added 361 g (2.82 mol) of n-butyl acrylate as a monomer at a rate of 5 g/min after 1 minute. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 45,000 and Mw/Mn of 1.15. Further, the block efficiency (F2) of the step (1) to the step (2) was 99%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C while adding 1.76 g (24.0 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. After a mixture of 50.4 g (503 mmol) of 56.16 g, the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 90 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 51.2 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,300 and an Mw/Mn of 1.16.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The supernatant recovered from the evaporator was removed at 60 ° C, and then dried at 100 ° C and 30 Pa to obtain 470 g of a (meth)acrylic block copolymer (hereinafter referred to as "(meth)acrylic acid). Block copolymer (16)"). The evaluation results of the cured product of the active energy ray-curable composition containing the obtained (meth)acrylic block copolymer (16) are shown in Table 1.

[Comparative Example 8] (step 1))

After adding 1.39 kg of toluene to a 3 L flask which was internally dried and replaced with nitrogen, the 1,1,4,7,10,10-hexamethyltriethylidene group as a Lewis base was further added thereto while stirring. amine 1.74 g (7.56 mmol) and a toluene solution containing 25.9% by mass of isobutyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound, 28.3 g (14.0 mmol) ) and cooled to -20 ° C. 4.62 g (7.20 mmol) of a cyclohexane solution containing 9.98 mass% of a second butyllithium as an organolithium compound was added thereto, and then 1,1-dimethylpropane-1,3 as a monomer was added in one portion. A mixture of 4.90 g (20.4 mmol) of diol dimethacrylate and 132 g (1.32 mol) of methyl methacrylate was added and anion polymerization was initiated. After the end of the addition of the mixture for 300 minutes, the reaction liquid became colorless from the original yellow color. After stirring for an additional 20 minutes, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (1) was 100%. Further, the obtained polymer had Mn (Mn(R1)) of 19,700 and Mw/Mn of 1.20. Further, the polymerization initiation efficiency (F1) in the step (1) was 97%.

(Step (2))

Next, the reaction liquid was stirred at -20 ° C while adding a toluene solution containing butyl bis(2,6-di-t-butyl-4-methylphenoxy)aluminum as an organoaluminum compound in an amount of 5.9 % by mass. g (3.96 mmol), after 1 minute, 111 g (868 mmol) of n-butyl acrylate as a monomer was added at a rate of 5 g/min. The reaction solution was sampled immediately after the addition of the monomer.

The consumption rate of n-butyl acrylate in the step (2) was 100%. Further, the obtained polymer had Mn (Mn(R2)) of 36,700 and Mw/Mn of 1.24. Further, the block efficiency (F2) of the step (1) to the step (2) was 97%.

(Step (3))

Then, the reaction liquid was stirred at -20 ° C while adding 1.32 g (18.0 mmol) of 1,1-dimethylpropane-1,3-diol dimethacrylate as a monomer and methyl methacrylate in one portion. After 121.32 g of a mixture of 117 g (1.17 mol), the temperature was raised to 20 ° C at a rate of 2 ° C / min. After 240 minutes from the addition of the above mixture, the reaction solution was sampled.

The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in the step (3) was 100%.

(Step (4))

Then, the reaction liquid was stirred at 20 ° C while anion polymerization was stopped by adding 38.4 g of 50% by mass acetic acid water to obtain a (A)-(meth)acrylic polymer block containing a methacrylic polymer block. A solution of a (meth)acrylic block copolymer of a triblock copolymer in which the block (B)-methacrylic polymer block (A) (ABA) is bonded. The (meth)acrylic block copolymer sampled from the solution had an Mn of 50,200 and an Mw/Mn of 1.19.

(Step (5))

Next, the obtained solution was stirred at 90 ° C under a nitrogen gas flow while the acetate of the catalyst metal was formed by heating for 90 minutes. After the solution was cooled to 25° C., the mixture was centrifuged at 18,800 G for 30 minutes using a centrifugal separator (manip CR22GII, manufactured by Hitachi Industrial Co., Ltd.) to precipitate acetate, and the supernatant was recovered. The recovered supernatant was dropped to 5 times the amount of hexane to reprecipitate, and further dried at 80 ° C and 30 Pa to obtain 350 g of a (meth)acrylic block copolymer (hereinafter, referred to as "(A) Base) acrylic block copolymer (17)"). Will contain the obtained (meth)acrylic block copolymer (17) The evaluation results of the cured product of the active energy ray-curable composition are shown in Table 1.

As is clear from Table 1, the (meth)acrylic block copolymer of the present invention is excellent in curability, and the cured product obtained by irradiation with an active energy ray is excellent in stretchability and does not have an adhesive feeling.

Claims (3)

A (meth)acrylic block copolymer containing a methacrylic polymer block having an active energy ray-curable group having a partial structure (1) represented by the following formula (1) ( A) and a (meth)acrylic block copolymer of the (meth)acrylic polymer block (B) having no active energy ray-curable group, wherein the (meth)acrylic block is formed relative to The content of part of the structure (1) of all the monomer units of the copolymer is 0.3 mol% or more and 5.0 mol% or less, and the methacrylic polymer block (A) in the (meth)acrylic block copolymer. The content is 30% by mass or more and 60% by mass or less, and the number average molecular weight of the (meth)acrylic block copolymer is 40,000 or more. (In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). An active energy ray-curable composition containing the (meth)acrylic block copolymer of claim 1. A cured product which is a (meth)acrylic block copolymer of claim 1 or a cured product of the active energy ray-curable composition of claim 2.