Active energy ray curable composition and method for producing same

Abstract

To provide an active energy ray-curable composition that provides a cured product having excellent mechanical physical properties, weather resistance and heat resistance.SOLUTION: An active energy ray-curable composition contains a (meth)acrylate polymer (A) modified with an unsaturated double bond-containing oligomer (a2) with a glass transition temperature of (Tg) of -30 to -90°C. The modified (meth)acrylate polymer (A) may be a polymer obtained by adding the unsaturated double bond-containing oligomer (a2) to a copolymer (a1) that includes a constitutional unit derived from a (meth)acrylate monomer and a constitutional unit derived from a (meth)acrylate monomer having a reactive group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate group, through the reactive group. The composition can be used suitably as a coating agent or an adhesive.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable composition having excellent weather resistance, heat resistance and mechanical properties, which can be suitably used as a raw material for adhesives, coating materials, inks, films, etc. [Background technology]

[0002] 2. Description of the Related Art Active energy ray-curable compositions can be cured by exposure to active energy rays such as ultraviolet rays, visible light, and electron beams for a very short period of time, and are highly productive, and therefore are widely used in inks, coating materials, adhesives, and the like.

[0003] For example, in the case of a top coating agent for decorative films, the cured product is required to have a high elongation rate and strength, and when used outdoors, high weather resistance is also required.

[0004] As the above-mentioned top coating agent, JP 2011-132288 A proposes a composition containing a (meth)acrylic resin having a (meth)acryloyl group in the side chain and a urethane (meth)acrylate. However, since the composition contains a certain amount or more of urethane acrylate in order to achieve elongation, there is a problem in that the weather resistance is insufficient.

[0005] On the other hand, as an active energy ray curable composition for forming an optical film such as a polarizer protective film, JP 2014-115538 A proposes an active energy ray curable composition containing a (meth)acrylate polymer having an acryloyl group in a side chain and a certain distance between the acryloyl group and the main chain. However, although the cured product of this polymer has excellent mechanical properties such as elongation, there is a problem that the weather resistance is insufficient because the acrylic equivalent is larger than 2400 g / eq. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2011-132288 A [Patent Document 2] JP 2014-115538 A Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention provides an active energy ray-curable composition which gives a cured product having excellent mechanical properties, weather resistance and heat resistance. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and as a result have found that an active energy ray-curable composition containing an unsaturated double bond-containing oligomer having a glass transition temperature (hereinafter referred to as "Tg") of -30 to -90°C and a polymer obtained by modifying a (meth)acrylate polymer can solve the above problems and can be suitably used as a raw material for adhesives, coating materials, inks, films, etc., thereby completing the present invention.

[0009] That is, the present invention relates to an active energy ray-curable composition containing a (meth)acrylate polymer (A) (hereinafter also referred to as "component (A)") modified with an unsaturated double bond-containing oligomer (a2) (hereinafter also referred to as "unsaturated oligomer (a2)") having a Tg of -30 to -90°C. According to a preferred embodiment of the present invention, the component (A) is preferably a reaction product of a copolymer (a1) (hereinafter referred to as "copolymer (a1)") containing a structural unit (a1-1) derived from a (meth)acrylate monomer having no reactive group and a structural unit derived from a (meth)acrylate monomer having a reactive group (a1-2), and an unsaturated oligomer (a2) having an ethylenically unsaturated group and a group reactive with the reactive group via the reactive group. Furthermore, as the component (A), the (meth)acrylate monomer (a1-2) having a reactive group constituting the copolymer (a1) is preferably a (meth)acrylate monomer having a reactive group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an isocyanate group. According to another preferred embodiment of the present invention, the weight average molecular weight (Mw) of the component (A) is 3,000 to 50,000. According to another preferred embodiment of the present invention, the acrylic equivalent of the component (A) is 2,500 g / eq or less. According to another preferred embodiment of the present invention, the unsaturated oligomer (a2) of the component (A) contains a ring-opened caprolactone structure as a constituent unit. According to another preferred embodiment of the present invention, the composition further contains a compound (B) having ethylenic unsaturation other than component (A) (hereinafter also referred to as "component (B)"). According to another preferred embodiment of the present invention, the composition further contains a photopolymerization initiator (C) (hereinafter, also referred to as "component (C)"). When the composition contains the component (B) per 100 parts by weight of the component (A), the composition contains 1 to 20 parts by weight of the component (C) per 100 parts by weight of the component (A) and the component (B). According to another preferred embodiment of the present invention, the composition further contains an organic solvent (D) (hereinafter referred to as "component (D)"), and when the component (B) is contained per 100 parts by weight of the component (A), the composition contains 150 parts by weight or less of the component (D) per 100 parts by weight of the component (A) and the component (B).

[0010] Furthermore, the present invention also relates to a method for producing an active energy ray-curable composition, comprising a step of reacting the unsaturated oligomer (a2) with a copolymer (a1) comprising a structural unit derived from a (meth)acrylate monomer (a1-1) having no reactive group and a structural unit derived from a (meth)acrylate monomer (a1-2) having a reactive group, to add the unsaturated oligomer (a2) to the copolymer (a1) via the reactive group. According to a preferred embodiment of the present invention, the (meth)acrylate monomer (a1-2) having a reactive group constituting the copolymer (a1) is a (meth)acrylate monomer having a reactive group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an isocyanate group.

[0011] In addition, the present invention is preferably an active energy ray-curable composition for a coating agent, which comprises the above-mentioned active energy ray-curable composition of the present invention. In addition, the present invention preferably provides an active energy ray-curable composition for adhesives, which comprises the above-mentioned active energy ray-curable composition of the present invention. Effect of the Invention

[0012] The active energy ray-curable composition of the present invention contains, as an active ingredient, a (meth)acrylate polymer (component (A)) modified with an unsaturated double bond-containing oligomer (unsaturated oligomer (a2)) having a Tg of -30 to -90°C. Therefore, the cured product thereof has excellent mechanical properties, weather resistance, and heat resistance, and can be suitably used as a raw material for adhesives, coating materials, inks, films, etc. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention relates to an active energy ray-curable composition containing, as an essential component, a specific polymer, that is, a (meth)acrylate polymer (A) (component (A)) modified with an unsaturated double bond-containing oligomer (unsaturated oligomer (a2)) having a Tg of −30 to −90° C. The component (A), the active energy ray-curable composition, and the method of use will be described in detail below. In the present invention, the term "(meth)acrylate-based polymer" refers to a polymer containing (meth)acrylate as a main component of a structural unit, "(meth)acrylate" refers to acrylate and / or methacrylate, "(meth)acrylic" refers to acrylic and / or methacrylic, and "(meth)acryloyl" refers to acryloyl and / or methacryloyl.

[0014] 1. Component (A) The component (A) is a (meth)acrylate polymer modified with an unsaturated oligomer (a2). As described above, the (meth)acrylate polymer means a polymer containing (meth)acrylate as a main component of the structural units, and means a polymer containing 80 to 100% by weight of (meth)acrylate in all the structural monomer units.

[0015] Representative examples of the component (A) include compounds in which an unsaturated oligomer (a2) is bonded to the end or side chain of a (meth)acrylate polymer. As component (A), a copolymer (a1) consisting of a structural unit derived from a (meth)acrylate monomer (a1-1) having no reactive group (hereinafter referred to as "monomer (a1-1)") and a structural unit derived from a (meth)acrylate monomer (a1-2) having a reactive group (hereinafter referred to as "monomer (a1-2)") is preferably used, and a reaction product of a group reactive with the reactive group and an unsaturated oligomer (a2). That is, as component (A), a polymer having an ethylenically unsaturated group bonded as a side chain, obtained by reacting a reactive group of the trunk polymer, copolymer (a1), with a reactive group of an unsaturated oligomer (a2), is preferred. In addition, the "reactive group" in the monomer (a1-1) and the monomer (a1-2) means a functional group other than a (meth)acryloyl group. The copolymer (a1), the unsaturated oligomer (a2), the method for producing the component (A), and the physical properties of the component (A) will be described below.

[0016] (1) Copolymer (a1) Copolymer (a1), which is the raw material copolymer of component (A), is a copolymer comprising structural units derived from monomer (a1-1) and structural units derived from monomer (a1-2). The monomer (a1-1) and the monomer (a1-2) will be described below.

[0017] (1-1) Monomer (a1-1) The monomer (a1-1) is a (meth)acrylate monomer (a1-1) having no reactive group. Specific examples of the monomer (a1-1) are not particularly limited as long as they are (meth)acrylate-based monomers that do not have the above-mentioned reactive group, and examples thereof include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetradecyl (meth)acrylate, and stearyl (meth)acrylate; alicyclic (meth)acrylates such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate; N-(meth)acryloylmorpholine; Acrylamides such as (meth)acrylamide, N-methylol acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide; and Examples include acrylonitrile and methacrylonitrile (meth)acrylonitrile.

[0018] (1-2) Monomer (a1-2) The monomer (a1-2) is a (meth)acrylate monomer having a reactive group. The monomer (a1-2) is preferably a (meth)acrylate monomer having a reactive group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an isocyanate group.

[0019] Examples of the monomer (a1-2) having an epoxy group as a reactive group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0020] Examples of the monomer (a1-2) having a hydroxyl group as a reactive group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and an ε-caprolactone adduct of 2-hydroxyethyl (meth)acrylate.

[0021] An example of the monomer (a1-2) having an isocyanate group as a reactive group is (meth)acryloxyethyl isocyanate, and specific products include "Karenz MOI" and "Karenz AOI" (both trade names, manufactured by Showa Denko K.K.).

[0022] Examples of the monomer (a1-2) having a carboxyl group as a reactive group include (meth)acrylic acid, monohydroxyethyl phthalate, ω-carboxy-polycaprolactone (n ≒ 2) monoacrylate, (meth)acryloyloxyethyl succinate, (meth)acryloyloxyethyl hexahydrophthalate, (meth)acryloyloxyethyl phthalate, (meth)acryloyloxyethyl-2-hydroxyethyl phthalate, β-carboxyethyl acrylate, a phthalic anhydride adduct of pentaerythritol triacrylate, a succinic anhydride adduct of pentaerythritol triacrylate, a succinic anhydride adduct of dipentaerythritol triacrylate, and a phthalic anhydride adduct of dipentaerythritol triacrylate.

[0023] (1-3) Polymerization method of copolymer (a1) The method for producing the copolymer (a1) before being modified with the unsaturated oligomer (a2) is not particularly limited, and known methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization can be used. Among these, bulk polymerization and solution polymerization are preferred because the polymer can be easily produced and they do not contain impurities such as emulsifiers.

[0024] (1-3-1) Solution polymerization The solution polymerization method includes a method in which the raw material monomer to be used is dissolved in an organic solvent, a thermal polymerization initiator is added, and the mixture is heated and stirred. When the solution polymerization method is used to synthesize the polymer by radical polymerization, the raw material monomer to be used is dissolved in an organic solvent, a thermal radical polymerization initiator is added, and the mixture is heated and stirred to obtain the polymer. If necessary, a chain transfer agent can be used to adjust the molecular weight of the polymer.

[0025] Examples of organic solvents used in the solution polymerization method include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; ethers such as propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene and xylene; and aliphatic hydrocarbons such as hexane, heptane, and mineral spirits.

[0026] Examples of the thermal polymerization initiator include azo-based initiators such as azobisisobutyronitrile, azobisisovaleronitrile, azobiscyclohexanecarbonitrile, and azobiscyanovaleric acid; organic peroxides such as t-butyl peroxypivalate, t-hexyl peroxypivalate, dilauroyl peroxide, di(2-ethylhexyl)peroxydicarbonate, di-t-butyl peroxide, and dicumyl peroxide; and hydrogen peroxide-iron(II) salt, peroxodisulfate-sodium hydrogensulfite, cumene hydroperoxide-iron(II) salt, and the like. The proportion of the thermal polymerization initiator used may be appropriately set depending on the target molecular weight. The proportion of the thermal radical polymerization initiator used is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total of all the monomers used.

[0027] (1-3-2) Bulk polymerization Examples of the bulk polymerization method include known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, and the like. For example, a method can be mentioned in which a pressurizable reactor is filled with a solvent, and then set at a predetermined temperature under pressure, and a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate, and a polymerization liquid is withdrawn in an amount corresponding to the supply amount of the monomer mixture. If necessary, a polymerization initiator can be added to the monomer mixture, and the amount of the initiator added is preferably 0.001 to 2 parts by weight per 100 parts by weight of the monomer mixture. The pressure depends on the reaction temperature and the boiling points of the monomer mixture and the solvent used, and may be any pressure that does not affect the reaction but can maintain a predetermined reaction temperature. The residence time of the monomer mixture is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomers may not react sufficiently, and if the residence time exceeds 60 minutes, the productivity may decrease. The preferred residence time is 2 to 40 minutes.

[0028] Examples of the polymerization initiator used to obtain the copolymer (a1) include any initiator that generates radicals at a predetermined reaction temperature.Specific examples of the polymerization initiator include organic peroxides such as di-t-butyl peroxide, di-t-hexyl peroxide, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide, and t-butyl hydroperoxide, and azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), azobiscyclohexacarbonitrile, azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-amidinopropane)dihydrochloride, and 4,4'-azobis(4-cyanovaleric acid). As the polymerization initiator, one of these may be used alone, or two or more of them may be used in combination.

[0029] The amount of the polymerization initiator used can be appropriately adjusted depending on the types of polymerization initiator and monomer, the desired molecular weight, polymerization conditions, etc., but is generally 0.001 to 10 parts by weight per 100 parts by weight of the monomer used.

[0030] When an organic solvent is used for producing the copolymer (a1), an organic hydrocarbon compound is suitable, and examples thereof include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and alcohols such as methanol, ethanol and isopropanol, and one or more of these can be used. Organic solvents that do not dissolve the (meth)acrylate copolymer well tend to cause scale growth on the walls of the reactor, which can lead to production problems in the cleaning process and the like.

[0031] The amount of the organic solvent used is preferably 80 parts by weight or less based on 100 parts by weight of the total vinyl monomers. By using 80 parts by weight or less, a high conversion rate can be obtained in a short time. More preferably, it is 1 to 50 parts by weight. In addition, a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate can also be added. In producing the copolymer (a1), a known chain transfer agent may be used.

[0032] The reaction liquid discharged from the reactor can be directly used for the next step, or the polymer can be isolated by removing volatile components such as unreacted monomers, organic solvents, and low molecular weight oligomers by distillation, etc. A part of the volatile components such as unreacted monomers, solvents, and low molecular weight oligomers distilled off from the reaction liquid can be returned to the raw material tank or directly to the reactor and reused in the polymerization reaction. The method of recycling the unreacted monomers and the solvent is economically preferable. When recycling, it is necessary to determine the mixing ratio of the monomer mixture to be newly fed so as to maintain the desired monomer ratio and the desired amount of the solvent in the reactor.

[0033] (1-3-3) Physical properties of copolymer (a1) The weight average molecular weight (hereinafter also referred to as "Mw") of the copolymer (a1) is usually 1,500 to 50,000, preferably 1,500 to 4,0000, more preferably 2,000 to 30,000, even more preferably 2,500 to 25,000, and particularly preferably 3,000 to 15,000. By having Mw of 50,000 or less, the obtained component (A) can be made to have a low viscosity even at a relatively high concentration, improving the coatability, and also improving the compatibility when mixed with other curable resins. By having Mw of 1,500 or more, the obtained cured product of the component (A) has excellent weather resistance and tensile properties. In the present invention, Mw means a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC) into polystyrene equivalent.

[0034] The Tg (glass transition temperature) of the copolymer (a1) is not particularly limited, but is usually from -40°C to 90°C, and preferably from 0°C to 90°C. A temperature of 0°C or higher leads to a cured product with excellent strength, and a temperature of 90°C or lower leads to a cured product with excellent flexibility. A temperature of 30 to 80°C is more preferable. The Tg of the copolymer (a1) can be adjusted by appropriately selecting the types and copolymerization ratio of the monomers constituting the copolymer.

[0035] In the present invention, Tg means a value determined from the intersection of the tangent line at the inflection point and the baseline of a heat flux curve obtained using a differential scanning calorimeter such as TA Instrument (Q-100). The heat flux curve is obtained under the following conditions: about 10 mg of a sample is cooled to -100°C in a nitrogen atmosphere, held for 5 minutes, heated to 300°C at 10°C / min, cooled to -100°C, held for 5 minutes, and heated to 350°C at 10°C / min.

[0036] In the case of a typical solution polymerization method such as that disclosed in JP2014-115538A, the polymerization temperature is relatively low, and therefore the number of functional groups is biased for each polymer molecule due to the influence of the copolymerization reactivity ratio. On the other hand, in the case of high-temperature polymerization, the influence of the copolymerization reactivity ratio is low, and in the case of continuous polymerization, a constant polymer continues to be produced, so the bias in the number of functional groups for each molecule is extremely small. In addition, when comparing normal solution polymerization with high-temperature polymerization, when synthesizing a polymer of the same molecular weight, high-temperature polymerization requires less polymerization initiator and leaves less initiator residue, resulting in better weather resistance. In particular, in the case of electron beam curing, since no polymerization catalyst such as a photoinitiator is used in the curing reaction, the amount of initiator residue contained in the polymer significantly affects weather resistance. Therefore, the copolymer (a1) used in the present invention generally has a terminal double bond concentration of 0.5 meq / g or less, and more preferably 0.4 meq / g or less. When the terminal double bond concentration is 0.5 meq / g or less, the decrease in the curing rate can be suppressed. In addition, in the present invention, when a copolymer obtained by high-temperature continuous polymerization is used as the copolymer (a1), the terminal double bond concentration of the copolymer (a1) is preferably 0.02 meq / g or more and 0.5 meq / g or less. By being 0.02 meq / g or more, rapid curing during curing is suppressed, and residual stress is less likely to remain, resulting in improved mechanical properties.

[0037] (2) Unsaturated oligomer (a2) The unsaturated oligomer (a2) is an unsaturated double bond-containing oligomer having a Tg of -30 to -90°C. Here, the unsaturated double bond is preferably an ethylenically unsaturated group, and specific examples include a (meth)acryloyl group and a vinyl group, of which a (meth)acryloyl group is more preferable, and an acryloyl group is particularly preferable. In the present invention, the oligomer means a compound having a molecular weight of 250 or more and 2,000 or less. As described above, component (A) is obtained by reacting the reactive group in the copolymer (a1) obtained by the above polymerization method, etc., with the reactive group of the unsaturated oligomer (a2). More specifically, it is obtained by chemically bonding and adding the unsaturated oligomer (a2) to the copolymer (a1) having the above reactive group via the above reactive group.

[0038] When the copolymer (a1) is an epoxy polymer or a copolymer having a hydroxyl group as a reactive group, the unsaturated oligomer (a2) can be a compound having a carboxyl group or an isocyanate group as a functional group that reacts with the reactive group.

[0039] An example of the unsaturated oligomer (a2) having a carboxyl group is an ε-caprolactone adduct of (meth)acrylic acid. Adducts of acrylic acid with ε-caprolactone are commercially available, and examples thereof include Aronix M-5300 (trade name, manufactured by Toagosei Co., Ltd., Tg=−78° C., polycaprolactone chain length≈2).

[0040] The unsaturated oligomer (a2) having an isocyanate group may be, for example, a urethane (meth)acrylate having an isocyanate group at one end. The urethane acrylate having an isocyanate group at one end can be produced by reacting a diol with a diisocyanate to produce a compound having isocyanate groups at both ends, and then reacting this with a hydroxyl group-containing acrylate. In this case, the diisocyanate can be isophorone diisocyanate or hexamethylene diisocyanate, and the diol can be polytetramethylene glycol. The hydroxyl group-containing acrylate can be 2-hydroxyethyl acrylate. Examples of methods for producing the compound include a method in which a diisocyanate and a diol are reacted in an organic solvent in the presence of a tin catalyst such as dioctyltin to obtain a urethane oligomer having isocyanate groups at both ends, and then a hydroxyl group-containing (meth)acrylate is reacted in the presence of a polymerization inhibitor.

[0041] When the copolymer (a1) is a copolymer having an isocyanate group or a carboxyl group as a reactive group, the unsaturated oligomer (a2) that can be used is a compound having a hydroxyl group as a functional group that reacts with the reactive group. Examples of the unsaturated oligomer (a2) having a hydroxyl group include ε-caprolactone adducts of hydroxyalkyl (meth)acrylates such as ε-caprolactone adducts of 2-hydroxyethyl (meth)acrylate, polypropylene glycol adducts of (meth)acrylic acid, polyethylene glycol adducts of (meth)acrylic acid, poly(3-hydroxybutyrate) adducts of 2-hydroxyethyl (meth)acrylate, and polytetramethylene glycol adducts of (meth)acrylic acid. Adducts of 2-hydroxyethyl (meth)acrylate with ε-caprolactone are commercially available, and examples thereof include PLACCEL FA2D (an adduct of 2-hydroxyethyl acrylate with ε-caprolactone, a product name manufactured by Daicel Corporation, the same applies below. Molecular weight: 344, Tg=-78°C), FA5 (an adduct of 2-hydroxyethyl acrylate with ε-caprolactone, molecular weight: 689), FM2D (an adduct of 2-hydroxyethyl methacrylate with ε-caprolactone, molecular weight: 358), FM3 (an adduct of 2-hydroxyethyl methacrylate with ε-caprolactone, molecular weight: 473), and FM5 (an adduct of 2-hydroxyethyl methacrylate with ε-caprolactone, molecular weight: 701). An example of a polypropylene glycol adduct of acrylic acid is a compound having a Tg of -75°C, an example of a polyethylene glycol adduct of acrylic acid is a compound having a Tg of -41°C, an example of a poly(3-hydroxybutyrate) adduct of 2-hydroxyethyl acrylate is a compound having a Tg of -40°C, and an example of a polytetramethylene glycol adduct of acrylic acid is a compound having a Tg of -84°C.

[0042] As the unsaturated oligomer (a2), a compound containing a ring-opened caprolactone structure is preferred. A composition containing component (A) obtained by using such a compound is preferred in that the cured product has excellent elongation. Specific examples of the compound include the compounds listed above. An example of the unsaturated oligomer (a2) having a carboxyl group is an ε-caprolactone adduct of (meth)acrylic acid. Examples of the unsaturated oligomer (a2) having a hydroxyl group include ε-caprolactone adducts of hydroxyalkyl (meth)acrylates, such as ε-caprolactone adducts of 2-hydroxyethyl (meth)acrylate.

[0043] (3) Production method of component (A) Component (A) is preferably produced by reacting a reactive group of copolymer (a1) with a group in unsaturated oligomer (a2) that is reactive with the reactive group described above. This reaction is hereinafter also referred to as a "modification reaction." That is, examples of the reaction for adding an unsaturated oligomer (a2) to a copolymer (a1) include a method of reacting an unsaturated oligomer (a2) having a carboxyl group with a copolymer (a1) having an epoxy group or a hydroxyl group as a reactive group, and a method of reacting an unsaturated oligomer (a2) having a hydroxyl group with a copolymer (a1) having an isocyanate group or a carboxyl group as a reactive group.

[0044] The reaction ratio of the copolymer (a1) and the unsaturated oligomer (a2) may be appropriately set depending on the type of the component (A) to be produced, etc. The amount of the reactive group in the unsaturated oligomer (a2) is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, and further preferably 0.9 to 1.1 mol, per 1 mol of the reactive group in the copolymer (a1).

[0045] As a method for reacting and adding the unsaturated oligomer (a2) having a carboxyl group to the copolymer (a1) having an epoxy group, there can be mentioned a method in which the copolymer (a1) having an epoxy group, the unsaturated oligomer (a2) having a carboxyl group, a catalyst, and an organic solvent are mixed and heated to 60 to 120°C for about 5 to 30 hours.

[0046] The reaction ratio of the copolymer (a1) having an epoxy group and the unsaturated oligomer (a2) having a carboxyl group is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1, of the carboxyl group of the unsaturated oligomer (a2) having a carboxyl group per 1 mol of the epoxy group of the copolymer (a1) having an epoxy group.

[0047] Examples of the catalyst include tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide, tetramethylammonium chloride, triphenylphosphine, tributylphosphine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,4-diazabicyclo[2,2,2]octane. Among these, triphenylphosphine is preferably used because it causes less coloring of the cured product after a heat resistance test.

[0048] The amount of the catalyst added is preferably about 0.5 to 5% by weight based on the total amount of the copolymer (a1) having an epoxy group and the unsaturated oligomer (a2) having a carboxyl group.

[0049] Examples of the organic solvent include ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, etc. When the copolymer (a1) having an epoxy group is in a liquid state, the modification reaction can be carried out without adding a solvent.

[0050] The method of reacting the copolymer (a1) having a hydroxyl group with the unsaturated oligomer (a2) having a carboxyl group includes a general dehydration esterification method, which includes a method of heating the copolymer (a1) having a hydroxyl group, the unsaturated oligomer (a2) having a carboxyl group, a catalyst, and an organic solvent in a mixed state at 100 to 120°C, and azeotropically dehydrating the organic solvent and the water produced to advance the reaction.

[0051] Examples of the catalyst include p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and sulfuric acid. The amount of the catalyst used is 0.05 to 5 mol % based on the number of moles of hydroxyl groups to be reacted.

[0052] As the organic solvent, it is preferable to use an organic solvent that has low solubility in water generated in the dehydration esterification reaction and allows the reaction to proceed while distilling off water by azeotropy. Preferred organic solvents include, for example, aromatic hydrocarbons such as toluene, benzene, and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, and ketones such as methyl ethyl ketone and cyclohexanone. The proportion of the organic solvent is preferably 30 to 70% by weight based on the total amount of the reaction liquid.

[0053] After the reaction, the acid is generally removed with water or an aqueous alkali solution.

[0054] Examples of the method of reacting and adding the unsaturated oligomer (a2) having a hydroxyl group to the copolymer (a1) having an isocyanate group include a method in which the copolymer (a1) having an isocyanate group and the unsaturated oligomer (a2) having a hydroxyl group are mixed, and then a curing catalyst such as dibutyltin dilaurate is added as necessary, and the mixture is heated to 60 to 100°C.

[0055] Examples of the method of reacting and adding the unsaturated oligomer (a2) having a hydroxyl group to the copolymer (a1) having a carboxyl group include a method in which the copolymer (a1) having a carboxyl group and the unsaturated oligomer (a2) having a hydroxyl group are mixed, and then a catalyst such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, sulfonated polystyrene, or Nafion-H is added, and the mixture is heated to 80 to 120°C in the presence of an organic solvent such as toluene, where necessary, to proceed with the esterification reaction while distilling off the water produced. Furthermore, the catalyst remaining after the reaction can be removed by one or a combination of two or more of the following methods: washing with water, alkali neutralization, ion exchange resins, chemical filters for catalyst removal, and filtration.

[0056] In any of the above modification reactions, it is preferable to add a polymerization inhibitor for the purpose of suppressing gelation or improving the storage stability of the modified product. Examples of the polymerization inhibitor include methoxyphenol, hydroquinone, dibutylhydroxytoluene, etc. From the viewpoint of suppressing coloration of the cured product, it is particularly preferable to use dibutylhydroxytoluene.

[0057] (4) Physical properties of component (A) ((meth)acrylic equivalent and molecular weight) The (meth)acrylic equivalent of component (A) is preferably 2,500 g / eq or less. More preferred ranges of the (meth)acrylic equivalent of component (A) are, in order, 150 g / eq or more and 2,500 g / eq or less, 300 g / eq or more and 2,000 g / eq or less, 400 g / eq or more and 1,400 g / eq or less, and 700 g / eq or more and 1,000 g / eq or less. By having a (meth)acrylic equivalent of 150 g / eq or more, the elongation and flexibility of the cured product can be ensured, and by having a (meth)acrylic equivalent of 2,500 g / eq or less, the strength and weather resistance of the cured product can be ensured and a good curing speed can be maintained.

[0058] In the present invention, the (meth)acrylic equivalent (g / eq) represents the weight (g) per equivalent (eq) of the (meth)acryloyl group, and the larger the value, the lower the concentration of the (meth)acryloyl group, and the smaller the value, the higher the concentration of the (meth)acryloyl group.

[0059] The acrylic equivalent can be calculated by the following formula: In the following formula, the number of moles of (meth)acryloyl groups in component (A) is the number of moles of (meth)acryloyl groups added to copolymer (a1) in the above modification reaction, and excludes (meth)acryloyl groups derived from unreacted unsaturated oligomer (a2) present after the above modification reaction.

[0060]

number

[0061] The molecular weight, Mw, of component (A) is preferably 3,000 to 50,000. When the Mw is 3,000 or more, the cured product has excellent weather resistance and tensile properties, and when the Mw is 50,000 or less, the viscosity can be reduced even at a relatively high concentration, resulting in excellent coatability and excellent compatibility when mixed with other curable compounds. More preferred ranges for Mw of component (A) are, in order, 3,000 to 40,000, 3,000 to 30,000, and 4,000 to 20,000.

[0062] 2. Actinic energy ray curable composition The present invention relates to an active energy ray-curable composition containing component (A). The composition can be produced by stirring and mixing component (A) and, if necessary, other components described below.

[0063] The viscosity of the composition may be appropriately set depending on the application and purpose of use, etc. The preferred viscosity is 100 to 20,000 mPa·s, and more preferably 200 to 8,000 mPa·s. In the present invention, the viscosity refers to a value measured at 25° C. using an E-type viscometer (cone-plate type viscometer).

[0064] The composition of the present invention essentially contains the above-mentioned component (A), but can also contain various other components as required. Preferred other components include component (B) (a compound (B) having an ethylenically unsaturated group other than component (A)), component (C) (a photoradical polymerization initiator), and component (D) (an organic solvent (D)). Components (B) to (D) and other components will be described below. In the following, components (A) and (B) are referred to as "curable components".

[0065] (1) Component (B) The composition of the present invention may contain, as necessary, an ethylenically unsaturated compound other than the above-mentioned component (A), which is component (B), for the purpose of reducing the viscosity of the entire composition or adjusting other physical properties.

[0066] Specific examples of component (B) include monomer (a1-1), monomer (a1-2), (meth)acrylates other than monomers (a1-1) and (a1-2) [hereinafter referred to as "other (meth)acrylates"], and N-vinyl-2-pyrrolidone.

[0067] Other examples of (meth)acrylates include compounds having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylates") and compounds having two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylates").

[0068] Specific examples of monofunctional (meth)acrylates include trimethylcyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, benzyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol EO-modified (n=1 to 4) (meth)acrylate, p-cumylphenol EO-modified (n=1 to 4) (meth)acrylate, phenyl (meth)acrylate, o-phenylphenyl (meth)acrylate, p-cumylphenyl (meth)acrylate, N-(meth)acryloylmorpholine, N-vinylformamide, N-(meth)acryloyloxyethyl hexahydrophthalimide, and N-(meth)acryloyloxyethyl tetrahydrophthalimide.

[0069] Specific examples of polyfunctional (meth)acrylates include urethane (meth)acrylates such as urethane acrylates having a polyester skeleton, and urethane (meth)acrylates such as urethane acrylates having a polycarbonate skeleton; Di(meth)acrylates having a bisphenol skeleton, such as bisphenol A EO-modified (n=1 to 2) di(meth)acrylate and bisphenol A di(meth)acrylate; (Poly)alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (n=5-14) di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol (n=5-14) di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polybutylene glycol (n=3-16) di(meth)acrylate, and poly(1-methylbutylene glycol) (n=5-20) di(meth)acrylate. Di(meth)acrylates of aliphatic diols, such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; Hydroxypivalic acid neopentyl glycol di(meth)acrylate; Di(meth)acrylates having an alicyclic skeleton, such as tricyclodecanedimethylol di(meth)acrylate; (Meth)acrylates with an isocyanurate skeleton, such as EO-modified isocyanuric acid diacrylate and ε-caprolactone-modified tris((meth)acryloxyethyl)isocyanurate Polyol poly(meth)acrylates such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, ditrimethylolpropane tri- or tetra(meth)acrylate, diglycerin tri- or tetra(meth)acrylate, and dipentaerythritol tri-, tetra-, penta- or hexa(meth)acrylate; and Examples of the poly(meth)acrylate include polyol alkylene oxide adducts such as tri(meth)acrylate of a glycerin alkylene oxide adduct, tri- or tetra(meth)acrylate of a pentaerythritol alkylene oxide adduct, tri- or tetra(meth)acrylate of a ditrimethylolpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of a diglycerin alkylene oxide adduct, and tri-, tetra-, penta- or hexa(meth)acrylate of a dipentaerythritol alkylene oxide adduct. In the above, EO-modified means ethylene oxide-modified, and n means the number of repeating alkylene oxide units. Among these compounds, the polyfunctional (meth)acrylate is preferably a urethane (meth)acrylate or a (meth)acrylate having an isocyanate skeleton.

[0070] As the component (B), the above-mentioned compounds may be used alone or in combination of two or more.

[0071] The amount of component (B) to be blended may be appropriately set depending on the purpose, as long as it does not reduce the flexibility of the resulting cured product. However, the amount of component (B) is preferably 1 to 50% by weight, more preferably 1 to 35% by weight, and even more preferably 1 to 25% by weight, based on 100% by weight of the total of components (A) and (B).

[0072] (2) Component (C) When ultraviolet light and visible light are used as the active energy rays, the composition of the present invention may contain component (C) (a photopolymerization initiator). When electron beams are used as the active energy rays, it is not always necessary to incorporate component (C), but a small amount of component (C) can be incorporated as necessary to improve curability.

[0073] Component (C) may be benzil dimethyl ketal, benzil, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propanone], 1-hydroxycyclohexyl phenyl ketone ... aromatic ketone compounds such as 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, ADEKA Optomer N-1414 (manufactured by ADEKA Corporation), phenylglyoxylic acid methyl ester, ethyl anthraquinone, and phenanthrenequinone; benzophenone-based compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate and bis(2,6-dimethoxybenzo acylphosphine oxide compounds such as (yl)-2,4,4-trimethylpentylphosphine oxide; Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl]oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone; Acridone compounds such as acridone and 10-butyl-2-chloroacridone; Oxime esters such as 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)] and ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime); 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer; and Examples of the acridine derivatives include 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

[0074] These compounds can be used alone or in combination of two or more.

[0075] The blending ratio of component (C) is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of components (A) and (B) when component (B) is contained, per 100 parts by weight of component (A). By making the blending ratio of component (C) 1 part by weight or more, the composition can be cured with an appropriate amount of ultraviolet or visible light, improving productivity, while by making the blending ratio 20 parts by weight or less, the cured product can have excellent weather resistance and transparency.

[0076] (3) Component (D) The composition of the present invention may contain an organic solvent as component (D) for the purpose of improving the coatability onto a substrate, etc. Although organic solvents are the same compound, when they are used in a reaction system, they are referred to as "organic solvents", and when they are used in compositions such as paints, they are referred to as "organic solvents". In the present invention, these are collectively referred to as "organic solvents".

[0077] Specific examples of component (D) include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene, and cyclohexane; alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and propylene glycol monomethyl ether; Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether, and bis(2-butoxyethyl) ether; ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclopentanone, cyclohexanone, and methylcyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, and cellosolve acetate; Examples of the aprotic polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and γ-butyrolactone.

[0078] As component (D), one or more of the above-mentioned compounds can be used. Component (D) may be added separately to dilute component (A), or the organic solvent used in the production of component (A) may be used as it is without separating it.

[0079] The blending ratio of component (D) may be appropriately set taking into consideration the viscosity of the composition, the purpose of use, etc., but preferably, when component (B) is contained, the amount of component (D) is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, even more preferably 67 parts by weight or less, and particularly preferably 25 to 67 parts by weight, per 100 parts by weight of the total of components (A) and (B).

[0080] (4) Other components other than the above As other components than those mentioned above, various components can be blended depending on the purpose. When the composition of the present invention is used as a coating agent, examples of additives that can be used include polymerization inhibitors and / or antioxidants, light resistance improvers, inorganic particles, surface modifiers, pigments, dyes, and tackifiers. Among the other components, the polymerization inhibitor and / or antioxidant, and the light resistance improver will be described below.

[0081] <Polymerization inhibitor or / and antioxidant> The active energy ray-curable composition of the present invention may contain a polymerization inhibitor and / or an antioxidant in order to improve storage stability. The polymerization inhibitor is preferably hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, or various phenol-based antioxidants, but may also be a sulfur-based secondary antioxidant, a phosphorus-based secondary antioxidant, or the like. The total amount of these polymerization inhibitors and / or antioxidants is preferably 0.001 to 3 parts by weight, and more preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of component (A) and, in the case where component (B) is included, per 100 parts by weight of the total amount of components (A) and (B).

[0082] <Light resistance improver> The active energy ray-curable composition of the present invention may contain a light resistance improver such as an ultraviolet absorber or a light stabilizer. Examples of ultraviolet absorbers include benzotriazole compounds such as 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, and 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole; Triazine compounds such as 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine; Examples of benzophenone compounds include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. Examples of light stabilizers include low molecular weight hindered amine compounds such as N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, bis(1,2,6,6-)pentamethyl-4-piperidyl)-2-(3,5-ditertiarybutyl-4-hydroxybenzyl)-2-n-butylmalonate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate; Examples of the hindered amine light stabilizers include high molecular weight hindered amine compounds such as 2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate. The amount of the light resistance improver to be added is preferably 0 to 5 parts by weight, and more preferably 0 to 1 part by weight, per 100 parts by weight of component (A) and, in the case where component (B) is included, per 100 parts by weight of the total amount of components (A) and (B).

[0083] 3. Usage method The active energy ray-curable composition of the present invention can be used in various ways depending on the purpose. For example, when the composition of the present invention is used as a coating agent, the composition can be applied to a substrate, and if the composition contains an organic solvent, the organic solvent in the composition can be evaporated by heating, and then the composition can be cured by irradiating with active energy rays. In addition, when the composition of the present invention is used as an adhesive, the composition may be applied to a substrate, and if an organic solvent is contained in the composition, the organic solvent in the composition may be evaporated by heating, and the composition may then be attached to another substrate, and then the composition may be cured by irradiating the composition with active energy rays.

[0084] The composition of the present invention can be applied to a variety of substrates, including inorganic materials, plastics, and paper. Inorganic materials include glass, metal, mortar, concrete, and stone. Metals include steel sheets, aluminum, chrome, zinc oxide (ZnO), and indium oxide. Examples of the metal oxide include indium tin (ITO). Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate (hereinafter referred to as "PET resins"), polycarbonates, polyarylates, polyethersulfones, cyclic polyolefin resins having cyclic olefins as monomers such as norbornene, polyvinyl chloride, epoxy resins, polyurethane resins, etc. Thermoplastic plastics are preferred, and specific examples thereof include PET resins, acrylic resins, ABS resins, polycarbonates, polypropylene, polyethylene, etc., with PET resins being preferred. Of these materials, metals and plastics are preferred as the substrate. The shape of the substrate is not particularly limited, and may be any of a sheet, film, plate, and the like.

[0085] The method for applying the composition may be appropriately selected depending on the purpose, and examples of the method include coating methods using a conventional bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater, and microgravure coater.

[0086] The thickness of the cured film of the composition on the substrate may be appropriately set depending on the purpose. The thickness of the cured film may be selected depending on the substrate to be used and the application of the substrate having the produced cured film, but is preferably 1 to 100 μm, more preferably 2 to 40 μm.

[0087] Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention include electron beams, ultraviolet rays, and visible light. Of these, ultraviolet light is preferred since it can be cured using a relatively simple device and can be cured with low-energy irradiation in a short time. Electron beam irradiation is preferred in that it does not necessarily require the addition of component (C) (photopolymerization initiator) and the cured product has excellent heat resistance and weather resistance. Examples of ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs).

[0088] In the case of active energy ray irradiation, the irradiation conditions such as the dose, irradiation amount, irradiation intensity, etc. may be appropriately selected depending on the composition used, the base material, the purpose, etc. As an example of using ultraviolet light, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region is 100 to 8,000 mJ / cm 2 is preferable, and 200 to 3,000 mJ / cm 2 is more preferred. When an electron beam is used, it is preferable to irradiate with an acceleration voltage of 50 to 300 kV and an absorbed dose of 10 to 1,000 kGy.

[0089] The compositions of the present invention can be used in a variety of applications. Specific examples thereof include coating agents, adhesives, inks, and films, and the like, and the composition can be preferably used as a coating agent. Specific applications of the coating agent include various paints, decorative films, and topcoats. More specific applications of the coating agent include hard coat applications, in which the substrate includes plastic films used in polarizer protective films and antireflection films, and resin molded products used in home appliances and automobile interior and exterior parts. Other applications of the coating agent include its preferred use as a coating agent for metal substrates, and it can be used as an electrode protective coating agent for PDPs (plasma display panels), a circuit board protective material for electric bicycles, an electrode protective coating agent for lithium ion batteries, etc., and a coating agent for automotive interior and exterior components. EXAMPLES

[0090] The present invention will be described in more detail below with reference to examples and comparative examples. In the following, "parts" means parts by weight. In the Production Examples and Examples, the molecular weight, Tg, acid value, solid content, viscosity, and terminal double bond concentration were measured according to the following methods.

[0091] <Molecular weight measurement> Using a gel permeation chromatograph (model number "HLC-8320", manufactured by Tosoh Corporation), polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (hereinafter referred to as "Mn") were obtained under the following conditions. Measurement conditions Column: Tosoh Corporation TSKgel SuperMultiporeHZ-M x 4 Column temperature: 40℃ Eluent: Tetrahydrofuran Detector: RI

[0092] <Measurement of Tg> The Tg of the copolymer (a1) was measured by a differential scanning calorimeter (DSC) under the following conditions. Measurement conditions DSC: TA Instrument (Q-100) Temperature rise: 10℃ / min Measurement atmosphere: Nitrogen

[0093] <Measurement of acid value> The acid value measurement was carried out according to JIS K0070. That is, the sample was weighed out so that the titration amount was about 10 mL, and diluted with about 50 mL of tetrahydrofuran, and then titration was carried out using an automatic titration device COM-1600ST (manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 N KOH / ethanol solution as the titrant.

[0094] <Solid content> The solid content was calculated from the weight loss after drying in a ventilated dryer at 150°C for 1 hour. The solid content was adjusted to have an easy-to-coat viscosity (1,000-4,000 mPa s), so a high solid content is superior in that it requires less organic solvent.

[0095] <Viscosity at 25°C with 60% solid content> The solid content of each sample was adjusted to 60% by diluting with an organic solvent (butyl acetate or toluene) or by removing the organic solvent with an evaporator. The E-type viscosity of each sample was measured using a TVE-20H viscometer (cone / plate type, manufactured by Toki Sangyo Co., Ltd.) under the following conditions. Measurement conditions Cone shape: angle 1°34′, radius 24mm (less than 10000mPa·s) Angle 3°, radius 7.7mm (10000mPa s or more) Temperature: 25℃±0.5℃

[0096] <Terminal double bond concentration> 1 By H-NMR measurement, the double bond concentration per mass of the polymer was calculated from the ratio of the integral value of the signal derived from hydrogen bonded to the double bond near 5.5 ppm to the integral value of the signal derived from hydrogen bonded to the carbon adjacent to the ester group at 3.0 to 4.5 ppm, and the monomer composition ratio of the polymer.

[0097] 1. Production example (1) Production example 1 The temperature of a 1000 mL pressurized stirred tank reactor equipped with an oil jacket was kept at 263° C. Next, while keeping the pressure of the reactor constant, a monomer mixture consisting of 70 parts of methyl methacrylate (hereinafter referred to as "MMA"), 10 parts of ethyl acrylate (hereinafter referred to as "EA"), 20 parts of glycidyl methacrylate (hereinafter referred to as "GMA"), 12 parts of methyl ethyl ketone (hereinafter referred to as "MEK") as an organic solvent, 3 parts of trimethyl orthoacetate (manufactured by Nippoh Chemical, trade name "MOA", hereinafter referred to as "MOA"), and 1 part of di-t-hexyl peroxide (manufactured by NOF Corp., trade name "Perhexyl D", hereinafter referred to as "DTHP") as a polymerization initiator was continuously fed from a raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 min), and a reaction liquid equivalent to the amount of the monomer mixture fed was continuously withdrawn from the outlet. Immediately after the start of the reaction, the reaction temperature dropped once, and then a temperature rise due to the heat of polymerization was observed, but the reaction temperature was maintained at 187 to 189°C by controlling the temperature of the oil jacket.

[0098] The point at which the temperature stabilized after the start of the monomer mixture supply was set as the start point for collecting the reaction liquid, and the reaction was continued for 37 minutes from this point, resulting in 1.78 kg of monomer mixture being supplied and 1.78 kg of reaction liquid being collected. The reaction liquid was then introduced into a thin-film evaporator, and volatile components such as unreacted monomers were separated to obtain 1.08 kg of a (meth)acrylate polymer having an epoxy group (hereinafter referred to as "copolymer a1-1"). Table 1 shows the Mw, Tg and terminal double bond concentration of the copolymer a1-1.

[0099] Next, copolymer a1-1 (100 parts), dibutylhydroxytoluene (hereinafter referred to as "BHT") (0.15 parts) as a polymerization inhibitor, 45.7 parts of Aronix M-5300 (product name manufactured by Toagosei Co., Ltd.) (corresponding to an acid value of 1.1 equivalents of the epoxy group of copolymer a1-1), and butyl acetate (62.7 parts) as an organic solvent were placed in a 1 L flask, and the liquid temperature was raised to 95°C while bubbling a 5% oxygen-nitrogen mixed gas, to dissolve copolymer a1-1. After uniform dissolution, triphenylphosphine (hereinafter referred to as "TPP") (0.73 parts) was added as a reaction catalyst, and the mixture was stirred for 12 hours while maintaining the internal temperature at 95°C. Further, TPP (0.73 parts) was added, and the reaction was carried out for 12 hours. After that, the acid value was measured, and it was confirmed to be 4.5 mgKOH / g, and the reaction was terminated. As a result, polymer A-1, which was an M-5300 adduct (acrylate modified product) of copolymer a1-1, was obtained.

[0100] Table 1 shows the solids content, acid value, Mn, Mw, acrylic equivalent (g / eq), and viscosity at 25° C. with a solids content of 60% of Polymer A-1.

[0101] (2) Production examples 2 to 13, and 16 Polymers A-2 to A-13, and A-16 were obtained in the same manner as in Production Example 1, except for the changes shown in Table 1.

[0102] Table 1 shows the solid content, acid value, Mn, Mw, acrylic equivalent (g / eq) and viscosity at 25° C. with a solid content of 60% for Polymers A-2 to 13 and 16.

[0103] (3) Comparative production examples 1 and 2 Polymers A'-1 and A'-2 were obtained in the same manner as in Production Example 1, except for the changes shown in Table 1.

[0104] Table 1 shows the solids content, acid value, Mn, Mw, acrylic equivalent (g / eq) and viscosity at 25° C. with a solids content of 60% of Polymers A'-1 and 2.

[0105] (4) Production example 14 Except for the changes shown in Table 1, the same procedure as in Production Example 1 was carried out to obtain copolymer a1-14. Table 1 shows the Mw, Tg and terminal double bond concentration of the polymer a1-14.

[0106] Next, copolymer a1-14 (100 parts), dibutyl hydroxytoluene (hereinafter referred to as "BHT") (0.16 parts) as a polymerization inhibitor, Daicel Corporation's PLAXEL FA-2D (trade name, 66.6 parts, equivalent to 1.0 equivalent hydroxyl value of the isocyanate group of polymer A-14), dibutyltin dilaurate (0.16 parts) as a catalyst, and butyl acetate (71.0 parts) were added to a 1L flask, and the liquid temperature was raised to 80 ° C. while bubbling 5% oxygen-nitrogen mixed gas, and polymer a1-14 was dissolved. Subsequently, the mixture was stirred for 6 hours while maintaining the temperature at 80 ° C., and the absorption by isocyanate at 2200 cm-1 was confirmed to disappear using an ATR infrared spectrophotometer (Perkin Elmer's Spectrum100), and the reaction was terminated. As a result, polymer A-14, which was an FA-2D adduct (acrylate modified product) of copolymer a1-14, was obtained.

[0107] Table 1 shows the solid content, Mn, Mw, acrylic equivalent (g / eq), and viscosity at 25° C. with a solid content of 60% of Polymer A-14.

[0108] (5) Production example 15 Except for the changes shown in Table 1, the same procedure as in Production Example 1 was carried out to obtain a (meth)acrylic polymer a1-15. Table 1 shows the Mw, Tg, and terminal double bond concentration of copolymer a1-15.

[0109] Next, in a reactor equipped with a stirrer, a thermometer, and a water separator, copolymer a1-15 (100 parts), Plaxel FA-2D (66.5 parts), toluene (71 parts) as a solvent, p-toluenesulfonic acid (hereinafter referred to as "PTS") (1.6 parts) as a catalyst, and BHT (0.16 parts) as a polymerization inhibitor were charged, and refluxed at 80 kPa for 6 hours to distill off water (3.7 parts), thereby carrying out a dehydration esterification reaction. Then, water (50 parts) was added to the reaction solution, stirred, and then allowed to stand, and the lower layer (aqueous layer) was separated and removed. Next, 10% sodium hydroxide aqueous solution (50 parts) was added to the upper layer (organic layer), stirred, and then allowed to stand, and the lower layer (aqueous layer) was removed. BHT (0.16 parts) was added to the upper layer (organic layer) and dissolved, and then sodium sulfate was added to dehydrate, and the supernatant was removed to obtain polymer A-15, which is an FA-2D adduct (acrylate modified product) of copolymer a1-15.

[0110] Table 1 shows the solids content, acid value, Mn, Mw, acrylic equivalent (g / eq), and viscosity at 25° C. with a solids content of 60% of Polymer A-15.

[0111] (6) Production example 17 Except for the changes shown in Table 1, the same procedure as in Production Example 1 was carried out to obtain a copolymer a1-17. Table 1 shows the Mw, Tg, and terminal double bond concentration of copolymer a1-17. Furthermore, a modification reaction was carried out in the same manner as in Production Example 15, except for the changes shown in Table 1, to obtain Polymer A-17, which is an M-5300 adduct (acrylate modified product) of Copolymer a1-17.

[0112] Table 1 shows the solids content, acid value, Mn, Mw, acrylic equivalent (g / eq), and viscosity at 25° C. with a solids content of 60% of Polymer A-17.

[0113] [Table 1]

[0114] The abbreviations in Table 1 have the following meanings. Note that, in the following, some of the abbreviations already defined above are repeated. MMA: Methyl methacrylate ·BA: Butyl acrylate ·EA: Ethyl acrylate GMA: Glycidyl methacrylate ·AA: Acrylic acid HEMA: 2-hydroxyethyl methacrylate MOI: 2-isocyanate ethyl methacrylate (Karens MOI (product name), manufactured by Showa Denko K.K.) MEK: Methyl ethyl ketone MOA: Trimethyl orthoacetate (MOA (trade name), manufactured by Nippoh Chemical Co., Ltd.) DTHP: Di-t-hexyl peroxide (Perhexyl D (trade name), manufactured by NOF Corporation) M5300: ε-caprolactone adduct of acrylic acid [Aronix M-5300 (trade name), manufactured by Toagosei Co., Ltd., average degree of polymerization of caprolactone: 2, number average molecular weight: 300, Tg: -78°C, acid value: 186 mgKOH / g] FA-2D: ε-caprolactone adduct of 2-hydroxyethyl acrylate (Placcel FA2D (trade name), manufactured by Daicel Corporation, average degree of polymerization of caprolactone: 2, number average molecular weight: 344, Tg: -78°C, hydroxyl value: 163 mgKOH / g) TPP: Triphenylphosphine ·DBTDL: Dibutyltin dilaurate PTS: p-Toluenesulfonic acid BHT: Dibutyl hydroxytoluene

[0115] 2. Examples (1) Examples 1 to 22, Comparative examples 1 to 3 (UV curable composition) The raw materials shown in Table 2 were stirred and mixed in the amounts shown in Table 2 to prepare active energy ray-curable compositions, which were then evaluated as described below. The results are shown in Table 2.

[0116] <Evaluation of tensile properties> Lumirror T-60 (product name, PET film manufactured by Toray Industries, Inc., film thickness: 100 μm) was prepared as a base film, tape was attached to both ends of the film, and the active energy ray curable composition obtained in the above Examples and Comparative Examples was applied to the surface of the base film using a bar coater #0 so that the film thickness after drying was 60 to 80 μm. Next, the film was dried at 90° C. for 10 minutes in a ventilated dryer to obtain a coated film having a dried coating film of the composition. Next, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used in an air atmosphere, with a concentrated UVA irradiance of 500 mW / cm 2 , the irradiation dose per session is 800mJ / cm 2 The applied film was passed twice under the light irradiation on a conveyor. Next, the film having the cured layer was cut into a strip having a width of 1 cm, and then the cured layer was peeled off from the substrate film. The breaking elongation (%) and breaking strength (unit: MPa) of this cured film were measured at a tensile speed of 5 mm / min using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation). The breaking strength is preferably 5 MPa or more, and the breaking elongation is preferably 2% or more.

[0117] <Evaluation of heat resistance> Cosmoshine A-4300 (trade name, easy-adhesive PET film manufactured by Toyobo Co., Ltd., film thickness: 50 μm) was prepared as a base film, tape was attached to both ends, and the active energy ray curable composition obtained in the above Examples and Comparative Examples was applied to the surface of the base film using a bar coater #0 so that the film thickness after drying was 50 to 60 μm. Then, it was dried at 90° C. for 10 minutes in a ventilated dryer to obtain a coated film having a dried coating film of the composition. Next, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used in an air atmosphere, with a concentrated UVA illuminance of 500 mW / cm 2 , the irradiation dose per session is 800mJ / cm 2 The applied film was passed twice under the light irradiation on a conveyor. The obtained film having the cured layer was heated in a ventilated dryer at 90° C. for 300 hours, and the color difference and haze before and after heating were measured.

[0118] (Measurement of color difference) The yellowness index (YI) was measured using a spectrophotometer SE-2000 (product name) manufactured by Nippon Denshoku Industries Co., Ltd. (YI is calculated according to the following formula). ΔYI is preferably 3 or less. YI = 100(1.28X-1.06Z) / Y (X, Y, Z are color coordinates) ΔYI = YI-YI0 (YI0 indicates YI before the heating test)

[0119] (Measurement of haze) The difference in haze (Δ haze) before and after heating was evaluated by measurement using NDH2000 (product name) manufactured by Nippon Denshoku Industries Co., Ltd. The Δ haze is preferably 2.5 or less.

[0120] <Evaluation of weather resistance> Zeonor (trade name, Zeon Corporation, 50 μm) was prepared as a substrate film, both ends of which were attached with tape, and the active energy ray curable compositions obtained in the above Examples and Comparative Examples were applied to the surface of the substrate film using a bar coater #0 so that the film thickness after drying was 50 to 60 μm. The film was then dried at 90° C. for 10 minutes in a forced air dryer to obtain a coated film having a dried coating film of the composition. Next, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used in an air atmosphere, with a concentrated UVA illuminance of 500 mW / cm 2 , the irradiation dose per session is 800mJ / cm 2 The applied film was passed twice under the light irradiation on a conveyor. The obtained film having the cured layer was placed in a metal weather meter (Daipla Wintes Co., Ltd., "DAIPLA METAL WEATHER KU-R5NCI-A" (product name)) and subjected to an accelerated weather resistance test. The irradiation conditions were 63°C, 70% RH, and illuminance of 80 mW / cm. 2 The test was conducted for 300 hours with a two-minute shower once every two hours. The evaluation was made based on the color difference and haze before and after the test. The color difference and haze were measured in the same manner as above.

[0121] [Table 2]

[0122] The abbreviations in Table 2 have the following meanings. M-215: Isocyanuric acid EO modified diacrylate [Aronix M-215 (product name), manufactured by Toagosei Co., Ltd.] M-327: ε-caprolactone modified tris(acryloxyethyl) isocyanurate [Aronix M- (trade name), manufactured by Toagosei Co., Ltd.] M-1200: Non-yellowing polyester-based urethane acrylate (Mw=4,500) [Aronix M-1200 (product name), manufactured by Toagosei Co., Ltd.] Om184: 1-Hydroxycyclohexylphenyl ketone (manufactured by IGM RESINS BV, product name Omnirad184)

[0123] The results in Table 2 reveal the following. The compositions of Examples 1 to 22 containing the polymer of the present invention (component (A)) in which a (meth)acrylate polymer was modified with an oligomer containing an unsaturated double bond having a Tg of -30 to -90°C gave cured films excellent in tensile properties, heat resistance and weather resistance. In contrast, the cured films obtained from the compositions of Comparative Examples 1 and 2 in which a (meth)acrylate polymer was modified with acrylic acid had low elongation, poor heat resistance and were easily damaged. Furthermore, the cured film obtained from the composition of Comparative Example 3 in which a conventional urethane acrylate was used instead of the polymer (A) of the present invention had insufficient heat resistance and weather resistance. Furthermore, by comparing Examples 12 and 19 with Example 2, it can be seen that the higher the acrylic equivalent, the higher the elongation, but the poorer the weather resistance and heat resistance, so the acrylic equivalent is preferably 2500 g / eq or less, and more preferably 2000 g / eq or less. It can also be seen that according to the present invention, a coating having a breaking strength of 2.5 or more and an elongation of 2% or more can be obtained, and in a preferred embodiment, a breaking strength of 15 or more and an elongation of 4.5% or more, and in a more preferred embodiment, a breaking strength of 20 or more and an elongation of 4.5 to 15%, and excellent in weather resistance and heat resistance, can be obtained.

[0124] (2) Example 23 (Electron beam curable composition) Tape was applied to both ends of a smooth glass plate, and the composition shown in Table 2 was applied using bar coater #0 so that the film thickness after drying would be 60 to 80 μm, and the plate was dried in a forced air dryer at 90° C. for 10 minutes. Next, electron beam irradiation was performed using an electron beam irradiation device manufactured by NHV Corporation under conditions of an acceleration voltage of 150 kV, a dose of 150 kGy (adjusted by beam current and transport speed), and an oxygen concentration of 300 ppm or less, to obtain a cured product. The cured product was peeled off from the glass plate, and the tensile properties, heat resistance, and weather resistance were evaluated in the same manner as for the coated films of Examples 1 to 22. The results are shown in Table 2. It was found that the composition of the present invention, even when it did not contain a photoinitiator (Example 23), gave results equivalent to those when it contained component (D) (photopolymerization initiator) (Example 1).

[0125] (3) Examples 24 to 27, Comparative example 4 (Coating agent) (Creating evaluation samples) Cosmoshine A-4300 (product name, Toyobo's easy-adhesive PET film, film thickness: 50 μm) was prepared as a base film, and the active energy ray-curable composition having the formulation shown in Table 3 was applied to the surface of the base film using a bar coater #10 so that the film thickness after drying would be 4 to 5 μm. The film was then dried at 90° C. for 10 minutes in a forced air dryer to obtain a coated film having a dried coating film of the composition. Next, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used in an air atmosphere, with a concentrated UVA illuminance of 500 mW / cm 2 , the irradiation dose per session is 800mJ / cm 2 The applied film was passed once under the light irradiation on a conveyor. The obtained film having the cured layer was used to carry out pencil hardness and mandrel tests according to the following methods. The results are shown in Table 3.

[0126] (Pencil hardness) The surface of the cured film was scratched with a pencil under a load of 750 g, and the hardness of the hardest pencil that did not leave a scratch was recorded as the pencil hardness. (Mandrel test) The test was carried out according to the method specified in JIS K5600-5-1. (Curling test) The obtained film having the cured layer was cut into a 10×10 cm square and placed on a horizontal table, and curling was evaluated based on the average height of the lift at the four corners.

[0127] [Table 3]

[0128] In terms of pencil hardness, Examples 24 to 26 were superior to Example 27. In the mandrel test, the order of superiority was Examples 24, 25, and 27 > Example 26 > Comparative Example 4. In terms of curling properties, the order of superiority was Examples 24 and 27 > Example 25 > Example 26 > Comparative Example 4. [Industrial Applicability]

[0129] INDUSTRIAL APPLICABILITY The active energy ray-curable composition of the present invention can be suitably used in fields that require a cured product having high mechanical properties, weather resistance, and heat resistance, and can be utilized in the fields of adhesives, coating materials, inks, films, etc.

Claims

1. An active energy ray-curable composition comprising a (meth)acrylate polymer (A) (hereinafter referred to as "component (A)") modified with an unsaturated double bond-containing oligomer (a2) (hereinafter referred to as "unsaturated oligomer (a2)") having a glass transition temperature (Tg) of -30 to -90°C, the component (A) is a reaction product obtained by reacting a copolymer (a1) (hereinafter referred to as "copolymer (a1)") containing a structural unit derived from a (meth)acrylate monomer (a1-1) having no reactive group and a structural unit derived from a (meth)acrylate monomer (a1-2) having a reactive group with an unsaturated oligomer (a2) having a group reactive with the reactive group and an ethylenically unsaturated group, via the reactive group; The acrylic equivalent of the component (A) is 1,400 g / eq or less, The (meth)acrylate monomer (a1-1) having no reactive group constituting the copolymer (a1) comprises at least an alkyl (meth)acrylate.

2. The active energy ray curable composition according to claim 1, wherein the (meth)acrylate monomer (a1-2) having a reactive group constituting the copolymer (a1) is a (meth)acrylate monomer having a reactive group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an isocyanate group.

3. 3. The active energy ray-curable composition according to claim 1, wherein the weight average molecular weight (Mw) of the component (A) is 3,000 to 50,000.

4. The active energy ray-curable composition according to any one of claims 1 to 3, wherein in the component (A), the unsaturated oligomer (a2) is an oligomer containing a ring-opened caprolactone structure.

5. The active energy ray-curable composition according to any one of claims 1 to 4, further comprising a compound (B) having an ethylenically unsaturated group other than the component (A) (hereinafter referred to as "component (B)").

6. The active energy ray-curable composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator (C) (hereinafter referred to as "component (C)"), and in the case where the component (B) is contained with respect to a total of 100 parts by weight of the component (A), the active energy ray-curable composition contains 1 to 20 parts by weight of the component (C) with respect to a total of 100 parts by weight of the component (A) and the component (B).

7. The active energy ray-curable composition according to any one of claims 1 to 6, further comprising an organic solvent (D) (hereinafter referred to as "component (D)"), and in a case where the component (B) is contained per 100 parts by weight of the component (A) in total, the active energy ray-curable composition contains 150 parts by weight or less of the component (D) per 100 parts by weight of the component (A) in total and the component (B).

8. A method for producing an active energy ray-curable composition, comprising a step of reacting a copolymer (a1) (hereinafter referred to as "copolymer (a1)") containing a structural unit derived from a (meth)acrylate monomer (a1-1) having no reactive group and a structural unit derived from a (meth)acrylate monomer (a1-2) having a reactive group with an unsaturated double bond-containing oligomer (a2) (hereinafter referred to as "unsaturated oligomer (a2)") having a group reactive with the reactive group and an ethylenically unsaturated group and having a glass transition temperature (Tg) of -30 to -90°C, to obtain a (meth)acrylate polymer (A) (hereinafter referred to as "component (A)") in which the unsaturated oligomer (a2) is added to the copolymer (a1) via the reactive group, The acrylic equivalent of the component (A) is 1,400 g / eq or less, The (meth)acrylate monomer (a1-1) having no reactive group constituting the copolymer (a1) contains at least an alkyl (meth)acrylate.

1. A method for producing an active energy ray-curable composition comprising the steps of:

9. The method for producing an active energy ray-curable composition according to claim 8, wherein the (meth)acrylate monomer (a1-2) having a reactive group constituting the copolymer (a1) is a (meth)acrylate monomer having a reactive group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an isocyanate group.

10. An active energy ray-curable composition for a coating agent, comprising the active energy ray-curable composition according to any one of claims 1 to 7.

11. An active energy ray-curable composition for adhesives, comprising the active energy ray-curable composition according to any one of claims 1 to 7.

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