JP2022086409A - Active energy ray-curable composition - Google Patents

Abstract

To provide an active energy ray-curable composition in which dripping or tackiness of a dry film is suppressed before curing, and, even when coated on a vertical surface or a complicated shape, an obtained cured material has excellent aesthetic property, improved mechanical properties such as hardness and film strength, and is also excellent in weather resistance.SOLUTION: (A)A composition comprising a compound having an ethylenically unsaturated group, in which the storage elastic modulus G'(measurement frequency 1 Hz) at 80°C of a dry film before active energy ray is irradiated is 10 Pa or larger. The (A) component is preferred that the component (A) contains a (meth) acrylate polymer having an ethylenically unsaturated group in a (A1) side chain. This composition can be suitably used for coating materials such as coatings.SELECTED DRAWING: None

Description

Since the present invention can suppress dripping and tacking of the dry film before curing, the obtained cured product has excellent aesthetics and hardness even when applied to a vertical surface or a complex shape. An active energy ray-curable composition having excellent mechanical properties and weather resistance can be suitably used for coating agents such as paints and adhesives.

A composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam has advantages such as low temperature curing, less energy required for curing, shorter curing time, and higher productivity than a thermosetting composition. Yes, it is applied in a wide range of fields such as coating agents and adhesives.

For example, Patent Documents 1, 2 and 3 describe an active energy ray-curable type containing a compound having two or more (meth) acryloyl groups and various other compounds having an ethylenically unsaturated group as curable components. Coating agent compositions are disclosed.

However, the coating agent compositions of Patent Documents 1, 2 and 3 have a problem that when they are applied to a vertical surface, dripping occurs before curing and the appearance of the cured product is spoiled.
Further, when these compositions are applied to a complex shape, the irradiation amount of the active energy ray changes remarkably depending on the site, and the physical properties such as hardness and film strength are remarkably poor in the site having a low irradiation amount. was there.

Japanese Patent Application Laid-Open No. 2015-120781 International Publication WO15 / 133560 Japanese Unexamined Patent Publication No. 2014-51654

In the present invention, dripping and tack of the dry film before curing are suppressed, and even when applied to a vertical surface or a complex shape, the obtained cured product has excellent aesthetics, and further, hardness, film strength, etc. It is an object of the present invention to provide an active energy ray-curable composition having improved mechanical properties and excellent weather resistance.

As a result of diligent research to solve the above problems, the present inventors set the storage elastic modulus of the dry film of the composition before irradiation to a certain value or more by measuring the viscoelasticity of the composition before irradiation. Since it is possible to suppress dripping and tacking of the dry film, it has been found that a cured product having excellent hardness, mechanical properties and weather resistance can be obtained even in a portion having a low irradiation dose or a portion not irradiated. The present invention has been completed.

The present invention is a composition containing (A) a compound having an ethylenically unsaturated group (hereinafter, also referred to as “component (A)”), and has a storage elastic modulus G of 80 ° C. of a dry film before irradiation with active energy rays. It relates to an active energy ray-curable composition having a (measurement frequency of 1 Hz) of 10 Pa or more.
The component (A) preferably contains a (meth) acrylate-based polymer having an ethylenically unsaturated group in the side chain (A1) (hereinafter, also referred to as “component (A1)”).
The component (A1) is selected from the group consisting of a structural unit derived from a (meth) acrylate-based monomer (a1-1) having no reactive group, and an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate group. The reaction with a copolymer (a1) containing a structural unit derived from a (meth) acrylate-based monomer (a1-2) having a reactive group (hereinafter referred to as “copolymer (a1)”). It is preferable to contain a reaction product of a compound (a2) having a group that reacts with a sex group and an ethylenically unsaturated group (hereinafter, referred to as “unsaturated compound (a2)”).
The unsaturated compound (a2) is preferably an unsaturated double bond-containing oligomer (a2-1) having a glass transition temperature (Tg) of −30 to −90 ° C.

As another embodiment of the present invention, a composition containing (B) a solvent is further preferable.
As another embodiment of the present invention, a composition containing a compound having an ethylenically unsaturated group other than the component (A1) (hereinafter, also referred to as “component (A2)”) is preferable as the component (A). ..
The active energy ray is preferably an electron beam.
As another embodiment of the present invention, a composition containing (C) a photopolymerization initiator is further preferable.

As the use of the composition of the present invention, an active energy ray-curable composition for a coating agent is preferable.

According to the present invention, in (A) an active energy ray-curable composition containing a compound having an ethylenically unsaturated group, the 80 ° C. storage elastic modulus G'(measurement frequency 1 Hz) of the dry film before irradiation with the active energy ray is determined. Since it was set to 10 Pa or more, not only was it possible to suppress dripping and tacking of the dry film of the composition before irradiation, but even when it was applied to a vertical surface or a complex shape, it was not irradiated to a site with a low irradiation dose. The hardness of the cured product can be improved even at the site, and as a result, a cured product having excellent aesthetics, mechanical properties such as hardness and film strength, and weather resistance can be obtained.

Hereinafter, the present invention will be described in detail.
The present invention is (A) a composition containing a compound having an ethylenically unsaturated group, and has an activity in which the 80 ° C. storage elastic modulus G'(measurement frequency 1 Hz) of the dry film before irradiation with active energy rays is 10 Pa or more. The present invention relates to an energy ray curable composition.
Hereinafter, the component (A), the active energy ray-curable composition, and the method of use will be described.
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 methacrylic, and "(meth) acryloyl" means acryloyl and / or methacryloyl.

1. 1. Component (A ) Component (A) is a compound having an ethylenically unsaturated group, which forms a curable component of an active energy ray-curable composition, and can be used alone or in combination with other components. It is not particularly limited as long as the 80 ° C. storage elastic modulus G'(measurement frequency 1 Hz) of the dry film before irradiation with active energy rays is 10 Pa or more. The composition is preferably composed of 30 to 100% by mass of the component (A) and 0 to 70% by mass of the other components.

As the component (A), a (meth) acrylate-based polymer having an ethylenically unsaturated group in the side chain of the component (A1) is preferable.
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%.
The component (A) of the present invention may be a compound having an ethylenically unsaturated group other than the component (A1) which is the component (A2).
Hereinafter, the component (A1) and the component (A2) will be described.

1-1. Component (A1 ) Component (A1) is a (meth) acrylate-based polymer having an ethylenically unsaturated group in the side chain.
The component (A1) is a reaction with a structural unit derived from a (meth) acrylate-based monomer (a1-1) having no reactive group (hereinafter, also referred to as “monomer (a1-1)”). A copolymer (a1) containing a structural unit derived from a (meth) acrylate-based monomer (a1-2) having a sex group (hereinafter, also referred to as “monomer (a1-2)”) and the above-mentioned A reaction product of a compound (a2) having a group that reacts with a reactive group and an ethylenically unsaturated group (hereinafter, also referred to as “unsaturated compound (a2)”) is preferable.
That is, as the component (A1), the copolymer (a1) is used as a stem polymer, and the reactive group of the stem polymer is reacted with the reactive group of the unsaturated compound (a2) to obtain ethylenic properties. 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 compound (a2) and the component (A1), and the physical properties of the component (A1) will be described.

(1) Copolymer (a1)
The copolymer (a1), which is the raw material copolymer of the component (A1), 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. , Acrylate (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 methacrylonitrile. Examples include nitrile.

(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 the reactive group include (meth) acryloxyethyl isocyanate, and specific products include "Karenzu MOI" and "Karenzu AOI" (either of them). (Product name, manufactured by Showa Denko).

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, pentaerythritol triacrylate anhydrous Examples thereof include phthalic acid adduct, anhydrous succinic acid adduct of pentaerythritol triacrylate, anhydrous succinic acid adduct of dipentaerythritol triacrylate, and anhydrous phthalic acid adduct of dipentaerythritol triacrylate.

(1-3) Polymerization method of copolymer (a1) The method for producing the copolymer (a1) before reacting the unsaturated compound (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 may be mentioned. When synthesizing 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. Further, if necessary, a chain transfer agent can be used to adjust the molecular weight of the polymer.

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. Hydrogens; and aliphatic hydrocarbons such as hexane, heptane and mineral spirits.

Examples of the thermal polymerization initiator include azo-based initiators such as azobisisobutyronitrile, azobisisovaleronitrile, azobiscyclohexanecarbonitrile and azobiscyanovaleric acid; t-butylperoxypivalate and t-hexyl. Organic peroxides such as peroxypivalate, dilauroyl peroxide, di (2-ethylhexyl) peroxydicarbonate, dit-butyl peroxide and dicumyl peroxide; and hydrogen peroxide-iron (II) salts, Examples thereof include peroxodisulfate-sodium hydrogen peroxide, 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 extracting a polymerization solution in an amount 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 may not affect the reaction, but may be a pressure that 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 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. Oxides, 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 generally, 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. In 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 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. Further, a dehydrating agent such as trimethyl orthoacetate and trimethyl ortho-formate can be added.
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 an unreacted monomer, an organic solvent, and a low molecular weight oligomer by distillation or the like. Can be isolated. Some of the volatile components such as unreacted monomers, organic 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 for the polymerization reaction.
Such a method of recycling the unreacted monomer and the organic solvent 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 amount of organic solvent in the reactor.

(1-3-3) Physical characteristics of the copolymer (a1) The weight average molecular weight (hereinafter, also referred to as “Mw”) of the copolymer (a1) is preferably 1,500 to 50,000, preferably 1,500 to. 40,000 is more preferable, still more preferably 2,000 to 30,000, even more preferably 2,500 to 25,000, and particularly preferably 3,000 to 15,000. When Mw is 50,000 or less, the obtained component (A1) 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 compatibility is good. Become. When the Mw is 1500 or more, the obtained cured product of the component (A1) has excellent weather resistance and tensile physical characteristics.
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 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. The Tg of the copolymer (a1) is more preferably 20 to 80 ° C, still more preferably 30 to 75 ° 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 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 a 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 reactivity 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 the initiator residue contained in the polymer is significantly affected by the influence of weather resistance.
Therefore, the copolymer (a1) used in the present invention is generally preferably one having 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. Further, in the present invention, when the 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 compound (a2)
The unsaturated compound is a compound having an unsaturated double bond and a group that reacts with the reactive group derived from the (meth) acrylate-based monomer (a1-2) constituting the copolymer (a1). The a2) is not particularly limited, but an unsaturated double bond-containing oligomer (a2-1) having a Tg of −30 to −90 ° C. is preferable.
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. Preferred, acryloyl groups are 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 (A1) 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 compound (a2). More specifically, it is obtained by chemically binding and adding an unsaturated compound (a2) to the copolymer (a1) having the above-mentioned reactive group via the above-mentioned reactive group.

When the copolymer (a1) is an epoxy polymer or a copolymer having a hydroxyl group as a reactive group, the unsaturated compound (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 compound (a2) having a carboxyl group include acrylic acid, acrylic acid dimer, γ-butyrolactone adduct of acrylic acid, and δ-valerolactone adduct of acrylic acid.
Other specific examples include unsaturated oligomers (a2-1) such as ε-caprolactone adducts 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 compound (a2) having an isocyanate group include unsaturated oligomers (a2-1) such as 2-((meth) acryloyloxy) ethyl isocyanate and 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-based catalyst such as dioctyltin, diisocyanates and diols are reacted in an organic solvent to obtain a urethane oligomer having isocyanate groups 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 compound (a2) includes a compound having a hydroxyl group as a functional group that reacts with the reactive group. Can be used.
Examples of the unsaturated compound (a2) having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, and 4-hydroxybutyl. Examples thereof include hydroxyalkyl acrylates such as acrylates.
Other specific examples include ε-caprolactone adducts of hydrochialkyl (meth) acrylates such as ε-caprolactone adducts of 2-hydroxyethyl (meth) acrylates, polypropylene glycol adducts of (meth) acrylic acid, and (meth). Unsaturated oligomers (a2-) such as polyethylene glycol adducts of acrylic acid, poly (3-hydroxybutyrate) adducts of 2-hydroxyethyl (meth) acrylate, and polytetramethylene glycol adducts of (meth) acrylic acid. 1) can be mentioned.
The ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate is commercially available, and is described by Pluxel FA2D [ε-caprolactone adduct of 2-hydroxyethyl acrylate, manufactured by Daicel Corporation, trade name, 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-). Examples thereof include ε-caprolactone adduct of hydroxyethyl methacrylate, molecular weight 473), FM5 (ε-caprolactone adduct of 2-hydroxyethyl methacrylate, molecular weight 701) and the like.
The polypropylene glycol adduct of acrylic acid is exemplified by a compound having Tg = −75 ° C., and the polyethylene glycol adduct of acrylic acid is exemplified by 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 adduct of polytetramethylene glycol of acrylic acid include a compound having Tg = −84 ° C.

As the unsaturated oligomer (a2-1), an unsaturated oligomer containing a ring-opened caprolactone structure (hereinafter, also referred to as “caprolactone-based unsaturated oligomer”) is preferable, and a caprolactone-based unsaturated oligomer having a Tg of −30 to −90 ° C. is preferable. Is more preferable. A composition containing the component (A1) 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 caprolactone-based unsaturated oligomer (a2-1) having a carboxyl group include the above-mentioned ε-caprolactone adduct of (meth) acrylic acid.
Examples of the caprolactone-based unsaturated oligomer (a2-1) having a hydroxyl group include the above-mentioned ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate and the ε-caprolactone adduct of hydrochialkyl (meth) acrylate. Can be mentioned.

(3) Method for Producing Component (A1) In the component (A1), the reactive group of the copolymer (a1) is reacted with the reactive group of the unsaturated compound (a2) and the reactive group. It is preferable to manufacture more. In addition, this reaction may be hereinafter referred to as a "denaturation reaction".
That is, as a reaction for adding an unsaturated compound (a2) to the copolymer (a1), an unsaturated compound (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 compound (a2) having a hydroxyl group with a copolymer (a1) having an isocyanate group or a carboxyl group as a reactive group.
Of these, a method of reacting a copolymer (a1) having an epoxy group as a reactive group with an unsaturated compound (a2) having a carboxyl group is preferable.

The reaction ratio between the copolymer (a1) and the unsaturated compound (a2) may be appropriately set according to the type of the component (A1) to be produced and the like.
The reactive group of the unsaturated compound (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 to 1.1 mol.

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

The reaction ratio between the copolymer (a1) having an epoxy group and the unsaturated compound (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 compound (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 weather 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 compound (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 an organic solvent.

Examples of the method for reacting the copolymer (a1) having a hydroxyl group with the unsaturated compound (a2) having a carboxyl group include a general dehydration esterification method. A mixture of a copolymer having a hydroxyl group (a1), an unsaturated compound having a carboxyl group (a2), a catalyst, and a solvent is heated at 100 to 120 ° C. to co-boiling and dehydrating the organic solvent and the water produced. There is a method of advancing the reaction by doing so.

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 the hydroxyl group to be reacted.

As the organic solvent, it is preferable to use an organic solvent which has low solubility in water produced by the dehydration esterification reaction and can proceed 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 methylethylketone and cyclohexanone. The ratio of the 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 compound (a2) having a hydroxyl group to a copolymer (a1) having an isocyanate group, a copolymer (a1) having an isocyanate group and an unsaturated compound having a hydroxyl group are used. After mixing with (a2), a method of adding a curing catalyst such as dibutyltin dilaurate and heating to 60 to 100 ° C., if necessary, can be mentioned.

As a method of reacting and adding an unsaturated compound (a2) having a hydroxyl group to a copolymer (a1) having a carboxyl group, an unsaturated compound (a2) having a hydroxyl group and the copolymer (a1) is used. After mixing, a catalyst such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, sulfonated polystyrene, Nafion-H is added, and in some cases, the mixture is heated to 80 to 120 ° C. in the presence of an organic solvent such as toluene to perform an esterification reaction. There is a method of distilling off the generated water while advancing the process.
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 characteristics of the component (A1) (acrylic equivalent and molecular weight)
The acrylic equivalent of the component (A1) is preferably 3000 g / eq or less. When the more preferable range of the acrylic equivalent of the component (A1) is described in order, it is 150 g / eq or more and 2500 g / eq or less, 300 g / eq or more and 2000 g / eq or less, 400 g / eq or more and 1400 g / eq or less, 700 g / eq. It is 1000 g / eq or less.
When the acrylic equivalent is 150 g / eq or more, the elongation rate and flexibility of the cured product can be ensured, and when it is 3000 g / eq or less, the strength and weather resistance of the cured product can be ensured. Moreover, the curing speed can be maintained well.

In the present invention, the 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, and the smaller the value. Indeed, the concentration of (meth) acryloyl groups is high.

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 (A1) is the number of moles of the (meth) acrylic loyl group of the unsaturated compound (a2) added to the copolymer (a1) in the above modification reaction. Exclude the (meth) acryloyl group derived from the unreacted unsaturated compound (a2) mixed after the modification reaction.

The molecular weight of the component (A1) is Mw, preferably 2,000 to 60,000, more preferably 2,000 to 50,000.
When Mw is 2,000 or more, the cured product has excellent weather resistance and tensile characteristics, and when it is 60,000 or less, the viscosity can be reduced even at a relatively high concentration, so that the coating property is excellent. Moreover, when mixed with other curable compounds, the compatibility becomes excellent. The more preferable ranges of the Mw of the component (A1) are described in order: 3,000 to 50,000, 3,000 to 40,000, 3,000 to 30,000, and 4,000. ~ 20,000.
The number average molecular weight of the component (A1) (hereinafter referred to as "Mn") is preferably 1,000 to 30,000.
When Mn is 1,000 or more, the cured product has excellent weather resistance and tensile characteristics, and when it is 30,000 or less, the viscosity can be reduced even at a relatively high concentration, so that the coating property is excellent. Moreover, when mixed with other curable compounds, the compatibility becomes excellent. The preferable range of the component (A1) from Mn is 1,500 to 15,000, 2,000 to 10,000, and 2,500 to 7,000.
The Mn in the present invention means a value obtained by converting the molecular weight measured by GPC into polystyrene.

1-2. (A2) component As the component (A) of the present invention, a component (A2) (that is, a compound having an ethylenically unsaturated group other than the component (A1)) may be used in addition to the component (A1). can.
As the composition of the present invention, when the 80 ° C. storage elastic modulus G'(measurement frequency 1 Hz) of the dry film before irradiation with the active energy ray shows 10 Pa or more only with the component (A2), the component (A2) is (A2). ) It may be only an ingredient.
In a preferred embodiment of the composition of the present invention, when the viscosity of the composition becomes high only with the component (A1), the purpose is to reduce the viscosity of the entire composition or to adjust other physical properties. Examples thereof include a composition in which the A1) component and the (A2) component are used in combination.

Specific examples of the component (A2) include (meth) acrylates other than the monomer (a1-1), the monomer (a1-2), the monomer (a1-1) and (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"). "Sensual (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) (Poly) alkylene glycol di (meth) acrylate such as di (meth) acrylate;
Di (meth) acrylates of aliphatic diols such as 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate;
Neopentyl glycol di (meth) acrylate hydroxypivalate;
Di (meth) acrylate with an alicyclic skeleton such as tricyclodecanedimethylol di (meth) acrylate;
A (meth) acrylate having an isocyanurate skeleton such as isocyanuric acid EO-modified diacrylate and ε-caprolactone-modified tris ((meth) achromiethyl) isocyanurate;
Glycerintri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, trimethylolpropane tri or tetra (meth) acrylate, diglycerin tri or tetra (meth) acrylate and Polypoly (meth) acrylates such as dipentaerythritol tri, tetra, penta or hexa (meth) acrylate; and tri (meth) acrylates of glycerin alkylene oxide adducts, tri or tetra (meth) of pentaerythritol alkylene oxide adducts. Tri or tetra (meth) acrylate of acrylate, trimethylolpropane propanealkylene oxide adduct, tri or tetra (meth) acrylate of diglycerin alkylene oxide adduct, tri, tetra, penta or hexa (meth) of dipentaerythritol alkylene oxide adduct. ) Poly (meth) acrylate of a polyol alkylene oxide adduct such as acrylate can be mentioned.
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 isocyanurate skeleton are preferable among these compounds.

As the component (A2), only one kind of the above-mentioned compound may be used, or two or more kinds thereof may be used in combination.

The blending ratio of the component (A2) 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 is 0 in the total 100% by weight of the component (A2). It is preferably from 70% by weight, more preferably 1 to 60% by weight, still more preferably 1 to 45% by weight.

2. 2. Active energy ray-curable composition The active energy ray-curable composition of the present invention contains at least the component (A), and the 80 ° C. storage elastic modulus G'(measurement frequency 1 Hz) of the dry film before irradiation with the active energy ray is 10 Pa. The above is shown.
In the present invention, the dry film is a film before irradiation with active energy rays, and when the composition does not contain the (B) solvent (hereinafter referred to as "(B) component"), it is obtained by coating on a base material. When the composition contains the component (B), it means a film obtained by coating the substrate and then heating and drying.
The composition satisfying the storage elastic modulus G'can be obtained by appropriately designing the above-mentioned components constituting the component (A) and various physical properties of the component, and / or other components such as the component (B) (A). ) Can be manufactured by mixing appropriately with the ingredients.
As the component (A), either a solid at room temperature or a solvent-free liquid at room temperature can be used, but a solid at room temperature is preferable. The component (A), which is solid at room temperature, can be appropriately mixed with the component (B) and used. Further, even when other components are contained, it is preferable that the dry film becomes a solid.
The component (A) can be used even if it is a mixture of a solid at room temperature and a solvent-free liquid at room temperature, as long as the composition as a whole satisfies the storage elastic modulus G'. Further, even if the component (A) is a solvent-free liquid at room temperature, it can be used as long as the composition as a whole satisfies the storage elastic modulus G'by mixing with other components.

In the present invention, the storage elastic modulus G'means a value obtained by measuring the temperature dispersion of dynamic viscoelasticity in the shear mode according to JIS K7244-6 (sample thickness 0.3 mm, strain 1). 0.0%, measurement frequency 1 Hz, heating rate 2 ° C / min).
The storage elastic modulus G'needs to be 10 Pa or more, preferably 30 Pa or more, and more preferably 100 Pa or more. When the storage elastic modulus G'is 10 Pa or more, dripping is suppressed, and when it is 30 Pa or more, dripping is less likely to occur even when the film thickness is thick, which is preferable. The preferable upper limit of the storage elastic modulus G'is 10,000 Pa. When it is within this upper limit, the leveling property of the coating film is excellent and a smooth coating film can be obtained.

The viscosity of the composition before forming the dry film may be appropriately set according to the intended use and purpose. The preferred viscosity is 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 ratio of the solid component at room temperature to the total amount of the composition is preferably 30% by weight or more, more preferably 50% by weight or more.

The composition of the present invention not only suppresses dripping, but also has the effect that the cured product has excellent tensile physical properties such as tensile strength and elongation, and weather resistance.
In terms of tensile characteristics, the breaking strength is preferably 20 MPa or more, more preferably 30 MPa or more.
Next, the elongation rate is preferably 2% or more, more preferably 5% or more.
As the tensile strength, 60 MPa or more is preferable, 150 MPa or more is more preferable, and 200 MPa or more is even more preferable. Since the breaking strength and the elongation rate are generally in a trade-off relationship, the higher the tensile strength (breaking strength × elongation rate / 2), the better the tensile characteristics.

The composition of the present invention requires the component (A), but as described above, the component (B) and various other components can be blended as needed.
Examples of the component other than the component (B) that can be blended include a photoradical polymerization initiator (hereinafter, also referred to as “component (C)”).
Hereinafter, the components (B) and (C) and other components will be described.

2-1. (B) Component The composition of the present invention can contain a solvent which is the component (B) for the purpose of improving the coatability on the substrate.
Examples of the component (B) include an organic solvent and water, and an organic solvent is preferable.
Hereinafter, the organic solvent and water will be described.

(1) Organic solvent Even if the organic solvent is the same compound, it is referred to as "organic solvent" when it is used in a reaction system, and it is referred to as "organic solvent" when it is used in a composition such as a paint. These are collectively referred to as "organic solvent" in the present invention.

Specific examples of the organic solvent 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-isopropoxyethanol, 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;
Ethereal 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, Methyl Pentyl Ketone, Di-n-propyl Ketone, Diisobutyl Ketone, Holon, Isophoron, 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 organic solvent, one or more of the above-mentioned compounds can be used.
The organic solvent 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 organic solvent may be appropriately set in consideration of the viscosity of the composition, the purpose of use, etc., but is preferably 70% by weight or less in the total 100% by weight of the components (A) and (B). 60% by weight or less is more preferable, 50% by weight or less is even more preferable, 40% by weight or less is even more preferable, and 15 to 40% by weight is particularly preferable.

(2) Water The composition of the present invention can contain water as the component (B).
When water is contained as the component (B), a composition in which the component (A) is dispersed in water is preferable.
The method (A) for dispersing the components in water (hereinafter, also referred to as “water-based”) may be carried out according to a conventional method.

In the production of the component (A1), when the reaction of the copolymer (a1) and the unsaturated compound (a2) is carried out in an organic solvent, the method is then made aqueous to form an aqueous dispersion of the component (A1). And so on.
As a more specific method for making water-based, water and a surfactant (dispersant) are added to the organic solvent solution of the component (A1) obtained in the above reaction, and the mixture is stirred and mixed to form the component (A1). Examples thereof include a method of dispersing the organic solvent in water and removing the organic solvent by heating under reduced pressure.

As another method of making water-based, it can also be carried out by adding water and a surfactant to the previously isolated component (A1) and stirring the mixture.
When the component (A1) is a mixed solution containing an organic solvent, it is common to distill off the organic solvent by heating under reduced pressure or distillation as described above.

Further, when the component (A1) (or its organic solvent mixture) is insoluble in water, the component (A1) precipitates even if water and a surfactant are added, and the uniformity of the system cannot be maintained. , A homogeneous dispersion may not be obtained.
In such a case, before or at the same time as adding water and a surfactant, a water-soluble organic solvent may be added to form an aqueous dispersion, and then the water-soluble organic solvent may be distilled off by distillation.

As the surfactant, various emulsifiers such as anionic emulsifier, nonionic emulsifier, cationic emulsifier, and amphoteric ionic emulsifier can be used, and among these, nonionic surfactant is particularly preferable.
The ratio of the surfactant added is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, as the pure content of the surfactant with respect to 100 parts by weight of the total amount of the component (A). , More preferably 2 to 7 parts by weight.

Examples of the water-soluble organic solvent include alkyl alcohols having 1 to 4 carbon atoms, ketones or keto alcohols, polyalkylene glycols, alkylene glycols having 2 to 6 carbon atoms in an alkylene group, lower alkyl ethers, and pyrrolidone. And 1,3-dimethyl-2-imidazolidinone and the like.

2-2. (C) component When the composition of the present invention uses ultraviolet rays and visible light as active energy rays, the composition of the (C) component (photopolymerization initiator) may be contained.
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 components (C) include benzyldimethylketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-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-morpholinopropane-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, 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 ethanone 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-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -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, etc. Dimers; as well as acridin 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 mixing ratio of the component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the component (A).
By setting the blending ratio of the component (C) to 0.01 parts 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 10 parts by weight or less. By doing so, it is possible to make the cured product excellent in weather resistance and transparency.

2-3. 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 other components, a polymerization inhibitor and / and an antioxidant, and a 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 / 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, and various phenolic antioxidants, but sulfur-based secondary antioxidants and phosphorus-based secondary agents. It may be an antioxidant or the like.

The total amount of these polymerization inhibitors and / and antioxidants is preferably 0.001 to 3 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total amount of the component (A). 0.5 parts by weight.

<Light resistance improver>
The active energy ray-curable composition of the present invention may contain a light resistance improving agent such as an ultraviolet absorber or 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'-diformylhexamethylenediamine 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) sebacate; N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformylhexamethylenediamine, bis (1,2, 2,6,6-Pentamethyl-4-piperidinyl) Hinderdamine-based photostabilizers such as high molecular weight hinderedamine compounds such as sebacate can be mentioned.

The blending amount of the light resistance improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight, based on 100 parts by weight of the total amount of the component (A).

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 substrate, 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. There is a method of irradiating and curing.
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 that, a method of further irradiating with active energy rays to cure the solvent can be mentioned.

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.
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).
Specific examples of the plastic include polyolefins such as polyethylene and polypropylene, ABS resin, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalates (hereinafter referred to as "PET resin"), polycarbonates and polys. Examples thereof include cyclic polyolefin resins using cyclic olefins such as allylate, polyether sulfone, 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 depending on the intended purpose, and is conventionally known as a bar coat, an applicator, a doctor blade, a knife coater, a comma coater, a reverse roll coater, a die coater, a lip coater, a gravure coater and a micro. A method of coating with a gravure coater or the like can be mentioned.

When the composition of the present invention contains an organic solvent, it is preferable that the composition is coated on a substrate and then heated and dried to evaporate the organic solvent.
The drying temperature is not particularly limited as long as the applied base material is at a temperature or lower that does not cause problems such as deformation. The preferred heating temperature is 40 to 100 ° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 20 minutes.

The film thickness of the composition cured film with respect to the substrate may be appropriately set according to the 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 manufactured 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 in that 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 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, substrate, purpose, and the like to be used.
Taking the case of using a high-pressure mercury lamp as an example of the case of using ultraviolet rays, the irradiation energy in the UV-A region is preferably 100 to 8,000 mJ / cm ² , and more preferably 200 to 3,000 mJ / cm ² .
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 coat agents for various base materials, 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 polarizing element protective film and an antireflection film, and a resin molded product used for home appliances and automobile interior / exterior parts.
Further, as another use of the coating agent, it can be used as an inorganic base material such as concrete or a coating agent for wood, and can be used for coating outer walls and constituent materials in civil engineering and construction applications.
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 for a lithium ion battery, and 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, and viscosity in the 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 Mn (number average molecular weight) in terms of polystyrene were obtained under the following conditions.
○ 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.

<Acrylic equivalent>
The acrylic equivalent (g / eq) was defined as the value obtained by dividing the weight (g) of the raw material excluding the organic solvent component by the number of moles of the compound having the reactive group used and the (meth) acryloyl group.

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 188 ° C. Then, 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 20 parts of glycidyl methacrylate (hereinafter referred to as "GMA"). , 12 parts of methyl ethyl ketone (hereinafter referred to as "MEK"), 3 parts of trimethyl orthoacetate (manufactured by Nippo Chemical Co., Ltd., trade name "MOA", hereinafter referred to as "MOA") as a solvent, and dit-hexyl as a polymerization initiator. A monomer mixture consisting of one part of peroxide (manufactured by Nichiyu, trade name "Perhexyl D", hereinafter referred to as "DTHP") is supplied from the raw material tank at a constant supply rate (48 g / min, residence time: 12 minutes). Continuous supply 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 Mw and Tg of the copolymer a1-1 in terms of polystyrene.

Next, the copolymer a1-1 (100 parts), the dibutyl hydroxytoluene (hereinafter referred to as “BHT”) (0.11 part) as the polymerization inhibitor, and acrylic acid (hereinafter “AA”” as the unsaturated compound (a2). (11.2 parts, equivalent to 1.05 equivalent acid value of the epoxy group of the copolymer a1-1) and butyl acetate (47.9 parts) as an organic solvent are put into a 1 L flask and 5% oxygen. The liquid temperature was raised to 95 ° C. while bubbling the nitrogen mixed gas to dissolve the copolymer a1-1.
After uniformly dissolving, triphenylphosphine (hereinafter referred to as "TPP") (0.56 parts) was added as a reaction catalyst, and the mixture was stirred for 12 hours while maintaining the internal temperature of 95 ° C. Further, TPP (0.56 part) was added and reacted for 12 hours. Then, the acid value was measured, and it was confirmed that the acid value was 3.6 mgKOH / g, and the reaction was terminated.
As a result, a butyl acetate solution containing the polymer A-1, which is an AA adduct of the copolymer a1-1, was obtained.

Table 2 shows the solid content, acid value, polystyrene-equivalent Mn, Mw, and acrylic equivalent (g / eq) of the polymer A-1 solution.

(2) Production Examples 2 to 9, Comparative Production Example 1
The (meth) acrylate polymers A-2 to 9 and A'-1 having an acryloyl group in the side chain were obtained by the same operation as in Production Example 1 except that the conditions shown in Table 1 were changed.
The M5300 in Table 1 is as defined later.

(3) Production example 10
A (meth) acrylic polymer having an isocyanate group (hereinafter referred to as “copolymer a1-8”) was obtained by the same operation as in Production Example 1 except that the conditions shown in Table 1 were changed.
The MOI in Table 1 is as defined later.
Then, the copolymer a1-8 (100 parts), dibutyl hydroxytoluene (0.12 parts) as a polymerization inhibitor, 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (24.7 parts, polymer a1- (Equivalent to 1.0 equivalent hydroxyl value of the isocyanate group of 8), dibutyltin dilaurate (0.03 part) and butyl acetate (64.3 part) as a catalyst are put into a 1 L flask, and 5% oxygen-nitrogen mixed gas is bubbled. The liquid temperature was raised to 80 ° C. to dissolve the copolymer a1-8.
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, a butyl acetate solution containing the polymer A-10, which is a HEA adduct (acrylate-modified product) of the copolymer a1-8, was obtained.

(4) Production Example 11
Polymer A-11, which is an FA-2D adduct (acrylate-modified product) of the copolymer a1-8, was obtained by the same operation as in Production Example 10 except that the conditions shown in Table 1 were changed.
The FA-2D in Table 1 is as defined later.

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-MOI: 2-Isocyanate Ethyl Methacrylate [Karenzu MOI (trade name), manufactured by Showa Denko KK]
-MEK: Methyl ethyl ketone-MOA: trimethyl orthoacetate [MOA (trade name), manufactured by Nippoh Chemicals]
-DTHP: Di-t-hexyl peroxide [Perhexyl D (trade name), manufactured by NOF Corporation]

The abbreviations in Table 2 mean the following. In the following, some of the ones already defined above are also described in duplicate.
-AA: Acrylic acid-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]
-HEA: 2-hydroxyethyl acrylate-FA-2D: ε-caprolactone adduct of 2-hydroxyethyl acrylate [Plaxel 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-BHT: dibutylhydroxytoluene

2. 2. Examples 1 to 14, Comparative Examples 1 to 2 (ultraviolet curable composition)
The raw materials shown in Table 3 were used, and the mixture was stirred and mixed according to the amount ratio shown in Table 3 to prepare an ultraviolet curable composition, which was evaluated according to the following. The results are shown in Table 3.

(1) Measurement of storage elastic modulus G'before irradiation For the composition containing the organic solvent, polyester film [manufactured by Mitsubishi Chemical Corporation, trade name: MRV-75. Film thickness 75 μm. Hereinafter referred to as MRV-75], tapes were applied to both ends, coated with a bar coater # 0 to a thickness of 80 to 120 μm, and then dried at 90 ° C. for 10 minutes in a ventilation dryer.
By stacking 3 to 4 of these samples and further pressure-bonding them with MRV-75 film from both sides at 90 ° C., a sample having a thickness of about 300 μm was obtained.
The composition containing no organic solvent was used as it was for the measurement.
* Although 20 parts of butyl acetate are shown in Comparative Examples 1 and 2 in Table 3, the measurement of storage elastic modulus and the evaluation of dripping are performed without adding butyl acetate, and other evaluations are performed. Was carried out by adding butyl acetate as shown in Table 3.

(Measurement condition)
Equipment: Rheometer MCR-301 (manufactured by Anton Pearl)
Measurement frequency: 1Hz
Measurement temperature: -30 to 100 ° C
Temperature rise rate: 2 ° C./min Measurement was performed under the above conditions, and the storage elastic modulus G'at 80 ° C. was determined.

(2) Evaluation of unirradiated material (before curing)>
(2-1) Evaluation of dripping Using bar coater # 30 (less than 30 parts of organic solvent) or # 40 (more than 30 parts of organic solvent) on the chromate-treated aluminum plate, the film thickness after drying becomes about 30 μm. So, the liquid was applied. After standing for 5 minutes, the coated plate was dried at 80 ° C. for 10 minutes in a ventilation dryer with the coated plate vertical. After that, the presence or absence of dripping was visually confirmed.

(2-2) Evaluation of tack and pencil hardness Using bar coater # 30 (less than 30 parts of organic solvent) or # 40 (more than 30 parts of organic solvent) on a chromate-treated aluminum plate, the film thickness after drying is about 30 μm. The liquid was applied so as to become. After standing for 5 minutes, the coated plate was dried at 90 ° C. for 10 minutes in a ventilation dryer with the coated plate horizontal. Then, the presence or absence of tack was evaluated by finger touch according to the following criteria.
・ Evaluation criteria 〇: No tack △: Tacked but not attached to fingers ×: Adhering to fingers The surface of the coating film is scratched with a pencil with a load of 750 g, and the hardness of the hardest pencil that does not scratch is penciled. It was set to hardness.

(3) Evaluation of physical properties of cured product (UV curing system)
(3-1) Evaluation of pencil hardness (UV curing system)
The composition was applied to the chromate-treated aluminum plate using bar coater # 30 (less than 30 parts of organic solvent) or # 40 (more than 30 parts of organic solvent) so that the film thickness after drying was 30 to 40 μm. Then, it was dried at 90 ° C. for 10 minutes in a ventilation dryer.
Next, using a high-pressure mercury lamp manufactured by Igraphics 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 surface of the coating film was scratched with a pencil under a load of 750 g, and the hardness of the hardest pencil without scratches was defined as the pencil hardness.

(3-2) Evaluation of tensile properties Prepare Lumirer T-60 (trade name, PET film manufactured by Toray Industries, Inc., film thickness; 100 μm) as a base film, attach tapes to both ends thereof, and apply the base film. The ultraviolet curable composition obtained in the above Examples and Comparative Examples was applied to the surface of the above-mentioned Example and Comparative Example so that the film thickness after drying was 60 to 80 μm using a bar coater # 0. 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 Igraphics 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. In addition, the tensile product was calculated by the following formula.
Tension product = breaking strength x elongation rate / 2

(3-3) Evaluation of weather resistance Zeono ZF14-100 (trade name, cycloolefin polymer manufactured by Nippon Zeon Co., Ltd., film thickness; 100 μm) was prepared as a base film, and tapes were attached to both ends of the base film. Using bar coater # 0, the ultraviolet curable composition obtained in the above Examples and Comparative Examples was applied to the surface of the film 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 Igraphics 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 performed. The conditions were irradiation 63 ° C., 70% RH, illuminance 80 mW / cm ² , and the test was carried out for 300 hours with a shower for 2 minutes once every 2 hours.
It was evaluated by the color difference and haze before and after the test.

<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 3.5 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 accelerated weathering test)

<Measurement of haze>
Measurement was performed using NDH2000 (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd., and the difference in haze (Δ haze) before and after the accelerated weather resistance test was evaluated. The Δ haze is preferably 2.0 or less.

The abbreviations in Table 3 mean the following.
-M1200: Polyester urethane acrylate (Mw = 4,500) [Aronix M-1200 (trade name), manufactured by Toagosei Co., Ltd.]
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]
Omnirad 184: 1-Hydroxycyclohexyl-phenylketone [Omnirad 184 (trade name), IGM RESINS B. V. Made by the company]

From the results in Table 3, the following can be seen.
<Evaluation of dry film (uncured product)>
In the compositions of Comparative Examples 1 and 2, the 80 ° C. storage elastic modulus G'of the dry film was less than 1 Pa, and dripping occurred. On the other hand, in the compositions of Examples 1 to 14, the 80 ° C. storage elastic modulus G'of the dry film showed a value of 10 Pa or more, and no dripping occurred. Further, Examples 1 to 14 were excellent in terms of tack and pencil hardness of the dry film, and even if an unirradiated portion and a low-irradiated portion were generated, the result did not cause a big problem.
Further, as in Examples 4, 6 and 7, a composition containing a solid (A1) component at room temperature and a liquid (A2) component (M-1200, M-5300) at room temperature as the component (A). In comparison, as in Examples 3 and 5, the composition containing only the component (A1) (polymer A-3, polymer A-4) which is solid at room temperature as the component (A) is more tacky and The pencil hardness was excellent.

<Evaluation of cured product>
Composition using a copolymer (A-1, A-3) to which a low molecular weight compound such as acrylic acid is added as an unsaturated compound (a2) as a component (A1) as in Examples 1, 3 and 4. As in Examples 2, 5 and 6, a copolymer having an unsaturated double bond-containing oligomer (a2-1) having a Tg of −30 to −90 ° C. such as M5300 added as a component (A1) is added to the compound. The composition using the union (A-2, A-4) was superior in terms of tensile properties (particularly elongation).
Regarding the molecular weight of the component (A1), from the comparison between Examples 8, 5, 9 and 10, the tensile physical characteristic is the optimum point in Example 5, while the weather resistance tends to be better when the molecular weight is higher. It turns out that it is in.
Regarding the acrylic equivalent of the component (A1), from the comparison between Examples 11, 5 and 12, the tensile strength is higher as the acrylic equivalent is lower, the breaking strength is higher, and the elongation rate is higher as the acrylic equivalent is higher. It can be seen that the lower the acrylic equivalent, the better the weather resistance.

3. 3. Examples 15 to 28, Comparative Examples 3 to 4 (electron beam curable composition)
The raw materials shown in Table 4 were used, and the mixture was stirred and mixed according to the amount ratio shown in Table 4 to prepare an electron beam curable composition.
Tapes are attached to both ends on a smooth glass plate, and the electron beam curable composition obtained in the above Examples and Comparative Examples is dried using a bar coater # 0 so that the film thickness becomes 60 to 80 μm. The film was applied and dried in a ventilation dryer at 90 ° C. for 10 minutes to obtain a coating film having a dry coating film of the composition.
Next, the coated film is irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV, a dose of 150 kGy (adjusted by the beam current and the transport speed), and an oxygen concentration of 300 ppm or less by an electron beam irradiation device manufactured by NHV Corporation. This was done to obtain a cured product.
The cured product was peeled off from the glass plate, and the pencil hardness, tensile characteristics and weather resistance of the cured product were evaluated in the same manner as in Examples 1 to 14. The results are shown in Table 4. The abbreviations in Table 4 are the same as those in Table 3.
The electron beam curable composition also showed the same tendency as the ultraviolet curable composition, but it can be seen that the electron beam curable composition tends to be better in terms of weather resistance.

The active energy ray-curable composition of the present invention can be applied to a vertical surface or a complex shape to obtain a cured product having a desired shape that is well cured. It can be used in fields where a cured product having weather resistance is required, and is particularly preferably used in the field of coating agents.

Claims (9)

(A) A composition containing a compound having an ethylenically unsaturated group (hereinafter referred to as "component (A)"), which has a storage elastic modulus of 80 ° C. G'(measurement frequency: 1 Hz) of a dry film before irradiation with active energy rays. ) Is 10 Pa or more, an active energy ray-curable composition. The active energy ray curing according to claim 1, wherein the component (A) contains a (meth) acrylate-based polymer having an ethylenically unsaturated group in the side chain (A1) (hereinafter referred to as "component (A1)"). Sex composition. The component (A1) is selected from the group consisting of a structural unit derived from a (meth) acrylate-based monomer (a1-1) having no reactive group, and an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate group. The reaction with a copolymer (a1) containing a structural unit derived from a (meth) acrylate-based monomer (a1-2) having a reactive group (hereinafter referred to as “copolymer (a1)”). The active energy ray according to claim 1 or 2, which comprises a reactant of a compound (a2) having a group that reacts with a sex group and an ethylenically unsaturated group (hereinafter referred to as "unsaturated compound (a2)"). Curable composition. The active energy ray-curable composition according to claim 3, wherein the unsaturated compound (a2) is an unsaturated double bond-containing oligomer (a2-1) having a glass transition temperature (Tg) of −30 to −90 ° C. thing. The active energy ray-curable composition according to any one of claims 1 to 4, further comprising (B) a solvent. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the component (A) contains the following component (A2).
Component (A2): A compound having an ethylenically unsaturated group other than the component (A1). The active energy ray-curable composition according to any one of claims 1 to 6, wherein the active energy ray is an electron beam. The active energy ray-curable composition according to any one of claims 1 to 7, further comprising (C) a photopolymerization initiator. An active energy ray-curable composition for a coating agent containing the composition according to any one of claims 1 to 8.