JP2021105170A - Active energy ray-curable composition and method for producing the same - Google Patents

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

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 an adhesive, a coating material, an ink, a film and the like.

The active energy ray-curable composition can be cured by irradiating it with active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time, and has high productivity. Therefore, it can be used for inks, coating materials, adhesives, etc. Widely used.

For example, in the case of a top coating agent for a decorative film, the elongation rate and strength of the cured product are required, and when used outdoors, high weather resistance is required.

As the top coating agent, Japanese Patent Application Laid-Open No. 2011-132288 proposes a composition containing a (meth) acrylic resin having a (meth) acryloyl group in the side chain and a urethane (meth) acrylate. Since it contains a certain amount or more of urethane acrylate for expression, there is a problem that the weather resistance is insufficient.

On the other hand, as an active energy ray-curable composition for forming an optical film such as a polarizer protective film, Japanese Patent Application Laid-Open No. 2014-115538 has an acryloyl group in the side chain, and the acryloyl group and the main chain are separated by a certain amount or more ( An active energy ray-curable composition containing a meta) acrylate-based polymer has been proposed. However, although the cured product of this polymer is excellent in 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.

Japanese Unexamined Patent Publication No. 2011-132288 Japanese Unexamined Patent Publication No. 2014-115538

The present invention provides an active energy ray-curable composition that provides a cured product having excellent mechanical properties, weather resistance and heat resistance.

As a result of diligent research to solve the above problems, the present inventors have obtained unsaturated double bond-containing oligomers having a glass transition temperature (hereinafter referred to as "Tg") of -30 to -90 ° C. (meth). We have found that an active energy ray-curable composition containing a polymer obtained by modifying an acrylate-based polymer can solve the above-mentioned problems and can be suitably used as a raw material for an adhesive, a coating material, an ink, a film, etc. Has been completed.

That is, the present invention is a (meth) acrylate-based polymer in which Tg is modified with an unsaturated double bond-containing oligomer (a2) at −30 to −90 ° C. (hereinafter, also referred to as “unsaturated oligomer (a2)”). The present invention relates to an active energy ray-curable composition containing (A) (hereinafter, also referred to as “component (A)”).
According to a preferred embodiment of the present invention, the component (A) has a structural unit (a1-1) derived from a (meth) acrylate-based monomer having no reactive group and a reactive group (a1-1). The copolymer (a1) containing a structural unit derived from the meta) acrylate-based monomer (a1-2) (hereinafter referred to as "copolymer (a1)") is subjected to the above-mentioned reactive group via the above-mentioned reactive group. A reaction product of an unsaturated oligomer (a2) having a group that reacts with a reactive group and an ethylenically unsaturated group is preferable.
Further, as the component (A), the (meth) acrylate-based monomer (a1-2) having a reactive group constituting the copolymer (a1) is an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate. A (meth) acrylate-based monomer having a reactive group selected from the group consisting of groups is preferable.
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-opening caprolactone structure as a constituent unit.
According to another preferred embodiment of the present invention, the composition further comprises a compound (B) having an ethylenically unsaturated other than the component (A) (hereinafter, also referred to as "component (B)").
According to another preferred embodiment of the present invention, the photopolymerization initiator (C) (hereinafter, also referred to as “component (C)”) is further contained, and the total amount of the component (A) is 100 parts by weight. When the component (B) is contained, the component (C) is contained in an amount of 1 to 20 parts by weight based on a total of 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)") with respect to a total of 100 parts by weight of the component (A). When the component (B) is contained, the component (D) is contained in an amount of 150 parts by weight or less with respect to a total of 100 parts by weight of the component (A) and the component (B).

Furthermore, the present invention comprises a structural unit derived from a (meth) acrylate-based monomer (a1-1) having no reactive group and a (meth) acrylate-based monomer (a1-2) having a reactive group. The unsaturated oligomer (a2) is reacted with the copolymer (a1) composed of the structural unit derived from the above, and the unsaturated oligomer (a1) is allowed to react with the copolymer (a1) via the reactive group. It also relates to a method for producing an active energy ray-curable composition including a step of adding a2).
According to a preferred embodiment of the present invention, the (meth) acrylate-based monomer (a1-2) having a reactive group constituting the copolymer (a1) is an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate. It is a (meth) acrylate-based monomer having a reactive group selected from the group consisting of groups.

Further, as the present invention, an active energy ray-curable composition for a coating agent, which comprises the above-mentioned active energy ray-curable composition of the present invention, is preferable.
Further, as the present invention, an active energy ray-curable composition for an adhesive, which comprises the above-mentioned active energy ray-curable composition of the present invention, is preferable.

The active energy ray-curable composition of the present invention is a (meth) acrylate-based polymer (component (component) in which Tg is modified with an unsaturated double bond-containing oligomer (unsaturated oligomer (a2)) at −30 to −90 ° C. Since A)) is contained as an active ingredient, the cured product is excellent in mechanical properties, weather resistance and heat resistance, and can be suitably used as a raw material for adhesives, coating materials, inks, films and the like.

In the present invention, a specific polymer, that is, a (meth) acrylate-based polymer (A) in which Tg is modified with an unsaturated double bond-containing oligomer (unsaturated oligomer (a2)) at −30 to −90 ° C. The present invention relates to an active energy ray-curable composition containing the component (A) as an essential component.
Hereinafter, the component (A), the active energy ray-curable composition, and the method of use will be described in detail.
In the present invention, the "(meth) acrylate-based polymer" means a polymer containing (meth) acrylate as the main component of the constituent unit, and the "(meth) acrylate" means an acrylate and / or Melating methacrylate, "(meth) acrylic" means acrylic and / or methacryl, and "(meth) acryloyl" means acryloyl and / or methacryloyl.

1. 1. Ingredient (A)
The component (A) is a (meth) acrylate-based polymer modified with an unsaturated oligomer (a2).
As described above, the (meth) acrylate polymer means a polymer containing (meth) acrylate as the main component of the constituent unit, and 80 to 100 weight of (meth) acrylate is contained in all the constituent monomer units. Means a polymer containing%.

A typical example of the component (A) is a compound in which an unsaturated oligomer (a2) is bound to the terminal or side chain of the (meth) acrylate-based polymer.
The component (A) is reactive with a structural unit derived from a (meth) acrylate-based monomer (a1-1) having no reactive group (hereinafter referred to as “monomer (a1-1)”). The above-mentioned reactive group is added to a copolymer (a1) composed of a constituent unit derived from a (meth) acrylate-based monomer (a1-2) having a group (hereinafter, referred to as “monomer (a1-2)”). A reaction product of a group that reacts with and an unsaturated oligomer (a2) is preferable.
That is, as the component (A), the ethylenic property obtained by using the copolymer (a1) as a stem polymer and reacting the reactive group of the stem polymer with the reactive group of the unsaturated oligomer (a2). A polymer in which an unsaturated group is bonded as a side chain is preferable.
The "reactive group" in the monomer (a1-1) and the monomer (a1-2) means a functional group other than the (meth) acryloyl group.
Hereinafter, the method for producing the copolymer (a1), the unsaturated oligomer (a2), the component (A), and the physical properties of the component (A) will be described.

(1) Copolymer (a1)
The copolymer (a1), which is the raw material copolymer of the component (A), is composed of a structural unit derived from the monomer (a1-1) and a structural unit derived from the monomer (a1-2). It is a copolymer.
Hereinafter, the monomer (a1-1) and the monomer (a1-2) will be described.

(1-1) Monomer (a1-1)
The monomer (a1-1) is a (meth) acrylate-based monomer (a1-1) having no reactive group.
Specific examples of the monomer (a1-1) are not particularly limited as long as it is a (meth) acrylate-based monomer having no reactive group, but for example, methyl (meth) acrylate and ethyl (meth) acrylate. , Chrylate (meth) acrylate, butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, and Alkyl (meth) acrylates such as stearyl (meth) acrylate;
Alicyclic (meth) acrylates such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate;
N- (meth) acryloyl morpholine;
Acrylamides such as (meth) acrylamide, N-methylolacrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide; and acrylonitrile and metaclo. Examples thereof include nitrile (meth) acrylonitrile.

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

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. Can be mentioned.

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 2-. Examples thereof include an ε-caprolactone adduct of hydroxyethyl (meth) acrylate.

Examples of the monomer (a1-2) having an isocyanate group as a reactive group include (meth) acryloxyethyl isocyanate, and specific products include "Karenzu MOI" and "Karenzu AOI" (both of them). Product name, Showa Denko Co., Ltd.).

Examples of the monomer (a1-2) having a carboxyl group as a reactive group include (meth) acrylic acid, monohydroxyethyl phthalate acrylate, ω-carboxy-polycaprolactone (n ≈ 2) monoacrylate, and (meth). Acryloyloxyethyl succinate, (meth) acryloyloxyethyl hexahydrophthalate, (meth) acryloyloxyethyl phthalate, (meth) acryloyloxyethyl-2-hydroxyethylphthalate, β-carboxyethyl acrylate, phthalan anhydride of pentaerythritol triacrylate Examples thereof include acid adducts, succinic anhydride adducts of pentaerythritol triacrylate, succinic anhydride adducts of dipentaerythritol triacrylate, and phthalic anhydride adducts of dipentaerythritol triacrylate.

(1-3) Polymerization method of copolymer (a1) The method for producing the copolymer (a1) before modification with the unsaturated oligomer (a2) is not particularly limited, but is limited to suspension polymerization and emulsion polymerization. , Solution polymerization, bulk polymerization and the like can be used.
Among these, bulk polymerization and solution polymerization are preferable because the polymer can be easily produced and does not contain impurities such as emulsifiers.

(1-3-1) Solution Polymerization As a solution polymerization method, a method of dissolving a raw material monomer to be used in an organic solvent, adding a thermal polymerization initiator, and heating and stirring can be mentioned. When it is synthesized by radical polymerization by a solution polymerization method, it is obtained by dissolving the raw material monomer to be used in an organic solvent, adding a thermal radical polymerization initiator, and heating and stirring. Also, if desired, a chain transfer agent can be used to regulate the molecular weight of the polymer.

Examples of the organic solvent 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. Hydrogens; and aliphatic hydrocarbons such as hexane, heptane and mineral spirits.

Examples of the thermal polymerization initiator include azo-based initiators such as azobisisobutyronitrile, azobisisobutyronitrile, azobiscyclohexanecarbonitrile and azobiscyanovaleric acid; t-butylperoxypivalate and t-hexyl. Organic peroxides such as peroxypivalate, dilauroyl peroxide, di (2-ethylhexyl) peroxydicarbonate, dit-butylperoxide and dicumylperoxide; and hydrogen peroxide-iron (II) salts, Examples thereof include peroxodisulfate-sodium hydrogen sulfite, cumenehydroperoxide-iron (II) salt and the like.
The ratio of the thermal polymerization initiator used may be appropriately set according to the target molecular weight. The ratio of the thermal radical polymerization initiator used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of all the monomers used.

(1-3-2) Bulk Polymerization As the bulk polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and the like are used. Can be mentioned.
For example, a reactor that can be pressurized is filled with a solvent, the temperature is set to a predetermined temperature under pressure, and then a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate. There is a method of supplying the polymerization solution to the above and extracting an amount of the polymerization solution corresponding to the supply amount of the monomer mixture.
Further, a polymerization initiator may be added to the monomer mixture, if necessary. The blending amount in the case of blending is preferably 0.001 to 2 parts by weight with respect to 100 parts by weight of the monomer mixture.
The pressure depends on the reaction temperature and the boiling point of the monomer mixture and the solvent used, and does not affect the reaction, but may be a pressure capable of maintaining 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 monomer may not react sufficiently, and if the residence time exceeds 60 minutes, the productivity may deteriorate. The preferred residence time is 2-40 minutes.

As an example of the polymerization initiator used to obtain the copolymer (a1), any initiator may be used as long as it generates radicals at a predetermined reaction temperature. Specifically, di-t-butyl peroxide, di-t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, cumenehydroper. Oxide, organic peroxides such as t-butyl hydroperoxide, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), azobiscyclohexacarbonitrile, Examples thereof include azo compounds such as 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 thereof may be used in combination.

The amount of the polymerization initiator used can be appropriately adjusted depending on the type of the polymerization initiator and the monomer, the desired molecular weight, the polymerization conditions, etc., but in general, it is based on 100 parts by weight of the monomer used. 0.001 to 10 parts by weight.

When an organic solvent is used for the production of the copolymer (a1), an organic hydrocarbon compound is suitable, and cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, ethyl acetate and Examples thereof include esters such as 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. With an organic solvent that does not dissolve the (meth) acrylate copolymer well, scale tends to grow on the wall of the reactor, and production problems are likely to occur in the washing process or the like.

The amount of the organic solvent used is preferably 80 parts by weight or less with respect to 100 parts by weight of the total vinyl monomer. By setting the content to 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. It is also possible to add a dehydrating agent such as trimethyl orthoacetate and trimethyl orthoate.
A known chain transfer agent may be used for the production of the copolymer (a1).

The reaction solution extracted from the reactor can be used as it is for the next step, or a polymer can be obtained by distilling off volatile components such as unreacted monomers, organic solvents, and low molecular weight oligomers by distillation or the like. Can be isolated. Some of the volatile components such as unreacted monomers, solvents, and low molecular weight oligomers distilled off from the reaction solution can be returned to the raw material tank or directly returned to the reactor and used again in the polymerization reaction.
The method of recycling the unreacted monomer and the solvent in this way is a preferable method from the economical point of view. When recycling, it is necessary to determine the mixing ratio of the newly supplied monomer mixture so as to maintain the desired monomer ratio and the desired solvent amount in the reactor.

(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, and 1,500. It is preferably from 4,000 to 4,000, more preferably 2,000 to 30,000, even more preferably 2,500 to 25,000, and particularly preferably 3,000 to 15,000. When the Mw is 50,000 or less, the obtained component (A) can have a low viscosity even at a relatively high concentration, so that the coatability is improved, and when mixed with other curable resins, the component (A) is compatible. Will improve. When Mw is 1,500 or more, the obtained cured product of the component (A) has excellent weather resistance and tensile properties.
The Mw in the present invention means a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC) into polystyrene.

The Tg (glass transition temperature) of the copolymer (a1) is not particularly limited, but is usually −40 ° C. or higher and 90 ° C. or lower, and preferably 0 ° C. or higher and 90 ° C. or lower. When the temperature is 0 ° C. or higher, the strength of the cured product is excellent, and when the temperature is 90 ° C. or lower, the flexibility of the cured product is excellent. More preferably, it is 30 to 80 ° C.
The Tg of the copolymer (a1) can be adjusted by appropriately selecting the type and copolymerization ratio of the monomers constituting the copolymer (a1).

In the present invention, Tg is determined from the intersection of the baseline and the tangent at the inflection point of the heat flux curve obtained by using a differential scanning calorimeter manufactured by TA Instrument (Q-100) or the like. means. The heat flux curve shows that about 10 mg of the sample is cooled to -100 ° C in a nitrogen atmosphere and held for 5 minutes, then heated to 300 ° C at 10 ° C / min, then cooled to -100 ° C and held for 5 minutes. It is obtained under the condition that the temperature is raised to 350 ° C. at 10 ° C./min.

In the case of a normal solution polymerization method as disclosed in JP-A-2014-115538, the polymerization temperature is relatively low, so that the number of functional groups is affected by the copolymerization sex ratio and the number of functional groups is the polymer molecule. There will be a bias for each. On the other hand, in the case of high-temperature polymerization, the influence of the copolymerization reactivity ratio becomes small, and in the case of continuous polymerization, a constant polymer continues to be produced, so that the bias in the number of functional groups for each molecule becomes extremely small.
Comparing ordinary solution polymerization and high temperature polymerization, when synthesizing polymers with the same molecular weight, high temperature polymerization uses less polymerization initiator and less initiator residue, so it is weather resistant. The sex improves. In particular, in the case of electron beam curing, since a polymerization catalyst such as a photoinitiator is not used in the curing reaction, the amount of initiator residue contained in the polymer is significantly affected by the influence of weather resistance.
Therefore, the copolymer (a1) used in the present invention generally preferably 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 curing rate can be suppressed. Further, in the present invention, when a copolymer (a1) obtained by high-temperature continuous polymerization is used, the terminal double bond concentration of the copolymer (a1) is 0.02 meq / g or more and 0.5 meq / g. The following is preferable. When it is 0.02 meq / g or more, rapid curing at the time of curing is suppressed, and residual stress is less likely to remain, so that the mechanical properties are improved.

(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 thereof include a (meth) acryloyl group and a vinyl group, of which the (meth) acryloyl group is more. Preferably, an acryloyl group is particularly preferred.
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, the component (A) is obtained by reacting the reactive group in the copolymer (a1) obtained by the above polymerization method or the like with the reactive group of the unsaturated oligomer (a2). More specifically, it is obtained by chemically bonding an unsaturated oligomer (a2) to the copolymer (a1) having the reactive group via the reactive group.

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

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

Examples of the unsaturated oligomer (a2) having an isocyanate group include urethane (meth) acrylate having an isocyanate group at one end.
Examples of the urethane acrylate having an isocyanate group at one end include a compound obtained by reacting a diol with a diisocyanate to produce a compound having an isocyanate group at both ends, and reacting this with a hydroxyl group-containing acrylate. In this case, examples of the diisocyanate include isophorone diisocyanate and hexamethylene diisoanate, and examples of the diol include polytetramethylene glycol and the like. Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl acrylate.
As a method for producing the compound, for example, in the presence of a tin catalyst such as dioctyltin, diisocyanates and diols are reacted in an organic solvent to obtain a urethane oligomer having an isocyanate group at both ends, and then a polymerization inhibitor is used. Examples thereof include a method of reacting hydroxyl group-containing (meth) acrylates in the presence.

When the copolymer (a1) is a copolymer having an isocyanate group or a carboxyl group as a reactive group, the unsaturated oligomer (a2) is a compound having a hydroxyl group as a functional group that reacts with the reactive group. Can be used.
Examples of the unsaturated oligomer (a2) having a hydroxyl group include ε-caprolactone adducts of hydrochialkyl (meth) acrylates such as ε-caprolactone adducts of 2-hydroxyethyl (meth) acrylates, and (meth) acrylic acids. Polypropylene glycol adduct, (meth) acrylic acid polyethylene glycol adduct, (meth) acrylic acid 2-hydroxyethyl poly (3-hydroxybutyrate) adduct, and (meth) acrylic acid polytetramethylene glycol adduct. And so on.
2-Hydroxyethyl (meth) acrylate ε-caprolactone adduct is commercially available, and Plaxel FA2D [2-hydroxyethyl acrylate ε-caprolactone adduct, trade name manufactured by Daicel Co., Ltd., and so on. Molecular weight 344, Tg = -78 ° C], FA5 (ε-caprolactone adduct of 2-hydroxyethyl acrylate. Molecular weight 689), FM2D (ε-caprolactone adduct of 2-hydroxyethyl methacrylate, molecular weight 358), FM3 (2- Ε-caprolactone adduct of hydroxyethyl methacrylate, molecular weight 473), FM5 (ε-caprolactone adduct of 2-hydroxyethyl methacrylate, molecular weight 701) and the like can be mentioned.
Examples of the polypropylene glycol adduct of acrylic acid include a compound having Tg = −75 ° C., and examples of the polyethylene glycol adduct of acrylic acid include a compound having Tg = −41 ° C., which is a poly of 2-hydroxyethyl acrylate. Examples of the (3-hydroxybutyrate) adduct include a compound having Tg = −40 ° C., and examples of the polytetramethylene glycol adduct of acrylic acid include a compound having Tg = −84 ° C.

As the unsaturated oligomer (a2), a compound containing a ring-opening caprolactone structure is preferable. A composition containing the component (A) obtained by using the compound is preferable in that the cured product has an excellent elongation rate.
Specific examples of the compound include the compounds mentioned above.
Examples of the unsaturated oligomer (a2) having a carboxyl group include an ε-caprolactone adduct of (meth) acrylic acid.
Examples of the unsaturated oligomer (a2) having a hydroxyl group include an ε-caprolactone adduct of a hydrochialkyl (meth) acrylate such as an ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate.

(3) Method for producing component (A) The component (A) is obtained by reacting the reactive group of the copolymer (a1) with the reactive group of the unsaturated oligomer (a2). It is preferable to manufacture. In addition, this reaction may be hereinafter referred to as a "denaturation reaction".
That is, as a reaction for adding the unsaturated oligomer (a2) to the copolymer (a1), the unsaturated oligomer (a2) having a carboxyl group is added to the 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.

The reaction ratio between the copolymer (a1) and the unsaturated oligomer (a2) may be appropriately set according to the type of the component (A) to be produced and the like.
The reactive group of the unsaturated oligomer (a2) is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1, with respect to 1 mol of the reactive group of the copolymer (a1). It is .2 mol, more preferably 0.9-1.1 mol.

As a method of reacting and adding an unsaturated oligomer (a2) having a carboxyl group to a copolymer (a1) having an epoxy group, a copolymer (a1) having an epoxy group and an unsaturated oligomer having a carboxyl group are used. (A2), a method in which the catalyst and the organic solvent are mixed, heated to 60 to 120 ° C., and heated for about 5 to 30 hours can be mentioned.

The reaction ratio of the copolymer (a1) having an epoxy group and the unsaturated oligomer (a2) having a carboxyl group is such that the copolymer (a1) having an epoxy group has a carboxyl group with respect to 1 mol of the epoxy group. The unsaturated oligomer (a2) preferably has a carboxyl group of 0.5 to 1.5 mol, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1.

As catalysts, tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide, tetramethylammonium chloride, triphenylphosphine, tributylphosphine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1, 4-diazabicyclo [2,2,2] octane can be mentioned. Of these, it is preferable to use triphenylphosphine in that the cured product is less colored after the heat resistance test.

The amount of the catalyst added is preferably about 0.5 to 5% by weight with respect to the total amount of the copolymer (a1) having an epoxy group and the unsaturated oligomer (a2) having a carboxylic xyl group.

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

Examples of the method for reacting the copolymer (a1) having a hydroxyl group with the unsaturated oligomer (a2) having a carboxyl group include a general dehydration esterification method. A copolymer having a hydroxyl group (a1), an unsaturated oligomer having a carboxyl group (a2), a catalyst, and an organic solvent are mixed and heated at 100 to 120 ° C. to azeotrope the organic solvent and the water to be produced. Examples thereof include a method in which the reaction proceeds by dehydration.

Examples of the catalyst include p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and sulfuric acid, and the amount of the catalyst used is 0.05 to 5 mol% with respect to the number of moles of hydroxyl groups to be reacted.

As the organic solvent, it is preferable to use an organic solvent having low solubility in water produced by the dehydration esterification reaction and capable of proceeding with the reaction while azeotropically distilling water. 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 ratio of the organic solvent is preferably 30 to 70% by weight based on the total amount of the reaction solution.

After the reaction, it is common to remove the acid with water or an alkaline aqueous solution.

As a method of reacting and adding an unsaturated oligomer (a2) having a hydroxyl group to a copolymer (a1) having an isocyanate group, a copolymer (a1) having an isocyanate group and an unsaturated oligomer having a hydroxyl group can be added. After mixing (a2), if necessary, a curing catalyst such as dibutyltin dilaurate is added, and the mixture is heated to 60 to 100 ° C. and the like.

As a method of reacting and adding an unsaturated oligomer (a2) having a hydroxyl group to a copolymer (a1) having a carboxyl group, the copolymer (a1) having a carboxyl group and an unsaturated oligomer having a hydroxyl group can be added. After mixing (a2), a catalyst such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, sulfonated polystyrene, and Nafion-H is added, and in some cases, the temperature is heated to 80 to 120 ° C. in the presence of an organic solvent such as toluene. Then, a method of distilling off the generated water while advancing the esterification reaction can be mentioned.
Further, the catalyst remaining after the reaction can be removed by combining one or more methods such as washing with water, alkali neutralization, an ion exchange resin, a chemical filter for removing the catalyst, and filtration.

Further, in any of the above-mentioned 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 and the like. It is particularly preferable to use dibutylhydroxytoluene from the viewpoint of suppressing coloration of the cured product.

(4) Physical properties of component (A) ((meth) acrylic equivalent and molecular weight)
The (meth) acrylic equivalent of the component (A) is preferably 2,500 g / eq or less. When the more preferable range of the (meth) acrylic equivalent of the component (A) is described in order, it is 150 g / eq or more and 2,500 g / eq or less, 300 g / eq or more and 2000 g / eq or less, and 400 g / eq or more and 1,400 g. / Eq or less, 700 g / eq or more and 1,000 g / eq or less.
When the (meth) acrylic equivalent is 150 g / eq or more, the elongation rate and flexibility of the cured product can be ensured, and when it is 2,500 g / eq or less, the strength and weather resistance of the cured product can be ensured. And the curing rate can be maintained well.

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

The acrylic equivalent is calculated by the following formula. In the following formula, the number of moles of the (meth) acryloyl group of the component (A) is the number of moles of the (meth) acrylicloyl group added to the copolymer (a1) in the above-mentioned modification reaction, and is mixed after the above-mentioned modification reaction. The (meth) acryloyl group derived from the unreacted unsaturated oligomer (a2) is excluded.

The molecular weight of the component (A) is Mw, preferably 3,000 to 50,000.
When Mw is 3,000 or more, the cured product has excellent weather resistance and tensile properties, and when it is 50,000 or less, the viscosity can be reduced even at a relatively high concentration, so that the coatability is excellent. Moreover, when mixed with other curable compounds, the compatibility becomes excellent.
The Mw of the component (A) is 3,000 to 40,000, 3,000 to 30,000, and 4,000 to 20,000, if a more preferable range is described in order.

2. Active Energy Ray Curable Composition The present invention relates to an active energy ray curable composition containing the component (A).
Examples of the method for producing the composition include a method of stirring and mixing the component (A) and, if necessary, other components described later.

The viscosity of the composition may be appropriately set according to the intended use and purpose. The viscosity is preferably 100 to 20,000 mPa · s, more preferably 200 to 8,000 mPa · s.
In the present invention, the viscosity means a value measured at 25 ° C. with an E-type viscometer (cone plate type viscometer).

The composition of the present invention requires the component (A), but various other components can be blended as needed.
Preferred other components include component (B) (compound (B) having an ethylenically unsaturated group other than component (A)), component (C) (photoradical polymerization initiator), and component (D) (organic). Solvent (D)) can be mentioned.
Hereinafter, the components (B) to (D) and other components will be described.
In the following, the component (A) and the component (B) are referred to as "curable components".

(1) Ingredient (B)
The composition of the present invention is an ethylenically unsaturated compound other than the above-mentioned component (A) which is a component (B), if necessary, for the purpose of lowering the viscosity of the entire composition or adjusting other physical properties. May be contained.

Specific examples of the component (B) include (meth) acrylates other than the monomer (a1-1), the monomer (a1-2), the monomer (a1-1) and the (a1-2) [hereinafter. , "Other (meth) acrylate"] and N-vinyl-2-pyrrolidone and the like.

Other (meth) acrylates include compounds having one (meth) acryloyl group [hereinafter referred to as "monofunctional (meth) acrylate"] and compounds having two or more (meth) acryloyl groups [hereinafter, "many". "Sensory (meth) acrylate"] and the like.

Specific examples of the monofunctional (meth) acrylate include trimethylcyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like. Benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, о-phenylphenol EO modified (n = 1-4) (meth) acrylate, p-cumyl Phenol EO modified (n = 1-4) (meth) acrylate, phenyl (meth) acrylate, о-phenylphenyl (meth) acrylate, p-cumylphenyl (meth) acrylate, N- (meth) acryloylmorpholine, N-vinylformamide , N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxyethyl tetrahydrophthalimide and the like.

Specific examples of the polyfunctional (meth) acrylate include urethane (meth) acrylate such as urethane acrylate having a polyester skeleton and urethane (meth) acrylate such as urethane acrylate having a polycarbonate skeleton;
Di (meth) acrylate having a bisphenol skeleton such as bisphenol A EO modified (n = 1-2) di (meth) acrylate and bisphenol A di (meth) acrylate;
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 (poly) alkylene glycol di (meth) acrylate such as di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di ( Di (meth) acrylate of aliphatic diols such as meta) acrylate;
Neopentyl glycol di (meth) acrylate of hydroxypivalate;
Di (meth) acrylate having an alicyclic skeleton such as tricyclodecanedimethylol di (meth) acrylate;
(Meta) acrylate glycerintri (meth) acrylate, trimethylolpropane tri (meth) acrylate, having an isocyanurate skeleton such as isocyanuric acid EO-modified diacrylate and ε-caprolactone-modified tris ((meth) acloxyethyl) isocyanurate, Tri or tetra (meth) acrylate of pentaerythritol, tri or tetra (meth) acrylate of dimethylolpropane, tri or tetra (meth) acrylate of diglycerin and tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol, etc. Polypoly (meth) acrylate; and tri (meth) acrylate of glycerin alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) of trimethylolpropane alkylene oxide adduct. Tri or tetra (meth) acrylate of acrylate, diglycerin alkylene oxide adduct, poly (meth) acrylate of polyol alkylene oxide adduct such as tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol alkylene oxide adduct, etc. And so on.
In the above, EO modification means ethylene oxide modification, and n means the number of repetitions of the alkylene oxide unit.
As the polyfunctional (meth) acrylate, urethane (meth) acrylate and (meth) acrylate having an isocyanate skeleton are preferable among these compounds.

As the component (B), only one kind of the above-mentioned compound may be used, or two or more kinds thereof may be used in combination.

The blending amount of the component (B) may be appropriately set according to the purpose and may be an amount that does not reduce the flexibility of the obtained cured product, but the total of the component (A) and the component (B) is 100% by weight. The component (B) is preferably contained in an amount of 1 to 50% by weight, more preferably 1 to 35% by weight, still more preferably 1 to 25% by weight.

(2) Ingredient (C)
When ultraviolet rays and visible rays are used as active energy rays, the composition of the present invention may contain the component (C) (photopolymerization initiator).
When an electron beam is used as the active energy ray, it is not always necessary to add the component (C), but a small amount of the component (C) can be added as needed to improve the curability.

The component (C) includes benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. , 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1-( Methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2-methyl- 1- [4- (Methylthio)] Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino -2- (4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, Adecocaoptomer N-1414 (manufactured by ADEKA Co., Ltd.), Phenylglycylic acid Aromatic ketone compounds such as methyl ester, ethyl anthraquinone, phenylanthrenquinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-benzoylphenyl sulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis Benzophenones such as (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone Compound;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6) Acylphosphine oxide compounds such as 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone, 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and esterone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Oxime esters such as -1- (O-acetyloxime);
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-Phenylphenyl) -4,5-diphenylimidazole dimer, 2- (p-Phenylphenyl) -4,5-Diphenylimidazole dimer, 2 2,4,5-Triarylimidazole, such as 4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer. Dimers; and acrydin derivatives such as 9-phenylaclydin and 1,7-bis (9,9'-acridinyl) heptane.

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

The blending ratio of the component (C) is 100 parts by weight of the component (A), and when the component (B) is contained, the total amount of the component (A) and the component (B) is 100 parts by weight. , 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, still more preferably 1 to 5 parts by weight.
By blending the component (C) in an amount of 1 part by weight or more, the composition can be cured with an appropriate amount of ultraviolet rays or visible light, and the productivity can be improved, while the amount is 20 parts by weight or less. As a result, the cured product can be made excellent in weather resistance and transparency.

(3) Ingredient (D)
The composition of the present invention can contain an organic solvent as a component (D) for the purpose of improving coatability on a base material.
Even if the same compound is used, the organic solvent is described as "organic solvent" when used in a reaction system, and is described as "organic solvent" when used in a composition such as a paint. In the present invention, these are collectively referred to as "organic solvent".

Specific examples of the component (D) include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropanolethanol, 2-butoxy Ethanol, 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 -Alcohol-based solvents such as methoxy-2-propanol, 1-ethoxy-2-propanol and propylene glycol monomethyl ether;
Ether-based 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;
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methylpentyl ketone, di-n-propyl ketone, diisobutyl ketone, holon, isophorone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc. Ketone solvent;
Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, cellosolve acetate;
Examples thereof include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and γ-butyrolactone.

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

The blending ratio of the component (D) may be appropriately set in consideration of the viscosity of the composition, the purpose of use, etc., but preferably, the component (B) is contained in a total of 100 parts by weight of the component (A). In this case, the component (D) is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 67 parts by weight or less, based on 100 parts by weight of the total of the component (A) and the component (B). 25 to 67 parts by weight is particularly preferable.

(4) Other components other than the above As the other components other than the above, various components can be blended depending on the purpose.
When the composition of the present invention is used as a coating agent, for example, a polymerization inhibitor and / or an antioxidant, a light resistance improver, inorganic particles, a surface modifier, a pigment, a dye, a tackifier, etc. Can be mentioned.
Hereinafter, among the other components, the polymerization inhibitor and / and the antioxidant, and the light resistance improving agent will be described.

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

<Light resistance improver>
The active energy ray-curable composition of the present invention may contain a light resistance improver such as an ultraviolet absorber and a light stabilizer.
Examples of the ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole, 2- (2). Benzotriazole compounds such as'-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;
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, or 2,2 Examples thereof include benzophenone compounds such as'-dihydroxy-4,4'-dimethoxybenzophenone.
Examples of the photostabilizer include N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylenediamine and bis (1,2,6,6). -) Pentamethyl-4-piperidyl) -2- (3,5-ditercious butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Low molecular weight hindered amine compounds such as piperidinyl) sevacate; N, N'-bis (2,
High molecular weight hindered amine compounds such as 2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylenediamine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate Hindered amine-based light stabilizers such as, etc. can be mentioned.
The blending amount of the light resistance improver is 0 with respect to 100 parts by weight of the component (A), and when the component (B) is contained, with respect to 100 parts by weight of the total amount of the component (A) and the component (B). It is preferably ~ 5 parts by weight, more preferably 0 to 1 part by weight.

3. 3. Method of Use The active energy ray-curable composition of the present invention can be used in various ways depending on the intended purpose.
For example, when the composition of the present invention is used as a coating agent, the composition is coated on a base material, and when an organic solvent is contained, the organic solvent in the composition is evaporated by heating, and then the active energy ray is applied. A method of irradiating and curing the solvent can be mentioned.
When the composition of the present invention is used as an adhesive, the composition is applied to a base material, and when an organic solvent is contained, the organic solvent in the composition is evaporated by heating, and then another base material is used. After bonding with, there is a method of further irradiating with active energy rays to cure.

Examples of the base material to which the composition of the present invention can be applied include inorganic materials, plastics, paper and the like, which can be applied to various materials.
Examples of the inorganic material include glass, metal, mortar, concrete and stone, and examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Can be mentioned.
Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, polyvinyl alcohols, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate (hereinafter referred to as "PET resin"), polycarbonates and polys. Examples thereof include cyclic polyolefin resins using cyclic olefins such as allylate, polyethylene terephthalone, and norbornene as monomers, polyvinyl chloride, epoxy resins, and polyurethane resins. As the plastic, a thermoplastic is preferable, and specific examples thereof include PET resin, acrylic resin, ABS resin, polycarbonate, polypropylene, polyethylene and the like, and PET resin is preferable.
Among these materials, metals and plastics are preferable as the base material.
The shape of the base material is not particularly limited, and may be any of a sheet shape, a film shape, a plate shape, and the like.

The coating method of the composition may be appropriately selected according to the purpose, and conventionally known bar coats, applicators, doctor blades, knife coaters, comma coaters, reverse roll coaters, die coaters, lip coaters, gravure coaters and micros. A method of coating with a gravure coater or the like can be mentioned.

The film thickness of the composition cured film with respect to the base material may be appropriately set according to the intended purpose. The thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 to 100 μm, more preferably 2 to 40 μm. ..

Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention include electron beam, ultraviolet light, visible light and the like.
Of these, ultraviolet rays are preferable because they can be cured with a relatively simple device and can be cured with low energy irradiation for a short time.
The electron beam does not necessarily require the addition of the component (C) (photopolymerization initiator), and is preferable in that the cured product has excellent heat resistance and weather resistance.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).

Irradiation conditions such as dose, irradiation amount, and irradiation intensity in active energy ray irradiation may be appropriately selected according to the composition to be used, the base material, the purpose, and the like.
Taking the case of using a high pressure mercury lamp as an example of using ultraviolet, preferably 100~8,000mJ / cm ² irradiation energy in the UV-A region, 200~3,000mJ / cm ² is more preferable.
When an electron beam is used, it is preferable to irradiate the electron beam so that the acceleration voltage is 50 to 300 kV and the absorbed dose is 10 to 1,000 kGy.

The composition of the present invention can be used for various purposes.
Specific examples thereof include coating agents, adhesives, inks, films and the like, which can be preferably used as coating agents.
Specific uses of the coating agent include various paints, decorative films, top coating agents and the like.
More specific uses of the coating agent include hard coat applications. Examples of the base material in this case include a plastic film used for a polarizer protective film and an antireflection film, and a resin molded product used for home appliances and automobile interior / exterior parts.
As another application of the coating agent, it can be preferably used as a coating agent for a metal base material, and is used as an electrode protection material for PDP (plasma display panel), a substrate circuit protection material for an electric bicycle, an electrode protection used for a lithium ion battery, or the like. It can be used as a coating agent and a coating agent for interior and exterior members of automobiles.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, the "part" means a part by weight.
The molecular weight, Tg, acid value, solid content, viscosity, and terminal double bond concentration in Production Examples and Examples were measured according to the following methods.

<Molecular weight measurement>
Using a gel permeation chromatograph device (model name "HLC-8320", manufactured by Tosoh Corporation), Mw (weight average molecular weight) and number average molecular weight (hereinafter referred to as "Mn") in terms of polystyrene were obtained under the following conditions. Obtained.
○ Measurement conditions Column: TSKgel SuperMultipore HZ-M x 4 manufactured by Tosoh Corporation Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI

<Measurement of Tg>
The Tg of the copolymer (a1) was measured with a differential scanning calorimeter (DSC) under the following conditions.
○ Measurement conditions DSC: Made by TA Instrument (Q-100)
Temperature rise temperature: 10 ° C / min Measurement atmosphere: Nitrogen

<Measurement of acid value>
It was carried out according to JIS K0070 and acid value measurement. That is, the sample is weighed so that the titration amount becomes about 10 mL, diluted to about 50 mL of tetrahydrofuran, and then the automatic titrator COM-1600ST (manufactured by Hiranuma Sangyo Co., Ltd.) is used as a titrator with a 0.1 N KOH / ethanol solution. ) Was used for titration.

<Solid content>
The solid content was determined from the weight loss by drying in a ventilation dryer at 150 ° C. for 1 hour. Since the solid content is adjusted to have a viscosity (1,000 to 4,000 mPa · s) that is easy to apply, a high solid content is excellent in that the amount of organic solvent used is small. You can see that there is.

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

<Terminal double bond concentration>
^{1 By 1} H-NMR measurement, the integrated value of the signal derived from the hydrogen bonded to the double bond near 5.5 ppm, and the hydrogen bonded to the carbon adjacent to the ester group at 3.0 to 4.5 ppm. The double bond concentration per mass of the polymer was calculated from the ratio of the integrated values of the derived signals and the monomer composition ratio of the polymer.

1. 1. Manufacturing example
(1) Production Example 1
The temperature of a 1000 mL pressurized stirring tank reactor equipped with an oil jacket was maintained at 263 ° C. Next, while keeping the pressure of the reactor constant, 70 parts of methyl methacrylate (hereinafter referred to as "MMA"), 10 parts of ethyl acrylate (hereinafter referred to as "EA"), and glycidyl methacrylate (hereinafter referred to as "GMA") 20 parts, as an organic solvent, 12 parts of methyl ethyl ketone (hereinafter referred to as "MEK"), 3 parts of trimethyl orthoacetate (manufactured by Nihon Kagaku Co., Ltd., trade name "MOA", hereinafter referred to as "MOA"), polymerization initiator. A monomer mixture consisting of one part of di-t-hexyl peroxide (manufactured by Nichiyu, trade name "Perhexyl D", hereinafter referred to as "DTHP") is supplied at a constant supply rate (48 g / min, residence time:). 12 minutes), continuous supply from the raw material tank to the reactor was started, and the reaction solution corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet.
Immediately after the start of the reaction, the reaction temperature was once lowered, and then the temperature was increased due to the heat of polymerization. However, the reaction temperature was maintained at 187 to 189 ° C. by controlling the temperature of the oil jacket.

The time when the temperature became stable from the start of supply of the monomer mixture was set as the collection start point of the reaction solution, and as a result of continuing the reaction for 37 minutes from this point, 1.78 kg of the monomer mixture was supplied and 1.78 kg of the reaction was carried out. The liquid was recovered. After that, the reaction solution is introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and 1.08 kg of a (meth) acrylate polymer having an epoxy group (hereinafter referred to as "copolymer a1-1") is used. Obtained.
Table 1 shows the Mw, Tg, and terminal double bond concentrations of the copolymer a1-1.

Next, copolymer a1-1 (100 parts), dibutylhydroxytoluene (hereinafter referred to as "BHT") (0.15 parts) as a polymerization inhibitor, Aronix M-5300 (trade name manufactured by Toa Synthetic Co., Ltd.) 45. .7 parts (corresponding to 1.1 equivalent acid value of the epoxy group of copolymer a1-1) and butyl acetate (62.7 parts) as an organic solvent are put into a 1 L flask, and a 5% oxygen-nitrogen mixed gas is added. While bubbling, the liquid temperature was raised to 95 ° C. to dissolve the copolymer a1-1.
After uniformly dissolving, triphenylphosphine (hereinafter referred to as "TPP") (0.73 part) was added as a reaction catalyst, and the mixture was stirred for 12 hours while maintaining an internal temperature of 95 ° C. Further, TPP (0.73 part) was added and reacted for 12 hours. Then, the acid value was measured, and it was confirmed that the acid value was 4.5 mgKOH / g, and the reaction was terminated.
As a result, polymer A-1, which is an M-5300 adduct (acrylate-modified product) of copolymer a1-1, was obtained.

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

(2) Production Examples 2 to 13 and 16
Polymers A-2 to 13 and 16 were obtained by the same operation as in Production Example 1 except for the changes shown in Table 1.

Table 1 shows the viscosities of the polymers A-2 to 13 and 16 at 25 ° C., which are the solid content, acid value, Mn, Mw, acrylic equivalent (g / eq), and solid content of 60%.

(3) Comparative Production Examples 1 and 2
Polymers A'-1 and 2 were obtained by the same operation as in Production Example 1 except for the changes shown in Table 1.

Table 1 shows the viscosities of the polymers A'-1 and 2 at 25 ° C., which are the solid content, acid value, Mn, Mw, acrylic equivalent (g / eq), and solid content of 60%.

(4) Production Example 14
Copolymer a1-14 was obtained by the same operation as in Production Example 1 except for the changes shown in Table 1.
Table 1 shows the Mw, Tg, and terminal double bond concentrations of the polymer a1-14.

Next, the copolymer a1-14 (100 parts), dibutylhydroxytoluene (hereinafter referred to as "BHT") (0.16 parts) as a polymerization inhibitor, and Praxel FA-2D (trade name, 66.6 parts) manufactured by Daicel Co., Ltd. , 1.0 equivalent of the hydroxyl value of the isocyanate group of the polymer A-14), dibutyltin dilaurate (0.16 parts) and butyl acetate (71.0 parts) as catalysts were put into a 1 L flask and 5% oxygen. While bubbling the nitrogen mixed gas, the liquid temperature was raised to 80 ° C. to dissolve the polymer a1-14. Subsequently, the mixture was stirred for 6 hours while maintaining 80 ° C., and using an ATR infrared spectrophotometer (Spectrum 100 manufactured by Perkin Elmer), it was confirmed that the absorption by isocyanate of 2200 cm-1 had disappeared, and the reaction was terminated. did.
As a result, polymer A-14, which is an FA-2D adduct (acrylate-modified product) of copolymer a1-14, was obtained.

Table 1 shows the viscosities of the polymer A-14 having a solid content, Mn, Mw, an acrylic equivalent (g / eq), and a solid content of 60% at 25 ° C.

(5) Production Example 15
A (meth) acrylic polymer a1-15 was obtained by the same operation as in Production Example 1 except for the changes shown in Table 1.
Table 1 shows the Mw, Tg, and terminal double bond concentrations of the copolymer a1-15.

Next, in a reactor equipped with a stirrer, a thermometer, and a water separator, copolymer a1-15 (100 parts), praxel FA-2D (66.5 parts), toluene as a solvent (71 parts), and catalyst. Add p-toluenesulfonic acid (hereinafter referred to as "PTS") (1.6 parts) and BHT (0.16 parts) as a polymerization inhibitor, reflux at 80 kPa for 6 hours, and add water (3.7 parts). Distillation was carried out and a dehydration esterification reaction was carried out.
Then, water (50 parts) was added to the reaction solution, and the mixture was stirred and then allowed to stand to separate and remove the lower layer (aqueous layer). Next, a 10% aqueous sodium hydroxide solution (50 parts) was added to the upper layer (organic layer), stirred and allowed to stand, and then the lower layer (aqueous layer) was removed. After adding and dissolving BHT (0.16 part) to the upper layer (organic layer), dehydration is performed by adding sodium sulfate, the supernatant is taken out, and the FA-2D adduct (acrylate modified product) of the copolymer a1-15 is taken out. Polymer A-15 was obtained.

Table 1 shows the viscosities of the polymer A-15 at 25 ° C., which are the solid content, acid value, Mn, Mw, acrylic equivalent (g / eq), and solid content of 60%.

(6) Production Example 17
A copolymer a1-17 was obtained by the same operation as in Production Example 1 except for the changes shown in Table 1.
Table 1 shows the Mw, Tg, and terminal double bond concentrations of the copolymer a1-17.
Further, the modification reaction was carried out in the same manner as in Production Example 15 except for the changes shown in Table 1, and the polymer A-, which is an M-5300 adduct adduct (acrylate modified product) of the copolymer a1-17. I got 17.

Table 1 shows the viscosities of the polymer A-17 at 25 ° C., which are the solid content, acid value, Mn, Mw, acrylic equivalent (g / eq), and solid content of 60%.

The abbreviations in Table 1 mean the following. In the following, some of the ones already defined above are also described in duplicate.
-MMA: Methyl Methacrylate-BA: Butyl Acrylate-EA: Ethyl Acrylate-GMA: Glysidyl Methacrylate-AA: Acrylic Acid-HEMA: 2-Hydroxyethyl Methacrylate-MOI: 2-Isocyanate Ethyl Methacrylate [Karens MOI (trade name), Showa Made by Denko Co., Ltd.]
-MEK: butanone ketone-MOA: trimethyl orthoacetate [MOA (trade name), manufactured by Nippoh Chemicals, Inc.]
-DTHP: Di-t-hexyl peroxide [Perhexyl D (trade name), manufactured by NOF CORPORATION]
-M5300: Acrylic acid ε-caprolactone adduct [Aronix M-5300 (trade name), manufactured by Toa Synthetic Co., Ltd., average degree of polymerization of caprolactone: 2, number average molecular weight: 300, Tg: -78 ° C, acid value 186 mgKOH / g]
FA-2D: 2-hydroxyethyl acrylate ε-caprolactone adduct [Placel FA2D (trade name), manufactured by Daicel Corporation, average degree of polymerization of caprolactone: 2, number average molecular weight: 344, Tg: -78 ° C, Hydroxylate value: 163 mgKOH / g]
-TPP: triphenylphosphine-DBTDL: dibutyltin dilaurate-PTS: p-toluenesulfonic acid-BHT: dibutylhydroxytoluene

2. Example
(1) Examples 1 to 22 and Comparative Examples 1 to 3 (ultraviolet curable composition)
The raw materials shown in Table 2 were stirred and mixed according to the amount ratio shown in Table 2 to prepare an active energy ray-curable composition, which was evaluated according to the following. The results are shown in Table 2.

<Evaluation of tensile properties>
As a base film, Lumirror T-60 (trade name, PET film manufactured by Toray Industries, Inc., film thickness; 100 μm) was prepared, tapes were attached to both ends thereof, and bar coater # 0 was used on the surface of the base film. The active energy ray-curable composition obtained in the above Examples and Comparative Examples was applied so that the film thickness after drying was 60 to 80 μm. Then, it was dried at 90 ° C. for 10 minutes in a ventilation dryer to obtain a coating film having a dry coating film of the composition.
Next, using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the UVA illuminance was adjusted to ^{500 mW / cm 2} and the irradiation amount per irradiation was 800 mJ / cm ^{2 in an air atmosphere.} , The coating film was passed through the conveyor twice under the light irradiation.
Next, a film having a cured film was cut into strips having a width of 1 cm, and then the cured film was peeled off from the base film.
Using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation), the breaking elongation (%) and breaking strength (unit: MPa) of this cured film under the condition of a tensile speed of 5 mm / min were determined. It was measured. The breaking strength is preferably 5 MPa or more, and the breaking elongation is preferably 2% or more.

<Evaluation of heat resistance>
Prepare Cosmo Shine A-4300 (trade name, easy-adhesive PET film manufactured by Toyobo Co., Ltd., film thickness; 50 μm) as a base film, attach tapes to both ends, and apply bar coater # 0 to the surface of the base film. The active energy ray-curable composition obtained in the above Examples and Comparative Examples was applied so that the film thickness after drying was 50 to 60 μm. Then, it was dried at 90 ° C. for 10 minutes in a ventilation dryer to obtain a coating film having a dry coating film of the composition.
Next, using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the UVA illuminance was adjusted to ^{500 mW / cm 2} and the irradiation amount per irradiation was 800 mJ / cm ^{2 in an air atmosphere.} , The coating film was passed through the conveyor twice under the light irradiation.
The obtained film having the cured film was heated in a ventilation dryer at 90 ° C. for 300 hours, and the color difference and haze before and after heating were measured.

(Measurement of color difference)
The yellowness (YI) was measured using a spectrocolorimeter SE-2000 (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd. (YI is as shown in the formula below). ΔYI is preferably 3 or less.
YI = 100 (1.28X-1.06Z) / Y (X, Y, Z are color coordinate systems)
ΔYI = YI-YI ₀ (YI ₀ indicates YI before the heating test)

(Measurement of haze)
The measurement was performed using NDH2000 (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd., and the difference in haze before and after heating (Δ haze) was evaluated. The Δ haze is preferably 2.5 or less.

<Evaluation of weather resistance>
Zeonoa (trade name, manufactured by Nippon Zeon Corporation, 50 μm) is prepared as a base film, tapes are attached to both ends thereof, and a bar coater # 0 is used on the surface of the base film, and the film thickness after drying is 50. The active energy ray-curable composition obtained in the above Examples and Comparative Examples was applied so as to have a thickness of about 60 μm. Then, it was dried at 90 ° C. for 10 minutes in a ventilation dryer to obtain a coating film having a dry coating film of the composition.
Next, using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the UVA illuminance was adjusted to ^{500 mW / cm 2} and the irradiation amount per irradiation was 800 mJ / cm ^{2 in an air atmosphere.} , The coating film was passed through the conveyor twice under the light irradiation.
The film having the obtained cured film was placed in a metal weather meter (“DAIPLA METAL WEATHER KU-R5NCI-A” (trade name) manufactured by Daipla Wintes), and an accelerated weather resistance test was conducted. The conditions were irradiation 63 ° C., 70% RH, illuminance 80 mW / cm ^2, and a 300-hour test was conducted with a shower for 2 minutes once every 2 hours.
It was evaluated by the color difference and haze before and after the test. The color difference and haze were measured in the same manner as above.

The abbreviations in Table 2 mean the following.
-M-215: Isocyanuric acid EO-modified diacrylate [Aronix M-215 (trade name), manufactured by Toagosei Co., Ltd.]
-M-327: ε-caprolactone-modified tris (acroxyethyl) isocyanurate [Aronix M- (trade name), manufactured by Toagosei Co., Ltd.]
M-1200: Non-yellowing polyester skeleton urethane acrylate (Mw = 4,500)
[Aronix M-1200 (trade name), manufactured by Toagosei Co., Ltd.]
-Om184: 1-Hydroxycyclohexyl-phenylketon [IGM RESINS B. V. Made by the company, product name Omnirad 184]

From the results in Table 2, the following can be seen. In the compositions of Examples 1 to 22, the polymer (component (A)) of the present invention in which the (meth) acrylate-based polymer is modified with an unsaturated double bond-containing oligomer having a Tg of -30 to −90 ° C. is contained. A cured film having excellent tensile properties, heat resistance and weather resistance was obtained. On the other hand, the cured films obtained from the compositions of Comparative Examples 1 and 2 in which the (meth) acrylate-based polymer was modified with acrylic acid had a low elongation rate, poor heat resistance, and were easily damaged. Further, the cured film obtained from the composition of Comparative Example 3 in which the conventional urethane acrylate was used instead of the polymer (A) of the present invention had insufficient heat resistance and weather resistance.
Further, from the comparison between Examples 12 and 19 and Example 2, the higher the acrylic equivalent, the higher the elongation rate, but since the weather resistance and heat resistance are inferior, the acrylic equivalent is preferably 2500 g / eq or less, and 2000 g / eq. It can be seen that the following are more preferable. Further, according to the present invention, a coating having a breaking strength of 2.5 or more and an elongation rate of 2% or more can be obtained. In a preferred embodiment, a breaking strength of 15 or more and an elongation rate of 4.5% or more, and in a more preferable embodiment, a breaking strength. It can be seen that a coating having excellent weather resistance and heat resistance can be obtained with an elongation rate of 4.5 to 15% at 20 or more.

(2) Example 23 (electron beam curable composition)
Tapes are attached to both ends on a smooth glass plate, and the composition shown in Table 2 is applied using bar coater # 0 so that the film thickness after drying is 60 to 80 μm, and the temperature is 90 ° C. in a ventilation dryer. It was dried for 10 minutes.
Next, an electron beam irradiation device manufactured by NHV Corporation was used to perform electron beam irradiation 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 physical characteristics, heat resistance and weather resistance were evaluated in the same manner as in the coating films of Examples 1 to 22. The results are shown in Table 2. From the results in Table 2, even when the composition of the present invention does not contain a photoinitiator (Example 23), the same result as when the composition (D) (photopolymerization initiator) is contained (Example 1) is obtained. It turned out to be.

(3) Examples 24-27, Comparative Example 4 (Coating agent)
(Creation of evaluation sample)
Cosmo Shine A-4300 (trade name, Toyobo's easy-adhesive PET film, film thickness; 50 μm) was prepared as the base film, and the film thickness after drying was 4 using bar coater # 10 on the surface of the substrate film. The active energy ray-curable composition of the formulation shown in Table 3 was applied so as to have a thickness of ~ 5 μm. Then, it was dried at 90 ° C. for 10 minutes in a ventilation dryer to obtain a coating film having a dry coating film of the composition.
Next, using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., the UVA illuminance was adjusted to ^{500 mW / cm 2} and the irradiation amount per irradiation was 800 mJ / cm ^{2 in an air atmosphere.} , The coating film was passed once under the light irradiation on a conveyor.
Using the obtained film having a cured film, a pencil hardness and a mandrel test were carried out according to the following method.
The results are shown in Table 3.

(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 scratch was taken as the pencil hardness (mandrel test).
The test was carried out by the method shown in JIS K5600-5-1.
(Curl property test)
The obtained film having the cured film was cut into 10 × 10 cm squares and placed on a horizontal table, and the curl property was evaluated from the average value of the floating heights at the four corners.

Examples 24 to 26 are superior to Example 27 in terms of pencil hardness, and in the mandrel test, Examples 24, 25, 27> Example 26> Comparative Example 4 are superior in this order, and in terms of curl property, the pencil hardness is improved. The results were excellent in the order of Examples 24 and 27> Example 25> Example 26> Comparative Example 4.

The active energy ray-curable composition of the present invention can be suitably used in fields where a cured product having high mechanical properties, weather resistance and heat resistance is required, and can be suitably used in fields such as adhesives, coating materials, and inks. , And can be used in fields such as film.

Claims (13)

A (meth) acrylate-based polymer (A) modified with an unsaturated double bond-containing oligomer (a2) having a glass transition temperature (Tg) of -30 to −90 ° C. (hereinafter referred to as “unsaturated oligomer (a2)”). ) (Hereinafter referred to as "component (A)"). The component (A) has a structural unit derived from a (meth) acrylate-based monomer (a1-1) having no reactive group and a (meth) acrylate-based monomer (a1-2) having a reactive group. ) Is contained in the copolymer (a1) (hereinafter, referred to as “copolymer (a1)”), the group that reacts with the reactive group via the reactive group, and the ethylenically non-ethylenically. The active energy ray-curable composition according to claim 1, which is a reaction product with an unsaturated oligomer (a2) having a saturated group. The (meth) acrylate-based monomer (a1-2) having a reactive group constituting the copolymer (a1) is a reactivity selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate group. The active energy ray-curable composition according to claim 2, which is a (meth) acrylate-based monomer having a group. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) of the component (A) is 3,000 to 50,000. The active energy ray-curable composition according to any one of claims 1 to 4, wherein the acrylic equivalent of the component (A) is 2,500 g / eq or less. The active energy ray-curable composition according to any one of claims 1 to 5, wherein in the component (A), the unsaturated oligomer (a2) is an oligomer containing a ring-opening caprolactone structure. The active energy ray curing according to any one of claims 1 to 6, further comprising a compound (B) having an ethylenically unsaturated group other than the component (A) (hereinafter referred to as "component (B)"). Sex composition. Further, when the photopolymerization initiator (C) (hereinafter referred to as "component (C)") is contained and the component (B) is contained with respect to a total of 100 parts by weight of the component (A), the component (hereinafter referred to as "component (C)"). The active energy ray-curable composition according to any one of claims 1 to 7, which contains 1 to 20 parts by weight of the component (C) with respect to 100 parts by weight of the total of A) and the component (B). .. Further, when the organic solvent (D) (hereinafter referred to as "component (D)") is contained and the component (B) is contained with respect to a total of 100 parts by weight of the component (A), the component (A) is contained. The active energy ray-curable composition according to any one of claims 1 to 8, which contains 150 parts by weight or less of the component (D) with respect to a total of 100 parts by weight of the component (B). A structural unit (a1-1) derived from a (meth) acrylate-based monomer having no reactive group and a structural unit derived from a (meth) acrylate-based monomer having a reactive group (a1-2). A step of reacting the unsaturated oligomer (a2) with the copolymer (a1) composed of the above, and adding the unsaturated oligomer (a2) to the copolymer (a1) via the reactive group. A method for producing an active energy ray-curable composition. The (meth) acrylate-based monomer (a1-2) having a reactive group constituting the copolymer (a1) is a reactivity selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate group. The method for producing an active energy ray-curable composition according to claim 10, which is a (meth) acrylate-based monomer having a group. 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 9. An active energy ray-curable composition for an adhesive comprising the active energy ray-curable composition according to any one of claims 1 to 9.