JP2011184678A - Active energy ray-curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition containing an acrylic block copolymer, excellent in curability with active energy rays and excellent in cohesive force, retention force, molding property and curability after shaped, and to provide a molded article, adhesive, pressure-sensitive adhesive and coating film comprising the composition. <P>SOLUTION: The active energy ray-curable composition contains an acrylic block copolymer (A) comprising a methacrylic polymer block (a) and an acrylic polymer block (b), wherein at least one polymer block of the methacrylic polymer block (a) and the acrylic polymer block (b) has an active energy ray-curable functional group (c). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable composition containing an acrylic block copolymer. Moreover, it is related with the molded object, adhesive, adhesive agent, and coating film which consist of this composition.

  An acrylic block copolymer consisting of a methacrylic polymer block and an acrylic polymer block is excellent in tackiness, moldability, weather resistance, etc., making use of these features, adhesives, adhesives, coating materials, various molding materials Development to such uses is expected (Patent Document 1).

  On the other hand, active energy ray-curable materials are known as materials that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams. The active energy ray-curable material has advantages such as being capable of rapid curing with low energy, high productivity, and being capable of curing at room temperature, and taking advantage of these advantages, adhesives, adhesives, paints, It is used for applications such as inks, coating materials, various electric / electronic materials, and optical modeling materials (Non-Patent Document 1).

  For this reason, since the acrylic block copolymer having active energy curability can be expected to be a material having the merits of the above acrylic block copolymer and the active energy ray curable material, its development is desired. It was.

  In addition, pressure-sensitive adhesives, which are one of the uses of acrylic block copolymers, have recently been required to have high cohesive force (holding force) at high temperatures, mainly for electric / electronic applications and automobiles. In general, as a method for improving the holding power of the pressure-sensitive adhesive, a method of cross-linking pressure-sensitive adhesive molecules is employed. However, this method has a problem that the pressure-sensitive adhesive force is reduced as the holding power is improved. Therefore, it has been desired to develop an active energy ray-curable composition having both high holding power and adhesive strength at high temperatures (Patent Document 2).

JP 2009-79120 A Japanese Patent Laid-Open No. 9-324165

'99 UV / EB Curing Material Product Market Handbook CMC Publishing Co., Ltd.

  An object of the present invention is to provide an active energy ray-curable composition that includes an acrylic block copolymer, has excellent curability by active energy rays, and has excellent adhesion, holding power, moldability, and curability after shaping. Is to get. Moreover, it is obtaining a molded object, an adhesive agent, an adhesive, and a coating film containing the said composition.

As a result of intensive studies, the present inventors have solved the above problems.

  That is, the present invention comprises a methacrylic polymer block (a) and an acrylic polymer block (b), and the weight of at least one of the methacrylic polymer block (a) and the acrylic polymer block (b). The present invention relates to an active energy ray-curable composition comprising an acrylic block copolymer (A) having an active energy ray-curable functional group (c) in a combined block.

  As a preferred embodiment, the active energy ray-curable composition is characterized in that the acrylic block copolymer (A) has an active energy ray-curable functional group (c) in the methacrylic polymer block (a). About.

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition further comprising a photoinitiator (B).

  In a preferred embodiment, the active energy ray-curable functional group (c) is at least one selected from the group consisting of an allyl group, a (meth) acryloyl group, and an epoxy group. Related to things.

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition, wherein the acrylic block copolymer (A) is a diblock copolymer, a triblock copolymer, or a mixture thereof.

  As a preferred embodiment, the number average molecular weight of the acrylic block copolymer (A) measured by gel permeation chromatography is 5,000 to 300,000. It relates to a sex composition.

  As a preferred embodiment, in the acrylic block copolymer (A), the proportion of the methacrylic polymer block (a) is 5 to 90% by weight, and the proportion of the acrylic polymer block (b) is 95 to 10% by weight. % Of the active energy ray-curable composition.

  In a preferred embodiment, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the acrylic block copolymer (A) is 1.8 or less. The present invention relates to a linear curable composition.

  As a preferred embodiment, the acrylic block copolymer (A) is a metal having an organic halide or a sulfonyl halide compound as an initiator and at least one selected from Fe, Ru, Ni, and Cu as a central metal. The present invention relates to an active energy ray-curable composition produced by an atom transfer radical polymerization method using a complex as a catalyst.

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition comprising one or more active energy ray-curable functional groups (c) per molecule of the acrylic block copolymer (A).

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition, wherein the photoinitiator (B) is a compound that generates radicals upon irradiation with active energy rays.

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition, wherein the photoinitiator (B) is a compound that generates a cation by irradiation with active energy rays.

  As a preferred embodiment, the present invention relates to an active energy ray-curable composition, wherein the photoinitiator (B) is a compound that generates a base upon irradiation with active energy rays.

  In a preferred embodiment, the amount of the photoinitiator (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). It relates to a sex composition.

  Furthermore, this invention relates to the molded object characterized by including said active energy ray curable composition.

  Furthermore, this invention relates to the adhesive which contains said active energy ray curable composition.

  Furthermore, this invention relates to the adhesive agent characterized by including said active energy ray curable composition.

  Furthermore, this invention relates to the coating film characterized by including said active energy ray curable composition.

  According to the present invention, a composition containing an acrylic block copolymer, which has been difficult to cure with active energy rays, can be cured with active energy rays. An active energy ray-curable composition that is excellent in moldability and curability after shaping can be obtained.

  Moreover, the molded object, adhesive agent, adhesive, and coating film containing the said composition can be obtained.

  Hereinafter, the present invention will be described in more detail.

  The present invention comprises a methacrylic polymer block (a) and an acrylic polymer block (b), and at least one of the methacrylic polymer block (a) and the acrylic polymer block (b). An active energy ray-curable composition comprising an acrylic block copolymer (A) having an active energy ray-curable functional group (c) in a block.

  When the composition of the present invention contains an active energy ray-curable functional group itself or a photoinitiator (B) by irradiating active energy rays such as ultraviolet rays and electron beams, the photoinitiator (B) is active. As a result, the active energy ray-curable functional group (c) of the acrylic block copolymer reacts to form a crosslinked structure. By forming the crosslinked structure, various properties such as heat resistance, tackiness, adhesiveness, mechanical strength, compression set, oil resistance, rubber elasticity, and the like can be improved.

  In the present invention, (meth) acryl means both a methacrylic compound (methacrylic compound) and an acrylic compound.

  Further, in the present invention, the curability after shaping is a property that a molded body can be cured by irradiating with an active energy ray after giving a predetermined shape by various molding methods such as injection molding and extrusion molding. That's it.

  Generally, an acrylic block copolymer can be easily obtained at room temperature by adjusting the molecular design as appropriate, and is excellent in molding processability as a thermoplastic resin. On the other hand, many conventional active energy ray-curable resins are liquid, and they do not have the above-described moldability. Like the acrylic block copolymer composition of the present invention, if it can be cured by irradiation with active energy rays after shaping, various properties after molding (heat resistance, adhesiveness, Adhesiveness, mechanical strength, compression set, oil resistance, rubber elasticity, etc.) can be improved.

  In addition, the molded article, pressure-sensitive adhesive, adhesive, coating film and other uses of the present invention may contain an uncured active energy ray-curable composition, and can be obtained by irradiation with active energy rays. May be included. Moreover, both may be included in arbitrary ratios.

<Acrylic block copolymer>
The structure of the acrylic block copolymer (A) of the present invention is not particularly limited, and may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a block copolymer may be appropriately selected according to the required physical properties of the acrylic block copolymer, but in terms of cost and ease of polymerization, the linear block copolymer is preferable.

The linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the methacrylic polymer block (a ) Is expressed as a, and the acrylic polymer block (b) is expressed as b, (ab) _n- type, b- (ab) _n- type and (ab) _n- a-type (n is 1 An acrylic block copolymer having at least one structure selected from the group consisting of the above integers (for example, an integer of 1 to 3) is preferred. Among these, a diblock copolymer represented by ab, a triblock copolymer represented by abb, or a mixture thereof from the viewpoint of easy handling during processing and physical properties of the composition. A triblock copolymer is preferable from the viewpoint of heat resistance and mechanical properties.

  The molecular weight of the acrylic block copolymer (A) is not particularly limited, and may be determined from the molecular weights required for the methacrylic polymer block (a) and the acrylic polymer block (b). If the molecular weight is small, sufficient mechanical properties as an elastomer may not be exhibited. Conversely, if the molecular weight is larger than necessary, the processing properties may deteriorate. From such a viewpoint, the molecular weight of the acrylic block copolymer (A) is preferably 5,000 to 300,000 in terms of number average molecular weight, more preferably 10,000 to 200,000, still more preferably 10,000 to 150,000, most preferably 50,000-100,000. If the number average molecular weight is small, the viscosity is low, and if the number average molecular weight is large, the viscosity tends to be high. Therefore, the viscosity is appropriately set according to the required processing characteristics.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is not particularly limited, but is 1.8 or less. It is preferable that it is 1.5 or less. When Mw / Mn exceeds 1.8, the homogeneity of the acrylic block copolymer is deteriorated, and the expected physical properties such as viscosity and mechanical properties may be difficult to be expressed. For example, when it is used for a molded product, mechanical properties such as mechanical strength and elongation are lowered, and the viscosity is increased, so that the moldability is lowered and the compression set properties are lowered. Furthermore, when used for adhesives, etc., meltability and holding power at high temperatures may be reduced.

  The acrylic block copolymer has a methacrylic polymer block (a) and an acrylic polymer block (b) having a composition ratio of 5 to 90% by weight of the acrylacrylic polymer block (a). The block (b) is desirably 95 to 10% by weight, the methacrylic polymer block (a) is 10 to 70% by weight, and the acrylic polymer block (b) is 90 to 30% by weight. More preferably, the methacrylic polymer block (a) is 15 to 50% by weight and the acrylic polymer block (b) is 85 to 50% by weight. When the proportion of the methacrylic polymer block (a) is less than 5% by weight, the shape tends to be difficult to be maintained at the time of molding, and when the proportion of the acrylic polymer block (b) is less than 10% by weight, an elastomer is obtained. There is a tendency that the elasticity and flexibility, the meltability at the time of molding, and the tackiness when used as an adhesive are lowered.

  The hardness of the acrylic block copolymer (A) tends to be low when the proportion of the methacrylic polymer block (a) is small and high when the proportion of the methacrylic polymer block (a) is large. For this reason, the proportion of the methacrylic polymer block (a) may be appropriately set according to the required hardness. Further, the viscosity tends to be low when the proportion of the methacrylic polymer block (a) is small and high when the proportion of the methacrylic polymer block (a) is large. For this reason, the proportion of the methacrylic polymer block (a) may be appropriately set according to required processing characteristics.

The relationship between the glass transition temperatures of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is the glass transition of the methacrylic polymer block (a). Assuming that the temperature is Tg _a and the glass transition temperature of the acrylic polymer block (b) is Tg _b , it is preferable to satisfy the relationship of the following formula in terms of mechanical strength and rubber elasticity expression.
Tg _a > Tg _b
The glass transition temperature (Tg) of the polymer (methacrylic polymer block (a) and acrylic polymer block (b)) is set according to the following Fox formula: This can be done by setting the ratio.
_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ + ... + W _m = 1
(In the formula, Tg represents the glass transition temperature of the polymer portion, Tg ₁ , Tg ₂ ,..., Tg _m represents the glass transition temperature of each polymerization monomer. Also, W ₁ , W ₂ ,. _m represents the weight ratio of each polymerization monomer.)
As the glass transition temperature of each polymerization monomer in the Fox formula, for example, a value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.

  The glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity, but the methacrylic polymer block (a) and the acrylic polymer block (b). If the polarity is too close or the number of block monomer chains is too small, the measured values may deviate from the calculation formula based on the Fox equation.

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block obtained by polymerizing a monomer having a methacrylic acid ester as a main component. From the viewpoint of processability, the methacrylic acid ester is 50 to 100% by weight and It is preferable that it consists of 0-50 weight% of vinyl-type monomers copolymerizable with. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, transparency, etc., which are characteristics of the methacrylic acid ester, may be impaired.

  Moreover, as a method of introducing the active energy ray-curable functional group (c) into the methacrylic polymer block (a), the active energy ray-curable functional group (<active energy ray-curable functional group (c)>) ( There is a method of copolymerizing a (meth) acrylic acid ester or a vinyl monomer having c). The copolymerizable (meth) acrylic acid ester and the copolymerizable vinyl monomer will be described in detail in <Active energy ray-curable functional group (c)>. The methacrylic acid ester constituting the methacrylic polymer block (a) can be handled in the same manner as the vinyl monomer copolymerizable with the methacrylic acid ester. Moreover, the (meth) acrylic acid ester or vinyl monomer having the active energy ray-curable functional group (c) can be used alone or in combination of two or more.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (a) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n -Methacrylic acid fats such as pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate Group hydrocarbon (eg, alkyl having 1 to 18 carbon atoms) ester; methacrylic acid such as cyclohexyl methacrylate and isobornyl methacrylate Cyclic hydrocarbon esters; methacrylic acid aralkyl esters such as benzyl methacrylate; methacrylic aromatic hydrocarbon esters such as phenyl methacrylate and toluyl methacrylate; 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, etc. Esters of methacrylic acid and functional group-containing alcohols having etheric oxygen; hydroxyl group-containing methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate Trifluoromethyl methacrylate, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-trifluoroethyl methacrylate Acrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2- Methacrylic acid fluorinated alkyl esters such as perfluoromethyl-2-perfluoroethylmethyl methacrylate, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, And <epoxy group-containing methacrylic acid ester, oxetanyl group-containing methacrylic acid ester, hydrolyzable silyl group-containing methacrylic acid shown in <Active energy ray-curable functional group (c)> Examples include methacrylic acid esters containing active energy ray-curable functional groups (c) such as esters, vinyl group-containing methacrylic acid esters, allyl group-containing methacrylic acid esters, maleimide group-containing methacrylic acid esters, thiol group-containing methacrylic acid esters. Can do. These can be used alone or in combination of two or more. Among these, methyl methacrylate is preferable in terms of processability, cost, and availability. In addition, when the active energy ray-curable functional group (c) is introduced into the acrylic block copolymer (A) by polymerization, from the viewpoint of availability of monomers, ease of introduction, and crosslinking reactivity. Epoxy group-containing methacrylate ester, hydrolyzable silyl group-containing methacrylate ester, vinyl group-containing methacrylate ester, allyl group-containing methacrylate ester are preferable, epoxy group-containing methacrylate ester, allyl group-containing methacrylate ester are more preferable, Epoxy group-containing methacrylates are more preferred, and glycidyl methacrylate is particularly preferred.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, Halogen-containing unsaturated compound, silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, maleimide compound, epoxy group-containing vinyl compound represented by <active energy ray-curable functional group (c)>, oxetanyl group-containing vinyl compound , Vinyl compounds containing active energy ray-curable functional groups (c) such as hydrolyzable silyl group-containing vinyl compounds, allyl group-containing vinyl compounds, polyfunctional vinyl compounds, maleimide group-containing vinyl compounds, thiol group-containing vinyl compounds, etc. Can give.

  Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl. Acrylic aliphatic hydrocarbon (eg, alkyl having 1 to 18 carbon atoms) esters such as acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate; Acrylic alicyclic hydrocarbon esters such as cyclohexyl acrylate and isobornyl acrylate Acrylic aromatic hydrocarbon esters such as phenyl acrylate and toluyl acrylate Aralkyl acrylates such as benzyl acrylate Esters; esters of acrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate and functional group-containing alcohols having etheric oxygen; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4 Hydroxyl group-containing acrylates such as hydroxybutyl acrylate; trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl acrylate, 2-perfluoro Ethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl acetate Rate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate and other acrylic acid fluorinated alkyl esters, <active energy ray-curable functional group (c)> acrylic Examples include acid esters.

  Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

  Examples of the conjugated diene compound include butadiene and isoprene.

  Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

  Examples of the silicon-containing unsaturated compound include vinyltrimethoxysilane, vinyltriethoxysilane, and hydrolyzable silyl group-containing vinyl compounds represented by <active energy ray-curable functional group (c)>.

  Examples of the unsaturated dicarboxylic acid compound include maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid, and the like.

  Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and the like.

  Examples of the maleimide compound include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  These can be used alone or in combination of two or more. These vinyl monomers are used to adjust the glass transition temperature required for the methacrylic polymer block (a), to be compatible with the acrylic polymer block (b), and to be active energy ray curable as necessary. What is necessary is just to select suitably from viewpoints, such as the ease of introduction | transduction of a functional group (c), and reactivity, Epoxy group containing acrylic ester, hydrolysable silyl group containing acrylic ester, allyl group containing acrylic ester, A vinyl group-containing acrylic ester is preferred from the viewpoint of reactivity during polymerization, an epoxy group-containing acrylic ester and an allyl group-containing acrylic ester are more preferred, and an epoxy group-containing acrylic ester is particularly preferred.

  From the viewpoint of thermal deformation of the acrylic block copolymer, the methacrylic polymer block (a) is preferably designed such that the glass transition temperature is 25 to 200 ° C, and is 40 to 150 ° C. It is more preferable that the temperature is 50 to 130 ° C. If the glass transition temperature of (a) is lower than the temperature of the environment in which the acrylic block copolymer is used, thermal deformation may easily occur due to a decrease in cohesive force.

  From the viewpoint described above, when the methacrylic polymer block (a) is mainly composed of methyl methacrylate and the active energy ray-curable functional group (c) is introduced by copolymerization, <active energy ray Curable functional group (c)> monomer, more preferably an epoxy group-containing vinyl compound, hydrolyzable silyl group-containing vinyl compound, allyl group-containing vinyl compound, polyfunctional vinyl compound, more preferably an epoxy group-containing ( At least one monomer selected from the group consisting of (meth) acrylic acid esters, hydrolyzable silyl group-containing (meth) acrylic acid esters, allyl group-containing (meth) acrylic acid esters, and vinyl group-containing (meth) acrylic acid esters Body, more preferably epoxy group-containing (meth) acrylic acid ester, allyl group-containing (meth) acrylic acid ester At least one monomer selected from Ranaru group, particularly preferably glycidyl methacrylate, allyl methacrylate, most preferably obtained by copolymerizing glycidyl methacrylate blocks are preferred. For the purpose of controlling the glass transition point, it is obtained by polymerizing at least one monomer selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-methoxyethyl acrylate and 2-ethylhexyl acrylate. A block is preferred, and among these, ethyl acrylate is particularly preferred from the viewpoint of compatibility with methyl methacrylate.

<Acrylic polymer block (b)>
The acrylic polymer block (b) is a block obtained by polymerizing a monomer having an acrylic ester as a main component, and includes 50 to 100% by weight of the acrylic ester and a vinyl monomer copolymerizable therewith. It is preferably composed of 0 to 50% by weight. If the proportion of the acrylic ester is less than 50% by weight, the physical properties of the composition, particularly flexibility and oil resistance, which are characteristic when the acrylic ester is used, may be impaired.

  Examples of the acrylic ester constituting the acrylic polymer block (b) include the same monomers as the acrylic ester exemplified as the monomer constituting the methacrylic polymer block (a). .

  These can be used alone or in combination of two or more. Among these, n-butyl acrylate is preferable in terms of balance between flexibility, rubber elasticity, low temperature characteristics, and cost. When oil resistance and mechanical properties are required, it is preferable to copolymerize ethyl acrylate. Further, when it is necessary to impart low temperature characteristics and oil resistance and to improve the surface tackiness of the resin, it is preferable to copolymerize 2-methoxyethyl acrylate. When low temperature characteristics and adhesive characteristics are required, it is preferable to copolymerize 2-ethylhexyl acrylate.

  Moreover, as a method for introducing the active energy ray-curable functional group (c) into the acrylic polymer block (b), the active energy ray-curable functional group (c) shown in <Active energy ray-curable functional group (c)> is used. There is a method of copolymerizing a (meth) acrylic acid ester or a vinyl monomer having). In the case of this method, the copolymerizable (meth) acrylic acid ester and the copolymerizable vinyl monomer will be described in detail in <Active energy ray-curable functional group (c)>. Can be handled in the same manner as the acrylic monomer constituting the acrylic polymer block (b) and the vinyl monomer copolymerizable with the acrylic ester. These can be used alone or in combination of two or more.

  Examples of vinyl monomers copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen, and the like. -Containing unsaturated compound, silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, maleimide compound, active energy ray-curable functional group (c) shown in <active energy ray-curable functional group (c)> Examples thereof include vinyl monomers.

  Methacrylate, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound, vinyl ester compound, maleimide compound, <activity Examples of the vinyl monomer containing the active energy ray-curable functional group (c) shown in the energy ray-curable functional group (c)> are examples of monomers constituting the methacrylic polymer block (a). Among these, monomers other than acrylic acid esters can be mentioned.

  These can be used alone or in combination of two or more. These vinyl monomers are appropriately selected in consideration of the balance of the glass transition temperature and oil resistance required for the acrylic polymer block (b), compatibility with the methacrylic polymer block (a), and the like. Select the preferred one. For example, when the purpose is to improve the oil resistance of the acrylic block copolymer (A), acrylonitrile may be copolymerized. In the case where the active energy ray-curable functional group (c) is introduced by copolymerization, an epoxy group-containing vinyl compound or hydrolyzable silyl is preferable from the viewpoint of availability of monomers, ease of introduction, and reactivity. Group-containing vinyl compound, allyl group-containing vinyl compound, polyfunctional vinyl compound, more preferably epoxy group-containing (meth) acrylic acid ester, hydrolyzable silyl group-containing (meth) acrylic acid ester, allyl group-containing (meth) acrylic acid At least one monomer selected from the group consisting of an ester and a vinyl group-containing (meth) acrylic acid ester, more preferably a group consisting of an epoxy group-containing (meth) acrylic acid ester and an allyl group-containing (meth) acrylic acid ester At least one monomer selected from the group consisting of glycidyl methacrylate and allyl methacrylate DOO, most preferably it is preferred to copolymerize glycidyl methacrylate.

  From the viewpoint of rubber elasticity of the acrylic block copolymer (A), the acrylic polymer block (b) preferably has a glass transition temperature of 25 ° C. or lower, more preferably 0 ° C. or lower, More preferably, it is −20 ° C. or lower. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the acrylic block copolymer (A) is used, flexibility, rubber elasticity, and adhesive properties are hardly exhibited.

  From the viewpoints described above, the acrylic polymer block (b) is at least one selected from the group consisting of -n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate. In addition, a block obtained by polymerizing 50 to 100% by weight of different acrylates copolymerizable with these and 50 to 0% by weight of vinyl monomers copolymerizable with these is preferable.

The Tg _b of the acrylic polymer block (b) can be set by setting the weight ratio of the monomers in each polymer portion according to the Fox formula.

<Active energy rays>
The active energy ray-curable composition of the present invention is cured by irradiation with active energy rays. As the active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet ray or electron beam irradiation is preferred, and curing by ultraviolet ray irradiation is more preferred from the viewpoint of availability and price. When the active energy ray-curable composition of the present invention contains the active energy ray-curable functional group (c) or the photoinitiator (B), the photoinitiator (B) is activated by the active energy ray, and the active energy ray The curable functional group (c) reacts. When irradiating high energy active energy rays such as electron beams, active energy ray-curable functional groups (c) such as (meth) acryloyl groups and allyl groups themselves are activated by active energy rays and react easily. In the case of irradiating ultraviolet rays, the photoinitiator (B) is included in the composition, and the photoinitiator (B) is activated by irradiation to activate the active energy ray-curable functional group such as a (meth) acryloyl group or an epoxy group. It may be preferable from the viewpoint of reactivity that the group (c) reacts.

  As a method of curing by ultraviolet irradiation, if an active energy ray is irradiated using 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, etc. Good.

  During irradiation after active energy ray irradiation or after irradiation, curing can be promoted by heating as necessary.

<Active energy ray-curable functional group (c)>
The acrylic block copolymer (A) of the present invention has an active energy ray-curable functional group (c). The active energy ray-curable functional group (c) means a functional group that is activated by irradiation with active energy rays or a functional group that is activated by a photoinitiator activated by irradiation with active energy rays. When the active energy ray is irradiated to the composition of the present invention, when the active energy ray-curable functional group (c) or the photoinitiator (B) is contained, the photoinitiator (B) is activated, and the active energy ray is cured. The functional group (c) reacts and cures, and a crosslinked structure can be introduced into the acrylic block copolymer.

  By introducing a crosslinked structure, properties such as heat resistance, tackiness, adhesiveness, mechanical strength, compression set, oil resistance, rubber elasticity, etc. can be improved.

  The active energy ray-curable functional group (c) is not particularly limited as long as it is a functional group that is cured by irradiating the composition of the present invention with active energy rays. From the viewpoint of availability of the compound having c), a (meth) acryloyl group, a vinyl group, an allyl group, a vinyl ether group, an epoxy group, an oxetanyl group, a thiol group, a maleimide group, and a hydrolyzable silyl group are preferable. Among these, (meth) acryloyl group, allyl group, and epoxy group are preferable from the viewpoint of ease of introduction and reactivity, and (meth) acryloyl group and epoxy group are more preferable from the viewpoint of reactivity. An epoxy group is most preferred from the balance of ease. However, from the viewpoint of reactivity, the (meth) acryloyl group may be better than the epoxy group or the allyl group.

  These functional groups are not limited to one type, and a plurality of types may be introduced into one molecule. The acrylic block copolymer (A) of the present invention is different from the acrylic block copolymer molecule having one type of active energy ray-curable functional group (c) and the acrylic block copolymer molecule. An acrylic block copolymer mixture composed of acrylic block copolymer molecules having various types of active energy ray-curable functional groups (c) may be used.

  The introduction amount per molecule of the active energy ray-curable functional group (c) is not particularly limited, but the average introduction number per molecule is preferably 1 or more from the viewpoint of curability, and is 2 or more. More preferably, it is more preferably 5 or more, and particularly preferably 10 or more. If it is less than 1, the curability may be insufficient.

  The crosslinkable functional group may be contained in only one of the methacrylic polymer block (a) and the acrylic polymer block (b), or may be contained in both blocks. Depending on the physical properties of the acrylic block copolymer composition required, it can be used separately.

  For example, it is preferably introduced into the methacrylic polymer block (a) in terms of improving heat resistance and heat decomposability, and acrylic polymer block (b) in terms of improving oil resistance, rubber elasticity, and compression set characteristics. ) Is preferably introduced. Although not particularly limited, either the methacrylic polymer block (a) or the acrylic polymer block (b) in terms of control of reaction points, heat resistance, rubber elasticity, mechanical strength, flexibility, etc. It is preferable to have in the methacrylic polymer block (a) from the viewpoint of the balance between adhesive strength and holding power.

  Since the number of introduction of the active energy ray-curable functional group (c) may be restricted when it is introduced at the molecular end, it may be preferable to be other than the end of the acrylic block copolymer (A).

  A method for introducing the active energy ray-curable functional group (c) into the acrylic block copolymer (A) is not particularly limited, but a method of copolymerizing a monomer having the active energy ray-curable functional group (c). , A method of generating an active energy ray-curable functional group (c) from a precursor by any method after copolymerizing a monomer having a precursor of an active energy ray-curable functional group (c), an acrylic block copolymer Examples thereof include a method in which an active energy ray-curable functional group (c) -containing compound containing a functional group having reactivity with a polymer in the molecule is reacted and introduced. Among these, from the viewpoint of ease of introduction, a method of copolymerizing a monomer having an active energy ray-curable functional group (c) and a functional group having reactivity with an acrylic block copolymer are incorporated in the molecule. A method in which the active energy ray-curable functional group (c) -containing compound contained in is reacted and introduced is preferable.

  In the introduction by copolymerization, the monomer having the active energy ray-curable functional group (c) is not particularly limited, but (meth) acryloyl group, vinyl group, allyl group, epoxy group, vinyl ether group, oxetanyl group, thiol And vinyl monomers containing a group, a maleimide group and a hydrolyzable silyl group. These monomers may have one or more types of the above functional groups per molecule.

  Examples of (meth) acryloyl group-containing vinyl monomers include allyl group-containing (meth) acrylates and polyfunctional (meth) acrylates. Allyl group-containing (meth) acrylates include allyl (meth) acrylate and butenyl ( And (meth) acrylate.

  Polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, ethoxylated 2-methyl-1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (Meta) acryle Tricyclodecane dimethanol di (meth) acrylate, glycerin di (meth) acrylate, ethoxylated isocyanuric acid di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) Di (meth) acrylates such as acrylate, propoxylated bisphenol A di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, etc. Compounds having a methacryloyl group and an acryloyl group in one molecule, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pro Xylated trimethylolpropane tri (meth) acrylate, tri (meth) acrylate such as ethoxylated isocyanuric acid tri (meth) acrylate, tetra (meth) acrylate such as ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) ) Penta (meth) acrylate such as acrylate, Hexa (meth) acrylate such as dipentaerythritol hexa (meth) acrylate, Bisphenol epoxy (meth) acrylate, Novolac epoxy (meth) acrylate, Polyester polyfunctional (meth) acrylate , Urethane polyfunctional (meth) acrylate, polyether polyfunctional (meth) acrylate, polybutadiene polyfunctional (meth) acrylate, silicon polyfunctional (meth) acrylic Rate, poly (meth) acrylic polyfunctional (meth) acrylate, and the like.

  Examples of the monomer containing a vinyl group include polyfunctional vinyl compounds such as divinylbenzene, trivinylbenzene, and diallyl phthalate.

  Examples of the monomer containing an allyl group include the above allyl (meth) acrylate.

Examples of monomers containing vinyl ether groups include polyfunctional vinyl ethers such as butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether, and sasolcinol divinyl ether. Examples of the monomer containing an epoxy group include epoxycyclo C5-8 alkenyl (meth) acrylate such as glycidyl (meth) acrylate, epoxycyclohexenyl (meth) acrylate, 2- (3,4-epoxy) (Cyclohexyl) ethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, epoxidized soybean oil (meth) acrylate, etc. have epoxy groups in the molecule Epoxy (meth) acrylate, and epoxy group-containing alkenyl compound such as allyl glycidyl ether.

  As a monomer containing an oxetanyl group, an oxetanyl group-containing vinyl compound such as (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl, and as a monomer containing a thiol group, 2-vinylbenzenethiol And thiol group-containing alkenyl compounds.

  Examples of the monomer containing a maleimide group include N, N′-1,4-phenylenedimaleimide and N, N ′-[4,4′-methylenebis (6-ethyl-2-methylphenyl)] dimaleimide. Examples thereof include dimaleimide compounds.

  As monomers containing hydrolyzable silyl groups, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethoxydimethylsilane, vinylmethyldiethoxysilane, vinyl Vinylalkoxysilanes such as ethoxydimethylsilane, vinylmethyldi (ethoxymethoxy) silane, vinylethyldimethoxysilane and vinyl (ethoxymethoxy) dimethylsilane, allylalkoxysilanes such as allyltriethoxysilane, vinylalkanoyloxysilanes such as vinyltriacetoxysilane , 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, β- (meth) acryloylo Alkoxysilyl group-containing (meth) acrylates such as (meth) acryloyloxyalkylalkoxysilane such as cyethyltrimethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, etc. Is mentioned.

  Here, the hydrolyzable silyl group is a functional group that can be crosslinked by forming a siloxane bond by hydrolysis, and the hydrolyzable group bonded to the silicon atom is not particularly limited, for example, hydrogen, Preferred examples include halogen groups, alkoxy groups such as methoxy groups, ethoxy groups, acyl oxide groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyl oxide groups. Particularly preferred are alkoxy groups which are easy and do not produce harmful by-products during the reaction. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, tert-butoxy group, phenoxy group, and benzyloxy group. Examples of the alkoxysilyl group to which the alkoxy group is bonded include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxysilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.

Among these, vinyl monomers having a (meth) acryloyl group, a vinyl group, an allyl group, an epoxy group, and a hydrolyzable silyl group are preferable from the viewpoint of ease of introduction and reactivity during irradiation with active energy rays. , Polyfunctional (meth) acrylate, allyl group-containing (meth) acrylate, epoxy group-containing (meth) acrylate, alkoxysilyl group-containing (meth) acrylate are more preferred, allyl group-containing (meth) acrylate, epoxy group-containing (meth) Acrylates are more preferred, epoxy group-containing (meth) acrylates are particularly preferred, and glycidyl (meth) acrylate is particularly preferred.
In introducing an allyl group or an epoxy group, a copolymerization method may be preferable from the viewpoint of ease of introduction. On the other hand, in the introduction of a (meth) acryloyl group, if a polyfunctional (meth) acrylate is used for introduction by copolymerization, gelation may occur. Therefore, a functional group having reactivity with an acrylic block copolymer may be used. A method in which the active energy ray-curable functional group (c) -containing compound contained in the molecule is reacted and introduced may be preferred.

  The method for reacting and introducing the active energy ray-curable functional group (c) -containing compound containing a functional group having reactivity with the acrylic block copolymer in the molecule is not particularly limited, but includes a hydroxyl group and an isocyanate group. The reactive functional group is introduced into the acrylic block copolymer by copolymerizing a monomer having a reactive functional group such as an epoxy group, and the reactive functional group reacts with the reactive functional group. There is a method of reacting and introducing a compound having the linear curable functional group (c).

  Specifically, hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like are used together. By introducing a hydroxyl group into an acrylic block copolymer by polymerization, an acid halide of (meth) acrylic acid such as (meth) acryloyl chloride, or a (meth) acryloyl group-containing carboxylic acid such as (meth) acrylic acid (Meth) acryloyl reacted with one selected from a compound, a metal salt of (meth) acrylic acid such as potassium (meth) acrylate, and an isocyanate group-containing (meth) acrylate such as 2- (meth) acryloyloxyethyl isocyanate Group introduction method, hydroxyl group-containing acrylic bromine After reacting diisocyanate compounds such as toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate with the copolymer, a (meth) acryloyl group is introduced by reacting with a hydroxyl group-containing (meth) acrylate. A method of reacting a hydroxyl group-containing (meth) acrylate after copolymerizing an isocyanate group-containing (meth) acrylate such as 2- (meth) acryloyloxyethyl isocyanate, an epoxy group-containing (meth) such as glycidyl (meth) acrylate Examples include a method in which an epoxy group is introduced into an acrylic block copolymer by copolymerizing an acrylate and reacted with (meth) acrylic acid or the like. In these methods, it is possible to increase the reactivity by using a catalyst or the like as necessary.

  When copolymerizing a hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of availability, and 2-hydroxyethyl is introduced into the methacrylic copolymer block from the viewpoint of compatibility. Methacrylate is preferred, and 2-hydroxyethyl acrylate is preferred when introduced into the acrylic polymer block.

  From the viewpoint of introduction efficiency and active energy ray curability after introduction, a method of reacting an acid halide of (meth) acrylic acid such as acryloyl chloride with a hydroxyl group-containing acrylic block copolymer in the presence of a base such as triethylamine, A method in which an isocyanate group-containing (meth) acrylate such as 2-acryloyloxyethyl isocyanate is reacted in the presence of one kind of catalyst selected from an organic tin compound such as dibutyltin (mercapto acid ester), a titanium compound, and a zirconium compound, and an epoxy group A method is preferred in which acrylic block copolymer is reacted with acrylic acid in the presence of a catalyst such as triphenylphosphine or dimethylaniline.

  Among these, a method using acryloyl chloride in the presence of a base and a method using 2-acryloyloxyethyl isocyanate in the presence of an organic tin catalyst are particularly preferable.

  The acrylic block copolymer of the present invention can also be used in combination with a compound having an active energy ray-curable functional group (c).

  As the compound having an active energy ray-curable functional group (c) that can be used in combination, a compound having a vinyl group, a (meth) acryloyl group-containing compound comprising a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate, an epoxy group-containing compound Examples thereof include compounds, oxetanyl group-containing compounds, thiol group-containing compounds, maleimide group-containing compounds, and compounds having vinyl ether.

  Styrene derivatives such as styrene, indene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, p-chloromethylstyrene, p-acetoxystyrene, divinylbenzene as compounds having a vinyl group And naphthalene derivatives such as 1-vinylnaphthalene and 2-vinylnaphthalene, compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate, N- And vinyl pyrrolidone. However, it is not limited to these.

  Among the (meth) acrylic group-containing compounds, as monofunctional (meth) acrylate, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meta Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) Acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Acrylate), tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , 7-amino-3,7-dimethyloctyl (meth) acrylate, trifluoromethyl ( (Meth) acrylate, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl 2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoro Ethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, allyl (meth) acrylate Rate, glycidyl (meth) acrylate, bisphenol and novolac monofunctional epoxy acrylates, monofunctional urethane acrylates, monofunctional polyester acrylates, monofunctional polyether acrylates, monofunctional polybutadiene acrylates, monofunctional silicon acrylates And monofunctional poly (meth) acrylic acrylates. However, it is not limited to these.

  Specific examples of polyfunctional (meth) acrylates among (meth) acrylic group-containing compounds include, for example, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyldimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neope Nthyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di ( Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, adduct of ethylene oxide or propylene oxide of hydrogenated bisphenol A Di (meth) acrylates of certain diols, cyclohexanedimethanol di (meth) acrylates, bisphenol and novolac epoxy acrylates, urethane acrylates Relate, polyester acrylates, polyether acrylates, polybutadiene acrylates, silicone acrylates, and poly (meth) acrylic acrylates. However, it is not limited to these.

  Epoxy group-containing compounds include monofunctional epoxy group-containing compounds such as butyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6 hexanediol diglycidyl ether, neopentyl glycol Diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, aliphatic cyclic epoxy resin, brominated epoxy resin, rubber modification Epoxy resin, urethane modified epoxy resin, glycidyl ester compound, epoxidized polybutadiene, epoxidized SBS (SBS is styrene-butane Ene - shows the styrene copolymer) compound having an epoxy group of the epoxy resin, such as, and the like. However, it is not limited to these.

  Examples of the oxetanyl group-containing compound include 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl- Monofunctional oxetanes such as 3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis And polyfunctional oxetanes such as {[1-ethyl (3-oxetanyl)] methyl} ether. However, it is not limited to these.

  As the thiol group-containing compound, 1,4-butanedithiol, 1,10-decanedithiol, 3,6-dioxa-1,8-octanedithiol, bis (2-mercaptoethyl) ether, 1,4-bis (mercaptomethyl) ) Benzene, 4,5-bis (mercaptomethyl) -o-xylene, 1,6-hexanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 2,3-dimercapto-1-propanol, s- Examples include thiol compounds such as triazine-2,4,6-trithiol. However, it is not limited to these. When curing a thiol group-containing acrylic block copolymer or a composition containing a thiol group-containing compound, it is preferable to use a compound having two or more carbon-carbon double bonds in one molecule.

  Examples of the maleimide group-containing compound include 4,4′-methylenebis (N-phenylmaleimide), 2,3-bis (2,4,5-trimethyl-3-thienyl) maleimide, 1,2-bismaleimide ethane, 1, 6-bismaleimide hexane, triethylene glycol bismaleimide, N, N'-m-phenylene dimaleimide, m-tolylene dimaleimide, N, N'-1,4-phenylene dimaleimide, N, N'-diphenylmethane dimaleimide N, N′-diphenyl ether dimaleimide, N, N′-diphenylsulfone dimaleimide, 1,4-bis (maleimidoethyl) -1,4-diazoniabicyclo- [2,2,2] octane dichloride, N— (9-acridinyl) maleimide and the like. However, it is not limited to these.

  Examples of the compound having vinyl ether include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, tritylene glycol methyl vinyl ether, benzoate (4-vinyloxy) butyl, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1 , 4-Geo Ru-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol-divinyl ether, di (4-vinyloxy) butyl isophthalate, di (4-vinyloxy) butyl glutarate, trimethylol Propane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol-monovinyl ether, diethylene glycol monovinyl ether 3-aminopropyl vinyl ether, 2- (N, N- Diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether, and the like. However, it is not limited to these.

  These compounds may be used alone or in combination of two or more. Moreover, the compound containing the said functional group may contain only 1 type of this functional group per molecule, and may contain it in combination of 2 or more types.

  Among these, a (meth) acryl group-containing compound and an epoxy group-containing compound are preferable from the viewpoint of availability and reactivity at the time of active energy ray irradiation.

<Method for producing acrylic block copolymer (A)>
Although it does not specifically limit as a method to manufacture an acryl-type block copolymer (A), It is preferable to use a control polymerization method. Controlled polymerization methods include living anion polymerization (JP-A-11-335432), polymerization using an organic rare earth transition metal complex as a polymerization initiator (JP-A-6-93060), radical polymerization using a chain transfer agent (special Kaihei 2-45511), a living radical polymerization method and the like.

  Living radical polymerization methods include, for example, a polymerization method using a chain transfer agent such as polysulfide, a polymerization method using a cobalt porphyrin complex, a polymerization method using a nitroxide (WO 2004/014926), and a high-cycle heteroelement compound such as an organic tellurium compound. And the like. (Polymer No. 3839829), Reversible Addition / Desorption Chain Transfer Polymerization (RAFT) (Patent No. 3639859), Atom Transfer Radical Polymerization (ATRP) (Patent No. 3040172), and the like. In the present invention, any of these methods is not particularly limited, but the atom transfer radical polymerization method is preferable from the viewpoint of easy control.

  As a method for producing the acrylic block copolymer (A) using the atom transfer radical polymerization method, for example, the method described in WO2004 / 013192 can be used.

  In particular, the acrylic block copolymer (A) of the present invention is a metal complex having an organic halide or a sulfonyl halide compound as an initiator and at least one selected from Fe, Ru, Ni and Cu as a central metal. Those produced by an atom transfer radical polymerization method using as a catalyst are preferred.

  However, when removing a metal complex from an acrylic block copolymer solution containing an epoxy group or oxetanyl group obtained by polymerization, a weakly acidic compound such as ascorbic acid or a weakly acidic adsorbent, activated alumina, or the like is blocked. A method of removing metals and the like by mixing with a polymer solution and removing solids by filtration is preferred.

<Photoinitiator (B)>
The active energy ray-curable composition of the present invention may contain a photoinitiator. However, when curing with a high energy beam such as an electron beam, the active energy beam curable functional group (c) is a functional group having reactivity with a high energy beam such as a (meth) acryloyl group or an allyl group. Even if it does not contain a photoinitiator, it can be cured.

  The photoinitiator (B) is not particularly limited as long as it can crosslink the acrylic block copolymer (A) having an active energy ray-curable functional group (c). , A compound that generates a cation or a base. The photoinitiator (B) can be appropriately selected depending on the type of the active energy ray-curable functional group (c).

  As the photoinitiator, when the acrylic block copolymer (A) has any one or more of radically polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, an allyl group, and a thiol group, Examples thereof include benzophenone initiators, acetophenone initiators, thioxanthone initiators, and phosphine oxide initiators, which are initiators that generate radicals. However, it is not particularly limited as long as it is a radical polymerization initiator. Specifically, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzyldimethyl ketal, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1- Carbonyl compounds such as phenylpropan-1-one, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, α, α-dimethoxy-α-phenylacetophenone, Sulfur compounds such as tramethylthiuram monosulfide and tetramethylthiuram disulfide, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, bis (cyclopentadienyl) -bis (2,6 -Radical polymerization initiators such as -difluoro-3- (pyrrolyl-1-phenyl) titanium can be mentioned, and these can be used alone or in combination of two or more.

  Among these, in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, α, α-Dimethoxy-α-phenylacetophenone is preferable in terms of reactivity, transparency, and price.

  Specific product names of the radical polymerization initiator include 2,2-dimethoxy-2-phenylacetophenone (manufactured by Tokyo Chemical Industry), IRGACURE 184 (1-hydroxy-cyclohexyl phenyl ketone; manufactured by Ciba Japan), IRGACURE 651 (2,2-dimethoxy). -1,2-diphenylethane-1-one; manufactured by Ciba Japan) DAROCUR 1173 (2-hydroxy-2-methyl-1-phenylpropane-1-one; manufactured by Ciba Japan), IRGACURE 2959 (manufactured by Ciba Japan), IRGACURE 127 (Ciba Japan), IRGACURE 907 (Ciba Japan), IRGACURE 369 (Ciba Japan), IRGACURE 379 (Ciba Japan), DAROCUR TPO (Ciba Japan), IRGACU E 819 (manufactured by Ciba Japan), IRGACURE 819DW (manufactured by Ciba Japan), IRGACURE 784 (manufactured by Ciba Japan), IRGACURE OX 01 (manufactured by Ciba Japan), IRGACURE OX 02 (manufactured by Ciba Japan), IRGACURE 754 (manufactured by Ciba Japan), IRGACURE 754 500 (manufactured by Ciba Japan), IRGACURE 1800 (manufactured by Ciba Japan), IRGACURE 1870 (manufactured by Ciba Japan), DAROCUR 4265 (manufactured by Ciba Japan), KAYACURE BP (manufactured by Nippon Kayaku), KAYACURE DETX-S (manufactured by Nippon Kayaku) ESACURE KIP 150 (manufactured by Lamberti), S-121 (manufactured by Shinko Giken), Seiko All BEE (manufactured by Seiko Chemical), Solvathron BIPE (manufactured by Kurogane Kasei), SO Basuron BIBE (Kurogane Kasei Co., Ltd.), and the like. However, it is not limited to this.

  When the acrylic block copolymer (A) has one or more of cationically polymerizable functional groups such as an epoxy group, a vinyl ether group, an oxetanyl group, and a hydrolyzable silyl group, it is a photocationic initiator. Examples include sulfonium salt initiators, onium salt initiators such as iodonium salts, sulfonic acid derivatives, carboxylic acid esters, aryldiazonium salts, iron arene complexes, pyridinium salts, quinolinium salts, and O-nitrobenzyl group-containing compounds. The However, the cationic initiator is not particularly limited. In the present invention, the photocation initiator is synonymous with the photoacid generator. More specifically, the initiator is p-hydroxyphenylbenzylmethylsulfonium salt such as p-phenylbenzylmethylsulfonium salt, p-phenyldimethylsulfonium salt, benzylmethyl p-hydroxyphenylsulfonium hexafluoroantimonate, etc. Benzylmethylsulfonium salts, triarylsulfonium salts such as triphenylsulfonium salts, diphenyl-4-thiophenoxyphenylsulfonium salts, and 4,4-bis [di (β-hydroxyethoxy) phenylsulfonio] phenisulfide bishexa Disulfonium salts having a bis- [4- (diphenylsulfonio) phenyl] sulfide skeleton such as fluoroantimonate, diphenyliodonium, bis (4-tert-butylphenyl) iodonium And iodonium salts such as (4-tert-butoxyphenyl) phenyliodonium and (4-methoxyphenyl) phenyliodonium. These can be used alone or in combination of two or more.

Of these, disulfonium salts and triarylsulfonium salts having a bis- [4- (diphenylsulfonio) phenyl] sulfide skeleton are particularly preferable from the viewpoint of thermal stability. Examples of the counter anion of these sulfonium salts include SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ^{− and the} like. From the viewpoint of reactivity and stability, SbF ₆ ⁻ , BF ₆ ⁻ and PF ₆ ⁻ may be used. Preferably used. Specific product names of these cationic polymerization initiators include Adeka optomer SP-172 (manufactured by ADEKA), Adeka optomer SP-170 (manufactured by ADEKA), Adeka optomer SP-152 (manufactured by ADEKA), Adeka optomer SP- 150 (manufactured by ADEKA), Sun Aid SI-60L (manufactured by Sanshin Chemical Industry), Sun Aid SI-80L (manufactured by Sanshin Chemical Industry), Sun Aid SI-100L (manufactured by Sanshin Chemical Industry), Sun Aid SI-150L (manufactured by Sanshin Chemical) Industrial), IRGACURE250 (manufactured by Ciba Japan), and the like.

  When the acrylic block copolymer (A) contains an epoxy group, photobase generators such as cobaltamine complexes, trimethylbenzhydrylammonium iodide, O-acyloxime, carbamic acid derivatives, formamide derivatives and the like can be mentioned. .

  The amount of such photoinitiator is appropriately adjusted according to the curability of the acrylic block copolymer of the present invention, but considering the reactivity, transparency, and price, 0.01 to 10 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, and still more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the composition. .

  The acrylic block copolymer composition of the present invention may contain a sensitizer together with the photoinitiator (B).

  The sensitizer is not particularly limited as long as it moves or broadens the active energy ray sensitivity and accelerates the curing reaction, but is not limited to triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylamino. Amine compounds such as methyl benzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and compounds having a structure containing a long conjugated double bond are preferred. Examples of the structure including a long conjugated double bond include a structure having a benzoyl group, a thiophene group, or a polycyclic aromatic group. Examples of the compound having a benzoyl group include benzophenone, benzoyl, and derivatives thereof. Examples of the compound having a thiophene group include thiophene and derivatives thereof. Examples of the compound having a polycyclic aromatic group include naphthalene, anthracene, phenanthrene, pyrene, pentacene, coumarin, thioxanthone, acetophenone, naphthoquinone, anthraquinone, and derivatives thereof. The photosensitizer is preferably a compound that can be easily obtained from the market. Examples thereof include DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.).

<Other ingredients>
The acrylic block copolymer composition of the present invention may contain various additives other than those described above as necessary for the purpose of adjusting various physical properties. As such additives, fillers, lubricants, stabilizers, plasticizers, flexibility imparting agents, flame retardants, pigments, antistatic agents, antibacterial antifungal agents, tackifiers, fluidity improvers, antiblocking agents, crosslinks An agent, a crosslinking aid, a dye, a conductive filler and the like may be added. These can be used alone or in combination of two or more. Moreover, a foaming agent, that is, various chemical foaming agents and physical foaming agents can be added.

  There is no restriction | limiting in particular as a manufacturing method of the composition (combination) containing the acryl-type block copolymer (A) of this invention, A well-known method is applicable.

  For example, it can mix | blend by using a batch type kneading apparatus and a continuous kneading apparatus. As a batch type kneading apparatus, for example, a pressure-resistant reaction vessel, a mixing roll, a Banbury mixer, a pressure kneader, or a high shear mixer can be used. Moreover, as a continuous kneading apparatus, a single screw extruder, a twin screw extruder, a KCK extrusion kneader, etc. can be used.

  In addition, the acrylic block copolymer (A) and the blending components are blended by mixing them in a soluble solvent, and the resulting composition is used as it is, or the solvent is removed using an evaporator or the like. It can also be removed and used.

  The blending order of each component is not particularly limited, and can be determined according to the equipment used, workability, or physical properties of the resulting composition.

  The shape of the resulting composition is not particularly limited, and examples thereof include a bale shape, a solution shape, a pellet shape, and a powder shape. Each shaping method can use an existing method. Further, for example, the pellets can be subjected to an adhesion preventing process by the method described in JP-A-2003-253005.

<Processing method of acrylic block copolymer composition>
The acrylic block copolymer composition of the present invention may be used alone, or may be used in a state dissolved in an appropriate solvent or in a state where various compounding agents are added.

  Moreover, it can be cured by irradiating active energy rays in a desired shape / state.

  The processing method of the acrylic block copolymer composition in the present invention is not particularly limited, and is an extrusion method, a profile extrusion method, an injection molding method, a multilayer molding method, a two-color molding method, an insert molding method, a sandwich molding method, Examples include foam molding, press molding, blow molding, calendar molding, rotational molding, slush molding, dip molding, and cast molding. Examples of the shape of the molded body obtained by such a processing method include a coating film, a film, a sheet, a tube, a bag, a pipe, various atypical materials, containers, and the like. Moreover, it can be hardened after shaping | molding by irradiating an active energy ray to the obtained molded object.

  The acrylic block copolymer composition of the present invention is excellent in curability by active energy rays, and is excellent in adhesive strength, holding power, moldability, and curability after shaping.

Therefore, the acrylic block copolymer composition of the present invention can be used as an adhesive, an adhesive, a coating film, a sealant, a film, a sheet, various molded articles, a resin modifier, and the like for automobiles, home appliances / light electrical appliances, industrial Applicable as parts, civil engineering / architecture, sporting goods / daily miscellaneous goods, packaging materials, medical / healthcare products, for example, adhesives, adhesives, paints, coating materials, sealants, stereolithography materials, resists It can be used for applications such as materials, inks, viscosity modifiers, vibration damping materials, soundproofing materials, foams, dispersion materials, binders, leather materials, gels, insulating materials, cosmetics, and resin modifiers. Among these, since it is excellent in adhesive force and holding power, it can be suitably used particularly as an adhesive.
Specific examples of applications are shown below.

(1) Adhesives Base resins or additives such as solvent-free adhesives, reactive adhesives, hot-melt adhesives, solvent-based adhesives, water-based adhesives, etc. produced by multilayer coextrusion molding, etc. As applicable. Further, it can be applied as a base resin or an additive for base sheets and films for pressure-sensitive adhesives.

  Applications include electronics, home appliances / light electrical appliances, industrial parts, automobiles, aviation, medical / healthcare, civil engineering / architecture, sports / daily necessities, and various adhesives used in packaging fields. Tapes, tack sheets, various ultraviolet and electron beam curing adhesives, more specifically displays, adhesives for surface protection sheets for precision equipment, adhesives for automobile bodies and bumpers, adhesives for bonding optical films , Adhesives for optical discs, Adhesives for LCDs, CDs, DVDs, Blue-ray disc adhesives, Double-sided adhesive tapes for fixing precision parts, Electronic material process adhesive tapes, Back grinding Tape, dicing scoop, electrical insulation tape, printed wiring board tape, anisotropic conductive film tape, coating masking tape Kraft adhesive tape, double-sided tape, double-sided tape without base material, foam tape, tape adhesive etc., office general adhesive products, medical adhesive products, such as a label product and the like.

(2) Adhesives Adhesives can be applied as base resins or additives for reactive adhesives, hot melt adhesives, aqueous adhesives, solvent adhesives, pressure sensitive adhesives, and powder adhesives. is there. Moreover, it can be used as a base material sheet and a film.

  Applications include electronics, home appliances / light electrical appliances, industrial parts, automobiles, aviation, medical / healthcare, civil engineering / architecture, sports / daily necessities, various adhesives used in the packaging field, and more specifically, For example, adhesives for fixing crystal resonators, adhesives for liquid crystal displays, adhesives for fixing various chip components to printed boards, optical disk adhesives, coil fixing adhesives, lens fixing adhesives, prism fixing adhesives Adhesives for fixing sensors, adhesives for fixing needles, adhesives for laminated inorganic boards, electrostatic flocking products for automobiles, adhesives for tapes to side protection moldings for automobiles, etc. Difficult polar materials (PMMA, PC, ABS, COP, etc.), adhesives for automobiles such as adhesives for rubber products and synthetic tree products, adhesives for synthetic leather, processing Adhesives for rubber, adhesives for fibers, adhesives for nonwovens, adhesives for propylene / PVC sheets, adhesives for metal parts, adhesives for foam sheets, adhesives for metal / polar resin laminates, adhesives for food packaging Uses such as agents, primers, sealants, etc.

(3) Coating film Examples of coating films include paints, coating agents, resist materials, and inks. More specifically, automobiles, steel pipes, woodwork products, floor materials, electronic parts / equipment, optical fibers, plastic films, metal cans, color filters, optical disks, building materials, aircraft, railway vehicle paints / coating materials, printed wiring boards Resists, semiconductor resists, photoresists such as screen printing resists, resist materials such as solder resists, and UV curable inks. It can also be used as a modifier for the above materials.

  Therefore, the molded body and the modifier made of the composition of the present invention can be widely used for various applications and have a great industrial value.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples.

  In the examples, BA, MMA, GMA, HEMA, and AMA represent n-butyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and allyl methacrylate, respectively.

<Molecular weight measurement method>
The molecular weight shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using chloroform as the mobile phase. As a system, a GPC system manufactured by Waters was used, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko Co., Ltd. was used for the column.

<Method for measuring conversion rate of polymerization reaction>
The conversion rate of the polymerization reaction shown in this example was measured using the following analyzer and conditions.
Equipment used: Gas chromatography GC-14B manufactured by Shimadzu Corporation
Separation column: J & W SCIENTIFIC INC, capillary column DB-17, 0.35 mmφ × 30 m
Separation conditions: Initial temperature 50 ° C., hold for 3.5 minutes
Temperature increase rate 40 ° C / min
Final temperature 140 ° C, hold for 1.5 minutes
Injection temperature 250 ° C
Detector temperature 250 ° C
Sample preparation: The sample was diluted about 10 times with ethyl acetate, and acetonitrile was used as an internal standard substance.

<Combination of acrylic block copolymer and photoinitiator>
Formulation in solution: Acrylic block polymer was dissolved in toluene to make a 30% solution. A predetermined amount of initiator was added to the obtained acrylic block polymer solution, a predetermined amount of sensitizer was added as necessary, and the mixture was stirred with a spatula for 1 minute to obtain a curable liquid composition. If necessary, the obtained solution was devolatilized under vacuum to remove the solvent.

  Blending by melt kneading: A predetermined amount of an initiator was added to the acrylic block polymer solution, and kneaded at a predetermined temperature for a predetermined time with a lab plast mill to obtain a curable composition.

<Irradiation of active energy rays>
Irradiation of ultraviolet rays: The sample was irradiated with a predetermined amount of ultraviolet rays using an ultraviolet irradiation device LIGHT HAMMER6 (manufactured by FUSION UV SYSTEMS, lamp; H bulb mercury lamp type).

  Electron beam irradiation: An electron beam of 10 Mrad (acceleration voltage 200 kv) was irradiated using an electron beam irradiation apparatus.

<Adjustment of samples for evaluating adhesive properties>
The curable liquid composition was coated on a PET film having a thickness of 50 μm using a coater, and an adhesive tape was prepared by removing the solvent. This adhesive tape was affixed to a stainless steel plate with a width of 25 mm and a length of 125 mm in accordance with JIS Z-0237 to form a test piece, and an adhesive strength test was performed. The thickness of the adhesive layer was measured using a thickness gauge.

<Adhesion test>
The force required to peel the test piece with the adhesive tape attached to the stainless steel plate under the conditions of an atmospheric temperature of 23 ° C., a peeling angle of 180 °, and a tensile speed of 300 mm / min was measured as the peeling force.

<Retention force test>
A holding force test was performed according to JIS Z-0237 using a test piece with an adhesive tape attached. The test temperature was 150 ° C. and the load was 1 kgf. A holding power tester 145-DT (manufactured by Yasuda Seiki Seisakusho) was used for the test.

<UV curability evaluation>
After measuring the weight of the sample, it was immersed in a toluene solution, and after 12 hours, the sample was taken out and the toluene was removed with a vacuum dryer. The weight of the sample after drying was measured, and the weight retention before and after the test was taken as the gel fraction. The higher the gel fraction, the better the curability.

<Electron beam curability evaluation>
The sample was immersed in a toluene solution, and after 12 hours, it was visually confirmed whether or not there was an undissolved substance in the solution.
Curability ○: Undissolved material can be confirmed.
Curability x: Undissolved material cannot be confirmed.

<Molding of acrylic block copolymer>
A curable composition obtained by melt-kneading, a coating composition, or an acrylic block copolymer is sandwiched between specular press plates and compressed with a press NSF-50 (manufactured by Shinto Metal Industries) at a predetermined temperature. A plate-like molded body having a predetermined thickness was obtained.

<Formability evaluation>
The obtained molded body was observed, and the moldability was evaluated based on the following criteria.
Criteria for forming formability: There is no large unevenness on the surface of the formed body, and there is no large distortion in the entire sheet.
X: Large irregularities are seen on the surface of the molded body, or the entire sheet is greatly distorted. Alternatively, the molded body is not a sheet.

Production Example 1 Polymerization of Epoxy Group-Containing Acrylic Block Copolymer (P (MMA / GMA) -b-PBA-bP (MMA / GMA)) Copper bromide 8 in a nitrogen-substituted 15 L pressure-resistant reactor .96 g, BA 1266 g, acetonitrile 111 g, and diethyl 2,5-dibromoadipate 9.0 g were added and stirred, and the temperature was raised to 75 ° C. Thereafter, 1.1 g of pentamethyldiethylenetriamine (hereinafter triamine) was added to initiate the polymerization. The polymerization solution was sampled as appropriate, and the conversion was measured by gas chromatography analysis. When the conversion rate of BA was 97%, 1263 g of toluene, 6.19 g of copper chloride, 477 g of MMA, and 79 g of GMA were added. Triamine was added as appropriate to adjust the reaction rate. When the conversion rate of MMA was 89% and the conversion rate of GMA was 94%, 3700 g of toluene was added and the reaction was stopped by cooling.

  To the acrylic block copolymer solution after polymerization, 140 g of activated alumina and 70 g of Kyoward 700 SEN (manufactured by Kyowa Chemical) were added, and an adsorption treatment was performed at 100 ° C. for 3 hours. The adsorbent was filtered off by filtering the solution after cooling using a pressure filter equipped with a polyester felt. The resulting purified solution of the acrylic block copolymer was vacuum-dried to obtain the desired epoxy group-containing acrylic block copolymer 1.

  When the GPC analysis of the obtained epoxy-group-containing acrylic block copolymer 1 was conducted, the number average molecular weight Mn was 10,7166 and the molecular weight distribution Mw / Mn was 1.33. In addition, the number of functional groups introduced from the results of the polymerization charge and the conversion rate measurement was 20.9 per molecule.

Production Example 2 Polymerization of Epoxy Group-Containing Acrylic Block Copolymer (P (MMA / GMA) -b-PBA-bP (MMA / GMA))
To a nitrogen-substituted 5 L pressure-resistant reactor, 4.98 g of copper bromide, 694.18 g of BA, 60.88 g of acetonitrile, and 5.0 g of diethyl 2,5-dibromoadipate were added and stirred, and the temperature was raised to 75 ° C. Thereafter, 0.602 g of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate polymerization. The polymerization solution was sampled as appropriate, and the conversion was measured by gas chromatography analysis. When the conversion rate of BA was 97%, 793 g of toluene, 3.44 g of copper chloride, 275 g of MMA, and 12.08 g of GMA were added. Triamine was added as appropriate to adjust the reaction rate. When the conversion rate of MMA was 90% and the conversion rate of GMA was 90%, 1190 g of toluene was added and the reaction was stopped by cooling.

  To the acrylic block copolymer solution after polymerization, 76 g of activated alumina and 38 g of Kyoward 700 SEN (manufactured by Kyowa Chemical) were added, and an adsorption treatment was performed at 100 ° C. for 3 hours. The adsorbent was filtered off by filtering the solution after cooling using a pressure filter equipped with a polyester felt. The resulting purified solution of the acrylic block copolymer was vacuum-dried to obtain the desired epoxy group-containing acrylic block copolymer 2.

  When the GPC analysis of the obtained epoxy-group-containing acrylic block copolymer 2 was conducted, the number average molecular weight Mn was 11,3475 and the molecular weight distribution Mw / Mn was 1.35. In addition, the number of functional groups introduced from the results of the polymerization charge and the conversion rate measurement was 5.5 per molecule.

(Production Example 3) Polymerization of hydroxyl-containing acrylic block copolymer (P (MMA / HEMA) -b-PBA-bP (MMA / HEMA)) and introduction of acryloyl group
To a 5 L pressure-resistant reactor purged with nitrogen, 11.26 g of copper bromide, 804.6 g of BA, 141.2 g of acetonitrile, and 5.65 g of diethyl 2,5-dibromoadipate were added and stirred, and the temperature was raised to 75 ° C. Thereafter, 1.36 g of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate polymerization. The polymerization solution was sampled as appropriate, and the conversion was measured by gas chromatography analysis. When the conversion rate of BA was 95%, 950 g of toluene, 7.77 g of copper chloride, 328 g of MMA, and 22.44 g of HEMA were added. Triamine was added as appropriate to adjust the reaction rate. When the conversion rate of MMA was 82% and the conversion rate of HEMA was 100%, 1190 g of toluene was added and the reaction was stopped by cooling.

To the acrylic block copolymer solution after polymerization, 17.9 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 3 hours. The precipitated insoluble part was removed by filtration with a Kiriyama funnel, and then 46 g of an adsorbent Kyoward 500SH (manufactured by Kyowa Chemical) was added to the polymer solution, followed by further stirring at room temperature for 3 hours. The adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution. This solution was dried to remove the solvent and residual monomer, and the target block copolymer was obtained. When the GPC analysis of the obtained block copolymer was conducted, it was number average molecular weight Mn109439 and molecular weight distribution Mw / Mn1.37. ^The composition ratio measured by ¹ H-NMR was BA / MMA / HEMA = 73.1 / 24.3 / 2.6 (% by weight).

The block copolymer was dissolved in toluene to make a 30% solution. To a 1 L separable flask, 100 g of a block copolymer solution and 1.41 g of triethylamine were added, and cooled in an ice water bath. The acryloyl chloride 1.25g was dripped here and it stirred for 2 hours. When sampled and ¹ H-NMR measurement was performed, the reaction rate was 70%.

  In order to remove the amine salt precipitated from the solution after the reaction, suction filtration was performed twice. Next, in order to remove toluene from the filtrate, it was devolatilized at room temperature. In order to remove the remaining amine salt, separation was performed with chloroform and an aqueous sodium hydrogen carbonate solution, and purification such as discarding the aqueous layer and suction filtration of the chloroform layer was repeated twice. Subsequently, separation was performed 3 times with chloroform and brine, and purification was performed. After purification by liquid separation, magnesium sulfate was added to the organic layer to remove moisture. Finally, in order to remove chloroform, remaining triethylamine and acrylic acid, devolatilization was carried out while heating at 70 ° C. to obtain the target block copolymer 3 having an acryloyl group. When the GPC analysis of the obtained acryloyl group containing acrylic block copolymer 3 was conducted, the number average molecular weight Mn was 11,0665 and molecular weight distribution Mw / Mn was 1.37. Further, the number of functional groups introduced from the results of the measurement of the polymerization charge and the conversion rate was 7.7 per molecule.

(Production Example 4) Polymerization of allyl group-containing acrylic block copolymer (P (MMA / AMA) -b-PBA-bP (MMA / AMA))
After substituting the inside of the polymerization vessel of the 2 L separable flask with nitrogen, 4.50 g (31.4 mmol) of copper bromide was weighed and 72.0 mL of acetonitrile (nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 30 minutes, 2.26 g (6.28 mmol) of diethyl 2,5-dibromoadipate initiator and 360 ml (2.51 mol) of BA were added. The mixture was heated and stirred at 85 ° C., and 0.66 ml (3.14 mmol) of ligand diethylenetriamine was added to initiate polymerization.

About 0.2 mL of the polymerization solution was extracted from the polymerization solution for sampling at regular intervals from the start of polymerization, and the conversion rate of BA was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of BA was 94%, MMA 201.3 ml (1.88 mol), AMA 12.66 ml (93.7 mmol), copper chloride 3.11 g (31.4 mmol), diethylenetriamine 0.66 ml (3. 14 mmol) and 635 ml toluene (nitrogen bubbled). Similarly, the conversion rate of MMA was determined. When the conversion rate of MMA was 56% and the conversion rate of AMA was 45%, 635 ml of toluene was added and the reactor was cooled in a water bath to complete the reaction. The reaction solution was diluted with 2.1 L of toluene, 7.80 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. The precipitated insoluble part was removed by filtration with a Kiriyama funnel, then 8.00 g of adsorbent Kyoward 500SH (manufactured by Kyowa Chemical) was added to the polymer solution, and the mixture was further stirred at room temperature for 3 hours. The adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution. This solution was dried to remove the solvent and residual monomer, and the target block copolymer 4 was obtained. When GPC analysis of the obtained block copolymer 4 was performed, the number average molecular weight Mn114600 was molecular weight distribution Mw / Mn1.74. ^The composition ratio measured by ¹ H-NMR was BA / MMA / AMA = 74.3 / 24.1 / 1.6 (% by weight). Further, the number of functional groups introduced from the results of the measurement of the polymerization charge and the conversion rate was 6.7 per molecule.

Production Example 5 Polymerization of Epoxy Group-Containing Acrylic Block Copolymer (PMMA-b-P (BA / GMA) -b-PMMA) In a nitrogen-substituted 15 L pressure-resistant reactor, 8.8 g of copper bromide, 1194 g of BA, 34.8 g of GMA, 110 g of acetonitrile, and 8.8 g of diethyl 2,5-dibromoadipate were added and stirred, and the temperature was raised to 75 ° C. Thereafter, 1.0 g of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate polymerization. The polymerization solution was sampled as appropriate, and the conversion was measured by gas chromatography analysis. When the conversion rate of BA was 50%, 34.8 g of GMA was added and polymerization was continued. When the conversion rate of BA was 97%, 1248 g of toluene, 6.1 g of copper chloride and 539 g of MMA were added. Triamine was added as appropriate to adjust the reaction rate. When the MMA conversion rate was 90%, 6950 g of toluene was added and the reaction was stopped by cooling. The conversion rate of GMA was 97%.

  To the acrylic block copolymer solution after polymerization, 140 g of activated alumina and 70 g of Kyoward 700 SEN (manufactured by Kyowa Chemical) were added, and an adsorption treatment was performed at 100 ° C. for 3 hours. The adsorbent was filtered off by filtering the solution after cooling using a pressure filter equipped with a polyester felt. The resulting purified solution of the acrylic block copolymer was vacuum-dried to obtain the desired epoxy group-containing acrylic block copolymer 5.

  When the GPC analysis of the obtained epoxy-group-containing acrylic block copolymer 5 was conducted, the number average molecular weight Mn was 10,8604 and molecular weight distribution Mw / Mn was 1.35. In addition, the number of functional groups introduced from the results of the polymerization charge and the conversion rate measurement was 19.4 per molecule.

(Production Example 6) Production of acrylic block copolymer containing no active energy ray-curable functional group (PMMA-b-PBA-b-PMMA) An acrylic polymer block is constructed in a nitrogen-substituted 500 L reactor. As a monomer, 83.0 kg of BA was charged, followed by 580 g of cuprous bromide, and stirring was started. Thereafter, a solution prepared by dissolving 583 g of diethyl 2,5-dibromoadipate in 7.3 kg of acetonitrile was charged, and the jacket was heated and held at an internal temperature of 75 ° C. for 30 minutes. Thereafter, 70 g of pentamethyldiethylenetriamine was added to initiate polymerization of the acrylic polymer block. About 100 g of the polymerization solution was sampled for sampling from the polymerization solution at regular intervals from the start of polymerization, and the conversion rate of BA was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed.

  When the conversion rate of BA reached 97%, 82.5 kg of toluene, 400 g of cuprous chloride, 70 g of pentamethyldiethylenetriamine, and 35.6 kg of MMA were added as monomers constituting the methacrylic polymer block, Polymerization of the methacrylic polymer block was started. When the MMA conversion rate reached 90%, 120 kg of toluene was added to dilute the reaction solution, and the reactor was cooled to terminate the polymerization.

  Toluene was added to the resulting acrylic block copolymer solution to make the polymer concentration 25% by weight. 1.6 kg of p-toluenesulfonic acid monohydrate was added to this solution, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C. for 3 hours. The reaction solution was sampled to confirm that the solution was colorless and transparent, and 2.3 kg of Radiolite # 3000 manufactured by Showa Chemical Industry was added. Thereafter, pressure filtration was performed at 0.1 to 0.4 MPaG using a pressure filter equipped with polyester felt as a filter medium to separate a solid content.

  The obtained acidic solution was again put into a 500 L reactor, 3.4 kg of Kyowa Chemical Kyodo 500SH was added as a solid base, and the mixture was stirred at 30 ° C. for 1 hour. Thereafter, using a pressure filter equipped with polyester felt as a filter medium, the solid content is separated by pressure filtration at 0.1 to 0.4 MPaG, and the target active energy ray-curable functional group (c) is obtained. A solution of acrylic block copolymer 6 not containing was obtained. After adding 0.6 part by weight of Irganox 1010 (manufactured by Ciba Japan Co., Ltd.) to the obtained polymer solution based on the weight of the polymer, SCP100 (manufactured by Kurimoto Steel Works, heat transfer area) 1m2) was used to evaporate the solvent component. The polymer was made into a strand through a φ4 mm die, cooled in a water bath, and polymer pellets were obtained by a pelletizer.

  When the GPC analysis of the obtained acrylic block copolymer 6 was conducted, the number average molecular weight (Mn) was 109,000 and the molecular weight distribution (Mw / Mn) was 1.31.

Example 1
The epoxy group-containing acrylic block copolymer 1 obtained in Production Example 1 was dissolved in toluene to give a 30% solution. 1 part by weight of Adekaoptomer SP-172 (manufactured by ADEKA), which is a cationic photoinitiator, was added to the obtained solution in a solution state to obtain a curable liquid formulation. About 1 mL of the blend was dropped onto a polyethylene plate and then devolatilized to obtain a coating composition. The coating composition was unirradiated or irradiated with ultraviolet rays so as to be 3600 mJ / cm ^2, and the curability of the obtained cured product was evaluated.

Further, an adhesive tape was prepared using the curable liquid composition, and the surface of the tape on which the acrylic block copolymer 1 was applied was irradiated, and irradiated with unirradiated or 3600 mJ / cm ² ultraviolet light, then stainless steel. Adhesive strength test and holding power test were carried out by pasting on the plate.
Further, 1 part by weight of Adeka optomer SP-172 was blended into the acrylic block copolymer 1 by melt kneading at 170 ° C. for 10 minutes, and press-molded at 170 ° C. The moldability of the obtained 2 mm thick molded body was evaluated. The molded body was unirradiated or irradiated with ultraviolet rays so as to be 20000 mJ / cm ^2, and the curability (curability after shaping) of the obtained cured product was evaluated. The results are shown in Table 1.

(Example 2)
Adhesive strength, holding power, and curability were evaluated in the same manner as in Example 1 except that the ultraviolet irradiation amount of Example 1 was not irradiated or 440 mJ / cm ² . The results are shown in Table 1.

(Example 3)
The acrylic block copolymer 1 of Example 1 was changed to the acrylic block copolymer 2, the ultraviolet irradiation amount was changed to unirradiated or 3000 mJ / cm ² , and the adhesive strength and curability were measured. Was evaluated in the same manner as in Example 1 except that the holding power test was performed at 3000 mJ / cm ² . The results are shown in Table 1.

Example 4
Except that the acrylic block copolymer 1 of Example 1 was changed to the acrylic block copolymer 3, the initiator was changed to 1 part by weight of DAROCUR 1173, and the UV irradiation amount was not irradiated or changed to 3000 mJ / cm ² The adhesive strength, holding power and curability were evaluated in the same manner as in Example 1. Also, a coating composition obtained by dropping a curable liquid composition containing 1.5 g of the acrylic block copolymer 3 was press-molded at 110 ° C. to obtain a 2 mm-thick molded body. . The moldability was evaluated using the obtained molded body. The molded body was unirradiated or irradiated with ultraviolet rays of 3000 mJ / cm ² , and the curability (curability after shaping) of the obtained cured product was evaluated. The results are shown in Table 1.

(Example 5)
The curability was evaluated in the same manner as in Example 1 except that the ultraviolet irradiation amount of Example 4 was not irradiated or was changed to 440 mJ / cm ² . Moreover, the moldability and the curability after shaping were evaluated by the same operation as in Example 4 except that the ultraviolet irradiation amount was not irradiated or 440 mJ / cm ² . The results are shown in Table 1.

(Example 6)
The acrylic block copolymer 1 of Example 1 was changed to the acrylic block copolymer 4, the initiator was changed to 5 parts by weight of IRGACURE 651, 5 parts by weight of N-methyldiethanolamine was used as a sensitizer, and ultraviolet irradiation was performed. The curability was evaluated by changing the amount to unirradiated or 12000 mJ / cm ² . The results are shown in Table 1.

(Example 7)
The acrylic block copolymer 4 was dissolved in 30% toluene, about 1 mL was dropped onto a polyethylene plate, and then devolatilized to obtain a coating composition. The coating composition was unirradiated or irradiated with an electron beam of 10 Mrad (acceleration voltage 200 kv) to evaluate the curability. Furthermore, the acrylic block copolymer 4 was press-molded at 170 ° C., and the moldability of the resulting 0.3 mm-thick molded product was evaluated. The molded body was unirradiated or irradiated with an electron beam of 10 Mrad (acceleration voltage 200 kv), and the curability (curability after shaping) of the obtained cured product was evaluated. The results are shown in Table 1.

(Example 8)
The acrylic block copolymer 1 of Example 1 was changed to the acrylic block copolymer 5 to measure the adhesive strength, curability, moldability, and curability after shaping, and the UV irradiation dose was 3600 mJ / cm. The same evaluation as in Example 1 was performed except that the holding power test was performed as ² . The results are shown in Table 1.

(Comparative Example 1)
Evaluation similar to Example 1 was performed except having changed the acrylic block copolymer 1 of Example 1 to the acrylic block copolymer 6. FIG. The results are shown in Table 1.

(Comparative Example 2)
The acrylic block copolymer 1 of Example 1 is an acrylic copolymer ARUFON-UG-4010 having an epoxy group in the molecule (manufactured by Toagosei: BA / GMA random copolymer, liquid resin having a weight average molecular weight of about 3000). The curable property and the moldability were evaluated in the same manner as in Example 1 except that the amount of irradiation with ultraviolet rays was changed to unirradiated or 6000 mJ / cm ² . The results are shown in Table 1.

  As can be seen from Table 1 (Examples 1 to 8, Comparative Examples 1 and 2), the compositions of Examples 1 to 8 are excellent in tackiness, curability, moldability, and curability after shaping. I understand. Especially the composition of Examples 1-4 is excellent in the adhesive force after hardening, and holding power with adhesiveness, sclerosis | hardenability, a moldability, and the sclerosis | hardenability after shaping. On the other hand, it can be seen that the compositions of Comparative Examples 1 and 2 are remarkably low in curability, moldability and holding power and hardly exist.

  From the above, it was shown that the acrylic block copolymer composition of the present invention is excellent in adhesive strength, holding power, curability, moldability, and curability after shaping.

Claims (18)

It comprises a methacrylic polymer block (a) and an acrylic polymer block (b), and at least one of the methacrylic polymer block (a) and the acrylic polymer block (b) has an active energy. An active energy ray-curable composition comprising an acrylic block copolymer (A) having a linearly curable functional group (c). 2. The active energy ray-curable composition according to claim 1, wherein the acrylic block copolymer (A) has an active energy ray-curable functional group (c) in the methacrylic polymer block (a). . The active energy ray-curable composition according to claim 1 or 2, further comprising a photoinitiator (B). 4. The activity according to claim 1, wherein the active energy ray-curable functional group (c) is at least one selected from the group consisting of an allyl group, a (meth) acryloyl group, and an epoxy group. Energy ray curable composition. 5. The active energy ray-curable composition according to claim 1, wherein the acrylic block copolymer (A) is a diblock copolymer, a triblock copolymer, or a mixture thereof. object. The active energy according to any one of claims 1 to 5, wherein the acrylic block copolymer (A) has a number average molecular weight of 5,000 to 300,000 as measured by gel permeation chromatography. A linear curable composition. In the acrylic block copolymer (A), the proportion of the methacrylic polymer block (a) is 5 to 90% by weight, and the proportion of the acrylic polymer block (b) is 95 to 10% by weight. The active energy ray-curable composition according to any one of claims 1 to 6. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic block copolymer (A) is 1.8 or less. The active energy ray-curable composition described in 1.   Acrylic block copolymer (A) is an atom having an organic halide or sulfonyl halide compound as an initiator and a metal complex having at least one selected from Fe, Ru, Ni and Cu as a central metal as a catalyst. The active energy ray-curable composition according to any one of claims 1 to 8, which is produced by a transfer radical polymerization method. The active energy ray-curable functional group (c) is contained in the acrylic block copolymer (A) at least one molecule per molecule of the active energy ray-curable functional group (c). Composition. The active energy ray-curable composition according to any one of claims 3 to 10, wherein the photoinitiator (B) is a compound that generates radicals upon irradiation with active energy rays. The active energy ray-curable composition according to any one of claims 3 to 10, wherein the photoinitiator (B) is a compound that generates cations upon irradiation with active energy rays. The active energy ray-curable composition according to any one of claims 3 to 10, wherein the photoinitiator (B) is a compound that generates a base upon irradiation with active energy rays. 14. The amount of the photoinitiator (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). Active energy ray-curable composition. A molded body comprising the active energy ray-curable composition according to any one of claims 1 to 14. An adhesive comprising the active energy ray-curable composition according to claim 1. An adhesive comprising the active energy ray-curable composition according to claim 1. A coating film comprising the active energy ray-curable composition according to claim 1.