Curable composition, active energy ray curable composition, and active energy ray curable coating agent composition

Abstract

[Problem] To provide a curable composition containing a polyfunctional urethane (meth)acrylate adduct that has a low viscosity, exhibits an excellent balance of surface hardness, scratch resistance, and flexibility as a cured film thereof, and also has exceptional curling properties, preferably to provide an active-energy-ray-curable composition, especially a composition that can be suitably used as a coating. [Solution] A curable composition containing component (A). Component (A): a reaction product of an organic polyisocyanate and a mixture (a1) of at least one compound selected from the group consisting of glycerin (meth)acrylates and diglycerin (meth)acrylates, the mixture having a hydroxyl value of 20-300 mg KOH / g.

Description

Technical Field

[0001] The present invention relates to a curable composition containing a urethane (meth) acrylate [hereinafter referred to as "polyfunctional urethane (meth) acrylate adduct"], which is a urethanization reaction product of a compound having one or more hydroxyl groups and two or more (meth) acryloyl groups and an organic polyisocyanate, and preferably relates to an active energy ray curable composition. The composition of the present invention can be used for various applications. In particular, it has a lower viscosity and faster curing properties than conventional polyfunctional urethane (meth) acrylate adducts. When used as a raw material for a hard coat agent, a composition with a good balance between the elastic modulus and flexibility of the resulting cured film can be obtained. Therefore, it can be preferably used as a coating agent composition and belongs to these technical fields. In this specification, an acryloyl group and / or a methacryloyl group are referred to as a (meth) acryloyl group, an acrylate and / or a methacrylate are referred to as a (meth) acrylate, and acrylic acid and / or methacrylic acid are referred to as a (meth) acrylic acid.

Background Art

[0002] The polyfunctional urethane (meth) acrylate adduct is a compound obtained by reacting a polyfunctional (meth) acrylate having one or more hydroxyl groups and two or more (meth) acryloyl groups with an organic polyisocyanate having two or more isocyanate groups. Since it is excellent in curability, tensile strength, elongation rate, and toughness of the cured film, it is used in various curable compositions such as coating agents, inks, adhesives, bonding agents, and sealants, particularly active energy ray curable compositions.

[0003] As an application where the above polyfunctional urethane (meth) acrylate adduct is widely used, a hard coat agent for plastics can be mentioned. Plastic substrates are lightweight and have excellent impact resistance and moldability, but they have the disadvantage of being easily scratched and having low hardness, which significantly impairs their appearance if used as is. For this reason, it is necessary to coat the surface of the plastic substrate with a paint composition, a so-called hard coat treatment, to impart scratch resistance and improve surface hardness. Conventionally, polyfunctional urethane (meth)acrylate adducts having 10 or more (meth)acryloyl groups in one molecule have been used as raw materials for hard coating agents.

[0004] Patent Document 1 discloses an active energy ray curable composition containing a reaction product of dipentaerythritol pentaacrylate and aliphatic divalent isocyanate, i.e., a polyfunctional urethane (meth)acrylate adduct having 10 (meth)acryloyl groups in one molecule. However, while the patented composition exhibited excellent cured film hardness, scratch resistance, and substrate adhesion, the hard-coated film substrate was prone to cracking and peeling when bent, indicating insufficient flexibility. On the other hand, attempting to improve flexibility resulted in insufficient cured film hardness and scratch resistance, making it difficult to achieve both properties simultaneously. Furthermore, the hard-coated film tended to curl, impairing its appearance quality. Furthermore, the polyfunctional urethane (meth)acrylate adduct material of the patent in question has high viscosity, and when used as a solvent-free composition without diluting solvents, it becomes extremely viscous, resulting in poor coating properties.

[0005] Patent Document 2 discloses an active energy ray curable composition containing a reaction product of dipentaerythritol pentaacrylate and a trivalent isocyanate having an isocyanurate skeleton, i.e., a polyfunctional urethane (meth)acrylate adduct having 15 (meth)acryloyl groups in one molecule. However, although the composition of the patent in question is excellent in terms of cured film hardness, scratch resistance, and resilience, the hard-coated film substrate is prone to cracking and peeling when bent, resulting in insufficient flexibility. Furthermore, similar to Patent Document 1, attempting to improve flexibility results in insufficient cured film hardness and scratch resistance, making it difficult to achieve both of these properties simultaneously. Also, similar to Patent Document 1, the hard-coated film is prone to curling, which impairs its appearance quality. In addition, the polyfunctional urethane (meth)acrylate adduct body of the patent in question also has the problem of high viscosity.

[0006] Thus, conventional polyfunctional urethane (meth)acrylate adducts used as raw materials for hard coating agents had the problem that increasing the number of (meth)acryloyl groups in the molecule improved the hardness of the cured film but worsened its flexibility. In addition, the high viscosity of polyfunctional urethane (meth)acrylate adducts also resulted in poor coating properties. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2011-12099 [Patent Document 2] International Publication No. 2012 / 86551 Brochure [Overview of the project] [Problems that the invention aims to solve]

[0008] The inventors of the present invention have diligently conducted research to find a curable composition containing a polyfunctional urethane (meth)acrylate adduct body that has low viscosity, whose cured film has a good balance of surface hardness, scratch resistance and flexibility, and also has excellent curlability, preferably an active energy ray curable composition, and in particular a composition that can be suitably used as a coating agent. [Means for solving the problem]

[0009] To solve the aforementioned problems, the present inventors have found that an active energy ray curable composition containing a polyfunctional urethane (meth)acrylate adduct obtained by the urethane reaction of a specific glycerin (meth)acrylate and / or diglycerin (meth)acrylate with an organic polyisocyanate is low viscosity, and the cured film exhibits excellent physical properties in terms of hardness, scratch resistance, flexibility, and curlability, thus completing the present invention. The present invention will be described in detail below. [Effects of the Invention]

[0010] According to the composition of the present invention, the viscosity is low, and the cured film can simultaneously satisfy a balance between surface hardness, scratch resistance, and flexibility, and also exhibits excellent curlability. Therefore, the compositions of the present invention can be preferably used as coating agents, and more preferably as hard coating agents. [Modes for carrying out the invention]

[0011] The present invention relates to the following curable composition.

[0012] [1] A curable composition containing the following component (A). (A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, having a hydroxyl value of 20 to 300 mg KOH / g (a1), and a reaction product of an organic polyisocyanate.

[0013] [2] The curable composition according to [1], wherein the organic polyisocyanate is an aliphatic polyisocyanate or an alicyclic polyisocyanate.

[0014] [3] The curable composition according to [1] or [2], wherein the mixture (a1) is a (meth)acrylate mixture obtained by subjecting glycerin or diglycerin and a compound having one (meth)acryloyl group [hereinafter referred to as "monofunctional (meth)acrylate"] to a transesterification reaction in the presence of the following catalysts X and Y, and the mixture has a hydroxyl value of 20 to 300 mgKOH / g. Catalyst X: at least one compound selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and a phosphine or a salt or complex thereof. Catalyst Y: a zinc-containing compound.

[0015] [4] The curable composition according to [3], wherein the monofunctional (meth)acrylate is an alkoxyalkyl (meth)acrylate.

[0016] [5] The curable composition according to [3] or [4], wherein the catalyst X is at least one compound selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof.

[0017] [6] The curable composition according to any one of [3] to [5], wherein the catalyst Y is a zinc organic acid or / and a zinc diketone enolate.

[0018] [7] The curable composition according to any one of [1] to [6], wherein the weight average molecular weight of the component (A) is 500 to 10,000.

[0019] [8] The curable composition according to any one of [1] to [7], further comprising the following component (B). Component (B): a compound having an ethylenically unsaturated group other than the component (A).

[0020] [9] An active energy ray curable composition containing the composition according to any one of [1] to [8].

[0021]

[10] The active energy ray curable composition according to [9] further comprising a photopolymerization initiator in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the total amount of component (A), or per 100 parts by weight of the total amount of component (A) and component (B).

[0022] An active energy ray curable coating agent composition comprising the composition described in

[11] , [9], or

[10] .

[0023] The following describes (A) component, curable composition, method of use, and applications.

[0024] 1. (A) Component Component (A) of the present invention is a reaction product of a mixture (a1) [hereinafter referred to as "mixture (a1)"], which is a mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, and which has a hydroxyl value of 20 to 300 mgKOH / g, and an organic polyisocyanate [hereinafter referred to as "compound (a2)"]. The following describes the methods for producing the mixture (a1), compound (a2), and component (A).

[0025] 1-1.Mixture (a1) The mixture (a1) is a mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, and has a hydroxyl value of 20 to 300 mg KOH / g.

[0026] If the mixture (a1) is a mixture of glycerin (meth)acrylates, a mixture mainly composed of glycerin diacrylate is preferred because it exhibits excellent reactivity with compound (a2). In the case of a mixture of diglycerin (meth)acrylates, a mixture mainly composed of diglycerin triacrylate is preferred because it exhibits excellent reactivity with compound (a2).

[0027] Mixture (a1) can be obtained by a transesterification reaction between glycerin and / or diglycerin (hereinafter collectively referred to as "(poly)glycerin") and a monofunctional (meth)acrylate [a compound having one (meth)acryloyl group]. Alternatively, mixture (a1) can also be obtained by a dehydration esterification reaction between (poly)glycerin and (meth)acrylic acid. When glycerin is used as a raw material, mixture (a1) is a mixture of glycerin mono(meth)acrylate, di(meth)acrylate, and tri(meth)acrylate. When diglycerin is used as a raw material, mixture (a1) is a mixture of diglycerin mono(meth)acrylate, as well as diglycerin di(meth)acrylate, tri(meth)acrylate, and tetra(meth)acrylate. The mixture (a1) is a mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, and has a hydroxyl value of 20 to 300 mg KOH / g. The hydroxyl value of mixture (a1) is preferably 30 to 290 mg KOH / g, and more preferably 40 to 280 mg KOH / g. If the hydroxyl value of mixture (a1) is less than 20 mgKOH / g, the hardness of the cured film of the resulting composition containing component (A) will decrease. Conversely, if the hydroxyl value exceeds 300 mgKOH / g, the resulting component (A) will have high viscosity. In this invention, the hydroxyl value refers to the value measured in accordance with the method specified in JIS K0070-1992.

[0028] Furthermore, as a mixture of glycerin (meth)acrylate, a mixture containing glycerin di(meth)acrylate (hereinafter also referred to as "GLY-DA") is more preferable. GLY-DA is a compound represented by the following formula (1) or formula (2).

[0029] [ka]

[0030] [In the above formula (1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a methyl group.

[0031] [ka]

[0032] [In the above equation (2), R 3 and R 4 Each of these independently represents either a hydrogen atom or a methyl group.

[0033] GLY-DA is obtained as a mixture of the compound represented by formula (1) and the compound represented by formula (2) during manufacturing unless specially purified. Therefore, these can be used as is, and there are no restrictions on the mixing ratio of the compound represented by formula (1) and the compound represented by formula (2); they can be used in any ratio without any problems.

[0034] The purity of GLY-DA contained in mixture (a1) is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more, when determined using the following formula (3). By making the purity of GLY-DA 30% or more, component (A), which is a reaction product with compound (a2), can be made to have excellent surface hardness and flexural coefficient.

[0035] GLY-DA purity (%) = [(D×2) / (M+D / 2+T / 3)]×100 ...Equation (3) In formula (3), D, M, and T refer to the following values ​​obtained by analyzing the mixture (a1) using a high-performance liquid chromatograph (hereinafter also referred to as "HPLC") equipped with an ultraviolet (UV) detector. • D: Peak area of ​​GLY-DA at 210 nm • M: Peak area of ​​glycerin mono(meth)acrylate at 210 nm • T: Peak area of ​​glycerin tri(meth)acrylate at 210 nm The peak area measured by HPLC refers to the value measured under the following conditions. • Detector: UV detector, detection wavelength 210nm • Column type: A column packed with silica gel modified with an alkyl group having 18 carbon atoms. Specifically, the ACQUITY UPLC BEH C18 column manufactured by Waters Co., Ltd. (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm) Column temperature: 40°C • Eluent composition: Mixture of 0.03 wt% trifluoroacetic acid aqueous solution and methanol. • Eluent flow rate: 0.3 mL / min

[0036] As the mixture (a1), those obtained by various manufacturing methods can be used. Examples include those obtained by the transesterification reaction of (poly)glycerin with a monofunctional (meth)acrylate in the presence of a transesterification catalyst, or those obtained by the dehydration esterification of (poly)glycerin with (meth)acrylic acid in the presence of an acidic catalyst.

[0037] As for mixture (a1), among the manufacturing methods described above, the one obtained by the transesterification reaction of (poly)glycerin and monofunctional (meth)acrylate is preferred because it contains fewer impurities and allows for the acquisition of the desired (meth)acrylate.

[0038] Furthermore, as a transesterification reaction, a transesterification reaction between (poly)glycerin and a monofunctional (meth)acrylate in the presence of catalysts X and Y described below is preferred. Catalyst X: One or more compounds selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or their salts or complexes (hereinafter also referred to as "azabicyclo compounds"), amidine or its salts or complexes (hereinafter also referred to as "amidine compounds"), compounds having a pyridine ring or their salts or complexes (hereinafter also referred to as "pyridine compounds"), and phosphine or its salts or complexes (hereinafter also referred to as "phosphine compounds"). Catalyst Y: A compound containing zinc.

[0039] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates having C1-C8 alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate, and N,N-dimethylaminoethyl (meth)acrylate. As the monofunctional (meth)acrylate, an alkoxyalkyl (meth)acrylate having an alkyl group with 1 to 2 carbon atoms that promotes the dissolution of (poly)glycerin and exhibits extremely good reactivity is preferred, and 2-methoxyethyl (meth)acrylate is more preferred. Furthermore, as a monofunctional (meth)acrylate, acrylates are particularly preferred due to their excellent reactivity.

[0040] As catalyst X, one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, and pyridine compounds are preferred from the aforementioned group of compounds. These compounds exhibit excellent catalytic activity and can readily produce mixture (a1). Furthermore, they form complexes with catalyst Y (described later) after the reaction is complete, and these complexes can be easily removed from the reaction solution by simple methods such as adsorption. In particular, azabicyclo compounds can be removed even more easily by filtration and adsorption because their complexes with catalyst Y are poorly soluble in the reaction solution.

[0041] Preferred catalysts include azabicyclo compounds such as quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane; hereinafter also referred to as "DABCO"), N-methylimidazole, 1,8-diazabicyclo[5.4.0]undeca-7-ene (hereinafter also referred to as "DBU"), and 1,5-diazabicyclo[4.3.0]nona-5-ene (hereinafter also referred to as "DBN"), as well as an amidine compound such as N,N-dimethyl-4-aminopyridine (hereinafter also referred to as "DMAP"). Among these compounds, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, and DMAP are more preferred because they show good reactivity with most polyhydric alcohols and are readily available.

[0042] Various compounds containing zinc can be used as catalyst Y, but zinc organic acids and zinc diketone enolates are preferred due to their excellent reactivity. As catalyst Y, preferred examples of zinc organic acids include zinc acetate, zinc propionate, zinc acrylate, and zinc methacrylate, while preferred is zinc acetylacetonate, an example of a zinc diketone enolate. Among these compounds, zinc acetate, zinc acrylate, and zinc acetylacetonate are particularly preferred as catalyst Y because they exhibit good reactivity with most polyhydric alcohols and are readily available.

[0043] There are no particular restrictions on the ratio of catalyst X and catalyst Y used in the method for producing mixture (a1), but it is preferable to use 0.005 to 10.0 moles of catalyst X per mole of catalyst Y, and more preferably 0.05 to 5.0 moles. By using 0.005 moles or more of catalyst X per mole of catalyst Y, the amount of the target polyfunctional (meth)acrylate produced can be increased, and by using 10.0 moles or less, the formation of by-products and discoloration of the reaction solution can be suppressed, and the purification step after the reaction can be simplified.

[0044] As for the combination of catalyst X and catalyst Y, a combination in which catalyst X is an azabicyclo compound and catalyst Y is an organic acid zinc is preferred, and a combination in which the azabicyclo compound is DABCO and the organic acid zinc is zinc acetate and / or zinc acrylate is particularly preferred. This combination yields mixture (a1) in good yield and exhibits excellent color after the reaction (e.g., low yellowness), making it suitable for applications where colorless transparency is important, such as clear varnishes and hard coats. Furthermore, since the catalysts mentioned above are relatively inexpensive and readily available, this method is economically advantageous.

[0045] The reaction temperature in the method for producing mixture (a1) is preferably 40 to 180°C, and more preferably 60 to 160°C. By raising the reaction temperature to 40°C or higher, the reaction rate can be increased, and by raising it to 180°C or lower, the thermal polymerization of (meth)acryloyl groups in the raw materials or product can be suppressed, the discoloration of the reaction solution can be suppressed, and the purification step after the reaction can be simplified.

[0046] The reaction pressure in the method for producing mixture (a1) is not particularly limited as long as the predetermined reaction temperature can be maintained, and the method may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

[0047] In the method for producing mixture (a1), monohydric alcohols derived from monofunctional (meth)acrylates may be produced as a by-product during the transesterification reaction. When converting a portion of the hydroxyl groups of (poly)glycerin (for example, about 50 mol%) into (meth)acrylates, a monohydric alcohol is brought into the reaction system to reach equilibrium. After adsorption removal or deactivation of the catalyst, the monohydric alcohol and the monofunctional (meth)acrylate of the starting material are removed by distillation. This allows for the stable production of a product with a controlled acrylate conversion rate.

[0048] The method for producing mixture (a1) can be carried out without using a solvent, but a solvent may be used if necessary. Specific examples of solvents include hydrocarbons, ethers, crown ethers, esters, ketones, carbonate compounds, sulfones, sulfoxides, ureas or their derivatives, phosphine oxides, ionic liquids, silicone oils, and water. Among these solvents, hydrocarbons, ethers, carbonate compounds, and ionic liquids are preferred. These solvents may be used individually, or two or more may be combined as a mixed solvent.

[0049] In the method for producing mixture (a1), an inert gas such as argon, helium, nitrogen, or carbon dioxide may be introduced into the system to maintain a good color tone of the reaction solution, or an oxygen-containing gas may be introduced into the system to prevent polymerization of the (meth)acryloyl group. Specific examples of oxygen-containing gases include air, a mixture of oxygen and nitrogen, and a mixture of oxygen and helium. Methods for introducing the oxygen-containing gas include dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

[0050] In the method for producing mixture (a1), it is preferable to add a polymerization inhibitor to the reaction solution in order to prevent polymerization of the (meth)acryloyl group. Polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include phenolic compounds such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, and 4-tert-butylcatechol, quinone compounds such as benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, and N-oxyl compounds. Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. As a polymerization inhibitor, it is preferable to use an N-oxyl compound among the compounds mentioned above. The compounds mentioned above are preferred as N-oxyl compounds. Furthermore, it is preferable to use an N-oxyl compound in combination with another polymerization inhibitor as the polymerization inhibitor. In this case, phenolic compounds and phenothiazines are preferred as polymerization inhibitors other than the N-oxyl compound, with phenolic compounds being more preferred. Polymerization inhibitors may be added individually or in any combination of two or more types. They may be added from the beginning of the manufacturing process of mixture (a1) or midway through. The desired amount may be added all at once or in installments. They may also be added continuously via a rectification column. The polymerization inhibitor is preferably added at a concentration of 5 to 30,000 wtppm relative to the total weight of the reaction solution, and more preferably at a concentration of 25 to 10,000 wtppm. Adding a polymerization inhibitor at a concentration of 5 wtppm or more allows the polymerization inhibitor to be effective, while adding it at a concentration of 30,000 wtppm or less suppresses discoloration of the reaction solution, simplifies the purification process after the reaction, and suppresses a decrease in the curing rate of the resulting mixture (a1).

[0051] 1-2. Compound (a2) Various compounds can be used as compound (a2) [organic polyisocyanate], which is the other raw material compound for component (A).

[0052] Examples of compound (a2) include diisocyanates and triisocyanates. Examples of compound (a2) include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates. Specific examples of aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, as well as the biuret and isocyanurate forms of these compounds, and reaction products with polyhydric alcohols such as trimethylolpropane. Specific examples of alicyclic isocyanates include isophorone diisocyanate, norbornane diisocyanate, 2,5(2,6)-bis(isocyanatemethyl)bicyclo[2,2,1]heptane, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and 1,3-bis(isocyanatemethyl)cyclohexane, as well as the biuret and isocyanurate forms of these compounds, and reaction products with polyhydric alcohols such as trimethylolpropane. Specific examples of aromatic isocyanates include tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate, as well as the biuret and isocyanurate forms of these compounds, and reaction products with polyhydric alcohols such as trimethylolpropane. Furthermore, as compound (a2), aliphatic polyisocyanates and alicyclic polyisocyanates are preferred for the reason of their excellent light resistance. As compound (a2), aliphatic polyisocyanates are more preferred, and hexamethylene diisocyanate is particularly preferred because the composition has low viscosity and the cured film has excellent hardness and flexibility.

[0053] 1-3. Method for producing component (A) Component (A) can be produced by heating and stirring the mixture (a1) and compound (a2) in the presence of a catalyst and solvent as needed to urethaneize them.

[0054] The reaction ratio of compound (a2) to mixture (a1) is preferably 0.3 to 1.3 moles of total isocyanate groups of compound (a2) for every 1 mole of total hydroxyl groups of mixture (a1), more preferably 0.5 to 1.2 moles, and particularly preferably 0.9 to 1.1 moles.

[0055] In this case, it is possible to charge the mixture (a1) and compound (a2) together and react them, but this would result in a large amount of heat being released during the reaction. Therefore, it is preferable to add compound (a2) sequentially in the presence of mixture (a1) and carry out the reaction. Similarly, it is also preferable to add the mixture (a1) sequentially in the presence of compound (a2).

[0056] Although the above reaction can proceed without a catalyst, to expedite the reaction quickly, a catalyst commonly used in urethane formation reactions can be used during synthesis. Specific examples of catalysts include tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, and dibutyltin diacetylacetonate; bismuth compounds such as bismuth dioctate; iron compounds such as acetylacetonate iron; zinc compounds such as acetylacetonate zinc; and amine compounds such as triethylamine. The catalysts described above may be used individually or in combination of two or more.

[0057] The amount of catalyst added can be a catalytic amount, for example, preferably 0.01 to 1,000 wtppm relative to the reaction solution, and more preferably 0.1 to 1,000 wtppm. By adding 0.01 wtppm or more of catalyst, the urethane reaction can be preferably carried out, and by adding 1,000 wtppm or less, the discoloration of the resulting component (A) can be suppressed.

[0058] (A) The reaction mixture containing component (A) may become highly viscous, making stirring difficult. Therefore, a solvent may be added to the reaction components. As a solvent, one that does not participate in the urethane reaction is preferred, and examples of organic solvents include aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. When using an organic solvent, the amount to be added can be set appropriately according to the viscosity of the resulting component (A), but it is preferable to set it to be 0 to 70% by mass in the reaction solution. Here, "reaction solution" refers to the total amount of the raw materials when only the raw materials are used, and to the total amount including the reaction solvent and other components when the raw materials are used in addition to the reaction solvent. Specifically, it is used to mean a solution that combines the mixture (a1), the compound (a2), and any catalysts, solvents, polymerization inhibitors, etc. used as needed.

[0059] (Meth)acrylate may be added as a solvent, either together with or in place of the above-mentioned organic solvent. Examples of (meth)acrylates include compounds having ethylenically unsaturated groups other than component (A) described later [hereinafter referred to as "component (B)"]. A curable composition containing the obtained component (A) and (meth)acrylate can be produced by carrying out a urethane reaction in the presence of these (meth)acrylates. This composition is preferable because, unlike the case in which the organic solvent is incorporated, it does not require drying after application. The amount of (meth)acrylate used as a solvent added to the reaction solution can be appropriately set according to the proportion of other (meth)acrylates ultimately added to the composition. However, it is preferable to set the amount to be 0 to 70% by mass and more preferably 0 to 50% by mass in the reaction solution.

[0060] In urethane formation reactions, it is preferable to use polymerization inhibitors to prevent polymerization of (meth)acryloyl groups in the raw materials or products, and furthermore, oxygen-containing gas may be introduced into the reaction solution. Examples of oxygen-containing gases include air, a mixture of oxygen and nitrogen, and a mixture of oxygen and helium. These are some examples. Polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include phenol compounds such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, and 4-tert-butylcatechol; quinone compounds such as benzoquinone; stable radicals such as garbinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; phenothiazine; and N-nitroso-N-phenylhydroxylamine ammonium. Specific examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate. Specific examples of organic salt polymerization inhibitors include nitroso compounds such as N-nitroso-N-phenylhydroxylamine aluminum salt and ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate. These can be used individually or in combination of two or more. The proportion of polymerization inhibitor in the reaction solution is preferably 5 to 20,000 wt ppm, and more preferably 25 to 3,000 wt ppm.

[0061] The reaction temperature can be set appropriately depending on the raw materials used and the structure and molecular weight of the target component (A), but is generally preferred at 25 to 150°C, and more preferably at 30 to 120°C. The reaction time can also be set appropriately depending on the raw materials used and the structure and molecular weight of the target component (A), but is generally preferred at 1 to 70 hours, and more preferably at 2 to 30 hours.

[0062] In the present invention, the weight-average molecular weight (hereinafter referred to as "Mw") of component (A) is preferably 500 to 10,000, more preferably 500 to 5,000, and even more preferably 500 to 2,000, from the viewpoint of improving the coating properties and adhesive strength of the composition.

[0063] In this invention, Mw refers to the value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") to polystyrene equivalent, and means the value measured under the following conditions. • Detector: Differential refractive system (RI detector) • Column type: Cross-linked polystyrene column Column temperature: 40°C • Eluent: Tetrahydrofuran • Molecular weight standard material: Polystyrene

[0064] (A) Ingredients can be used individually or in combination of two or more.

[0065] 2.Curing composition The present invention relates to a curable composition comprising component (A) above. The composition can be manufactured by any conventional method; for example, it can be produced by stirring and mixing component (A) with other components as needed. In this case, heating may be performed as needed. The heating temperature can be set appropriately depending on the components contained in the composition used, the substrate to which the composition is coated, and the intended use, but 30°C to 80°C is preferred.

[0066] The content of component (A) in the composition is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, and even more preferably 20 to 60% by weight, based on 100% by weight of the total amount of components (A) and (B). (A) By setting the proportion of component 1% by weight or more, it is possible to prevent the cured film of the composition from warping (curling) and to achieve excellent adhesive strength of the cured film of the composition. By setting the proportion to 90% by weight or less, it is possible to suppress the composition from becoming highly viscous and to achieve favorable coating properties.

[0067] The viscosity of the composition can be set appropriately depending on the purpose, and is preferably between 1 and 100,000 mPa·s. In this invention, viscosity refers to the value measured at 25°C using an E-type viscometer (cone plate viscometer).

[0068] The composition of the present invention can be used as an active energy ray curable composition and a thermosetting composition, and is preferably used as an active energy ray curable composition.

[0069] The composition of the present invention has (A) as an essential component, but various components can be blended depending on the purpose. Other components include (B) component [compounds having ethylenically unsaturated groups other than (A) component], photopolymerization initiators [hereinafter referred to as "(C) component"], thermal polymerization initiators, organic solvents, antioxidants, ultraviolet absorbers, pigments / dyes, leveling agents, silane coupling agents, surface modifiers, and polymers. The following explains these ingredients. Furthermore, the other components listed below may be one of the exemplified compounds used, or two or more may be used in combination.

[0070] 1)(B) Component Component (B) is an ethylenically unsaturated compound other than component (A), and is added for the purpose of imparting various physical properties to the cured film of the composition. Examples of ethylenically unsaturated groups in component (B) include (meth)acryloyl groups, (meth)acrylamide groups, vinyl groups, and (meth)allyl groups, with (meth)acryloyl groups being preferred. In the following, "monofunctional" means a compound having one ethylenically unsaturated group, "multifunctional" means a compound having a certain number of ethylenically unsaturated groups, and "polyfunctional" means a compound having two or more ethylenically unsaturated groups. (B) Examples of components include compounds having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compounds"), compounds having two (meth)acryloyl groups (hereinafter referred to as "bifunctional (meth)acrylates"), and compounds having three or more (meth)acryloyl groups (hereinafter referred to as "trifunctional or more (meth)acrylates"). In this specification, (meth)acrylates with three or more functionalities are also referred to as poly(meth)acrylates.

[0071] In component (B), specific examples of monofunctional unsaturated compounds include compounds having a (meth)acryloyl group, monofunctional (meth)acrylamides, and compounds having a vinyl group. Examples of compounds having a (meth)acryloyl group include: Compounds having a carboxyl group and an ethylenically unsaturated group, such as (meth)acrylic acid, Michael addition dimers of acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and monohydroxyethyl (meth)acrylate phthalate; Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate; Monofunctional (meth)acrylates having aromatic groups, such as benzyl (meth)acrylate, (meth)acrylates of alkylene oxide adducts of phenols, (meth)acrylates of alkylphenols, (meth)acrylates of paracumylphenols, orthophenylphenol (meth)acrylate, (meth)acrylates of orthophenylphenols, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; Monofunctional (meth)acrylates having alicyclic groups such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and tricyclodecanemethylol (meth)acrylate; and Examples include tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide, and monofunctional (meth)acrylates having heterocyclic rings such as N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0072] Examples of monofunctional (meth)acrylamides include N-alkyl (meth)acrylamides such as N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, N-methyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-sec-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, and Nn-hexyl(meth)acrylamide; N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; and Examples include N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, and N,N-dihexyl(meth)acrylamide, as well as other N,N-dialkyl(meth)acrylamides.

[0073] Examples of compounds containing a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam.

[0074] Difunctional (meth)acrylates include, specifically, di(meth)acrylates of aliphatic diols such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate; Polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate; and Examples include di(meth)acrylates of alkylene oxide adducts of bisphenol A, and di(meth)acrylates of alkylene oxide adducts of bisphenol F, and other di(meth)acrylates of alkylene oxide adducts of diols having a bisphenol skeleton.

[0075] In addition to the compounds mentioned above, other oligomers such as epoxy (meth)acrylates having a bisphenol skeleton, polyether skeleton, or polyalkylene skeleton, urethane (meth)acrylates having a polyester skeleton, polyether skeleton, or polycarbonate skeleton, and polyester (meth)acrylates can be used as bifunctional (meth)acrylates.

[0076] Examples of trifunctional or more (meth)acrylates include various compounds having three or more (meth)acryloyl groups, such as polyol poly(meth)acrylates including glycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri or tetra(meth)acrylate, ditrimethylolpropane tri or tetra(meth)acrylate, and dipentaerythritol tri, tetra, penta or hexa(meth)acrylate; Poly(meth)acrylates of polyol alkylene oxide adducts such as tri or tetra(meth)acrylates of pentaerythritol alkylene oxide adducts, tri or tetra(meth)acrylates of ditrimethylolpropane alkylene oxide adducts, and tri, tetra, penta, or hexa(meth)acrylates of dipentaerythritol alkylene oxide adducts; Tri(meth)acrylates of alkylene oxide adducts of isocyanuric acid; and Urethane (meth)acrylates, etc., are reaction products of compounds having hydroxyl groups and three or more (meth)acryloyl groups, such as pentaerythritol tri(meth)acrylate, with organic polyisocyanates. We can list some examples. Examples of alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts. Furthermore, examples of the aforementioned organic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and trimers of hexamethylene diisocyanate.

[0077] The content of component (B) is preferably 0 to 60% by weight, and more preferably 0 to 30% by weight, in 100 parts by weight of the total amount of component (A) and component (B) (hereinafter, component (A) and component (B) are collectively referred to as "curable components"). (B) If the content of component exceeds 60% by weight, the cured film may become brittle, especially in the case of polyfunctional ethylenically unsaturated compounds.

[0078] 2)(C) Component When the composition of the present invention is used as an active energy ray curable composition, and further used as an electron beam curable composition, it is also possible to omit component (C) (photopolymerization initiator) and cure it with an electron beam. When the composition of the present invention is used as an active energy ray curable composition, it is particularly preferable to further include component (C) when ultraviolet light and visible light are used as the active energy rays, from the viewpoint of ease of curing and cost. When using electron beams as the active energy source, it is not always necessary to include this ingredient, but a small amount can be added as needed to improve curing properties.

[0079] (C)Specific examples of components include benzyldimethyl 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-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propan-1-one] Aromatic ketone compounds such as pionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-octylcarbazole, methyl phenylglyoxyate, ethylanthraquinone, and phenanthrenequinone; Benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and fluorothioxanthone.

[0080] Among these compounds, α-hydroxyphenyl ketones are preferred because they exhibit good surface hardening properties even when used as thin film coatings in the atmosphere. Specifically, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one are more preferred. Furthermore, if it is necessary to increase the thickness of the cured film, for example, to 50 μm or more, it is preferable to use acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, or 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one in combination, for the purpose of improving the curability inside the cured film or when using ultraviolet absorbers or pigments in combination.

[0081] The content ratio of component (C) is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight, per 100 parts by weight of the total amount of curable components. By setting the ratio of component (C) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be made excellent, and by setting it to 10 parts by weight or less, the internal curing of the cured film can be improved and the adhesion to the substrate can be made good.

[0082] 3) Thermal polymerization initiator When the composition is used as a thermosetting composition, a thermal polymerization initiator may be added. The composition of the present invention can also be cured by heat after incorporating a thermal polymerization initiator. Various compounds can be used as thermal polymerization initiators, with organic peroxides and azo-based initiators being preferred. Specific examples of organic peroxides include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1, 1-Bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane Examples include t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide. Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane. These can be used individually or in combination of two or more. Furthermore, organic peroxides can be combined with reducing agents to produce redox reactions.

[0083] The amount of these thermal polymerization initiators used is preferably no more than 10 parts by weight per 100 parts by weight of the total amount of curable components. When using a thermal polymerization initiator alone, the process should follow the standard procedures for radical thermal polymerization. In some cases, it can be used in combination with a photopolymerization initiator, and thermal curing can be performed after photocuring to further improve the reaction rate.

[0084] 4) Organic solvents The composition of the present invention may include an organic solvent for purposes such as improving the coating properties on a substrate.

[0085] Specific examples of organic solvents include alcohol compounds such as methanol, ethanol, isopropanol, and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as benzene, toluene, and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone. Among these, alkylene glycol monoether compounds and ketone compounds are preferred, with alkylene glycol monoether compounds being more preferred.

[0086] The content of the organic solvent is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, and even more preferably 50 to 300 parts by weight, per 100 parts by weight of the total amount of curable components. Within this range, the composition can be made to have a viscosity suitable for coating, and the composition can be easily applied by the known coating method described later.

[0087] 5) Antioxidants Antioxidants are added to improve the durability of the cured film, such as its heat resistance and weather resistance. Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available examples include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA Corporation. Examples of phosphorus-based antioxidants include phosphines such as trialkylphosphines and triarylphosphines, as well as trialkyl phosphites and triaryl phosphites. Commercially available derivatives of these include, for example, Adeka Stub PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010, all manufactured by Adeka Corporation. Examples of sulfur-based antioxidants include thioether compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Corporation. These can be used individually or in combination of two or more types. Preferred combinations of these antioxidants include the combined use of a phenolic antioxidant and a phosphorus-based antioxidant, and the combined use of a phenolic antioxidant and a sulfur-based antioxidant. The antioxidant content can be set appropriately depending on the purpose, but is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of curable components. By setting the content ratio to 0.1 parts by weight or more, the durability of the composition can be improved, while by setting it to 5 parts by weight or less, good curability and adhesion can be achieved.

[0088] 6) UV absorbers UV absorbers are added to improve the light resistance of the cured film. Examples of UV absorbers include triazine-based UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130. The content ratio of the UV absorber can be set appropriately depending on the purpose, but it is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of curable components. By setting the content ratio to 0.01% by weight or more, the light resistance of the cured film can be made good, while by setting it to 5% by weight or less, the curability of the composition can be made excellent.

[0089] 7) Pigments and dyes Examples of pigments include organic pigments and inorganic pigments. Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, and pyrazolone red; soluble azo pigments such as litol red, heliobordeaux, pigment scarlet, and permanent red 2B; derivatives from vat dyes such as alizarin, indanthron, and thioindigo maroon; phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone-based organic pigments such as quinacridone red and quinacridone magenta; perylene-based organic pigments such as perylene red and perylene scarlet; and isoindone. Examples of pigments include isoindolone-based organic pigments such as linone yellow and isoindolone orange; pyranthrone-based organic pigments such as pyranthrone red and pyranthrone orange; thioindigo-based organic pigments; condensed azo-based organic pigments; benzimidazolon-based organic pigments; quinophthalone-based organic pigments such as quinophthalone yellow; isoindoline-based organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow, acylamido yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthaquinonyl red, and dioxazine violet. Furthermore, specific examples of the inorganic pigments include titanium dioxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, and synthetic iron black. Note that carbon black, as exemplified in the filler section, can also be used as an inorganic pigment. Various conventionally known compounds can be used as dyes.

[0090] 8) Silane coupling agents Silane coupling agents are added to improve the interfacial adhesion strength between the cured film and the substrate. The silane coupling agent is not particularly limited as long as it can contribute to improving adhesion to the substrate.

[0091] Examples of silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0092] The proportion of the silane coupling agent can be set appropriately according to the purpose, but is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of curable components. By increasing the blending ratio to 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by keeping it at 10 parts by weight or less, changes in adhesive strength over time can be prevented.

[0093] 9) Surface modifiers The composition of the present invention may contain a surface modifier for purposes such as improving leveling properties during application or enhancing scratch resistance by increasing the slipperiness of the cured film. Examples of surface modifiers include surface modifiers, surfactants, leveling agents, defoaming agents, lubricity-imparting agents, and antifouling agents, and these known surface modifiers can be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers are particularly preferred. Specific examples include silicone-based polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone-based polymers and oligomers having silicone chains and polyester chains, fluorine-based polymers and oligomers having perfluoroalkyl groups and polyalkylene oxide chains, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains. Furthermore, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in its molecule may be used for purposes such as increasing the durability of the lubricity.

[0094] The surface modifier content is preferably 0.01 to 1.0 part by weight per 100 parts by weight of the total amount of curable components. Within this range, the surface smoothness of the coating film is excellent.

[0095] 10) Polymers The composition of the present invention may further contain a polymer for purposes such as further improving the curl resistance of the resulting cured film. Suitable polymers include (meth)acrylic polymers, and suitable constituent monomers include methyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide. In the case of polymers copolymerized with (meth)acrylic acid, glycidyl (meth)acrylate may be added to introduce (meth)acryloyl groups into the polymer chain. The polymer content is preferably 0.01 to 10 parts by weight per 100 parts by weight of the total amount of curable components. Within this range, the resulting cured film exhibits superior curl resistance.

[0096] 3.How to use The composition of the present invention can be used according to conventional methods. For example, one method involves applying the composition to a substrate and then curing it by irradiating it with active energy rays or by heating it. Specifically, for applications such as coatings and adhesives, the composition is applied to the substrate using a conventional painting method, and then cured by irradiation with active energy rays in the case of an active energy ray-curable composition, or by heating in the case of a thermosetting composition. For applications such as molding materials, the composition is poured into a predetermined mold, and then cured by irradiation with active energy rays in the case of an active energy ray-curable composition, or by heating in the case of a thermosetting composition. The irradiation and heating methods using active energy rays are common methods known as conventional curing methods. You should adopt that method. Furthermore, a method can be employed in which component (C) (photopolymerization initiator) and a thermal polymerization initiator are used in combination in the composition, and then the mixture is irradiated with active energy rays and subsequently heated and cured to improve adhesion to the substrate.

[0097] The composition of the present invention can be applied to a variety of substrates, including plastics, wood, metals, inorganic materials, and paper. Specific examples of plastics include polyvinyl alcohol, cellulose acetate resins such as triacetylcellulose and diacetylcellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, cyclic polyolefin resins using cyclic olefins such as polyethersulfone and norbornene as monomers, polyvinyl chloride, epoxy resins, and polyurethane resins. Examples of wood include natural wood and synthetic wood. Examples of metals include steel plates, aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Examples of inorganic materials include glass, mortar, concrete, and stone. Among these, plastic substrates are particularly preferred.

[0098] The thickness of the cured film of the composition on the substrate can be set appropriately depending on the purpose. The thickness of the cured film can be selected according to the substrate used and the application of the substrate with the manufactured cured film, but it is preferably 1 to 500 μm, and more preferably 5 to 200 μm.

[0099] The method for coating the composition of the present invention onto a substrate can be appropriately set according to the purpose, and examples include coating with a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater, and microgravure coater.

[0100] Examples of active energy rays for curing the composition of the present invention include ultraviolet light, visible light, and electron beams, but ultraviolet light is preferred. Examples of ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs). The irradiation energy should be set appropriately depending on the type and composition of the active energy rays, but as an example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region should be 10 to 10,000 mJ / cm². 2 Preferably, 100-2,000 mJ / cm² 2 This is preferable.

[0101] 4.Applications The composition of the present invention can be used in a variety of applications, specifically including coating agents such as hard coats, inks for offset printing, adhesives, sealants, and more.

[0102] The composition of the present invention can preferably be used as an active energy ray curable composition, and because its cured film has an excellent balance of surface hardness, scratch resistance and flexibility, and also has excellent curlability, it can be more preferably used as a hard coat agent. Suitable applications for hard coating agents include, for example, front panels for display boards, building materials, lighting fixtures, displays and casings for mobile phones, smartphones, and tablet devices, casings for home appliances, and various lenses such as eyeglasses. Specific examples of front panels for display boards include electronic display boards, displays, billboards, advertisements, and signs. Examples of products using wood as a base material include wooden products such as stairs, floors, and furniture. Examples of products using metal as a base material include metal products such as kitchen panels and stainless steel sinks. [Examples]

[0103] The present invention will be described in more detail below with reference to examples and comparative examples. In the following, "parts" refers to parts by weight.

[0104] 1. Manufacturing example 1) Manufacturing Example 1 [Production of mixture (a1)] In a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and condenser, 302.75 parts (3.29 moles) of glycerin [purified glycerin (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd. (hereinafter referred to as "GLY")], 2312.84 parts (17.77 moles) of 2-methoxyethyl acrylate (hereinafter referred to as "MCA"), 6.51 parts (0.06 moles) of DABCO as catalyst X, 24.07 parts (0.12 moles) of zinc acrylate as catalyst Y, 1.19 parts (0.01 moles) of hydroquinone monomethyl ether (hereinafter referred to as "MEHQ"), and 0.21 parts (0.002 moles) of phenothiazine were charged, and oxygenated gas (5% oxygen by volume, 95% nitrogen by volume) was bubbled into the liquid. While heating and stirring the reaction mixture at a temperature of 100-130°C, the pressure in the reaction system was adjusted to a range of 110-760 mmHg. The mixture of MCA and 2-methoxyethanol (hereinafter referred to as "MEL"), a by-product of the transesterification reaction, was withdrawn from the reaction system via a rectification column and condenser. In addition, an equal weight of MCA to the withdrawn mixture was added to the reaction system as needed. After 18 hours from the start of heating and stirring, the pressure in the reaction system was returned to atmospheric pressure and the withdrawal was terminated. The acrylate rate of the hydroxyl group in GLY was determined from the amount of MEL produced, and it was found to be 57 mol%. After cooling the reaction mixture to room temperature and filtering out the precipitate, 58.7 parts of aluminum silicate [Kyoward 700SEN-S (product name), manufactured by Kyowa Chemical Industry Co., Ltd.; hereinafter referred to as "700SEN-S"] were added to the filtrate to adsorb and remove catalysts X and Y contained in the filtrate, and the mixture was stirred. The mixture was then heated and stirred for 1 hour in the range of 70-100°C. After filtering out the aluminum silicate after the adsorption treatment, the filtrate was placed in a flask connected to a stirrer, thermometer, gas inlet tube, distillation condenser, and vacuum tube. Vacuum distillation was performed for 10 hours at a temperature of 70-100°C and a pressure of 0.001-100 mmHg while bubbling dry air, and the distillate containing unreacted MCA was separated. 5.0 parts of diatomaceous earth [Radiolite (product name), manufactured by Showa Chemical Industry Co., Ltd.; hereinafter referred to as "Radiolite"] were added to the stockpot liquid and pressure filtration was performed, and the resulting filtrate was taken as mixture (a1). The yield of mixture (a1) was 647 parts. Hereafter, this will be referred to as mixture (a1-1). If all of the prepared GLY 302.75 parts were converted to glycerin diacrylate (hereinafter referred to as "GLY-DA"), the yield would be 658 parts. Based on this, the yield of the above mixture (a1-1) was calculated to be 98%. Using an HPLC equipped with a UV detector, the purity of GLY-DA contained in mixture (a1-1) was calculated using the following formula (3), and the result was 63%, with glycerin triacrylate (hereinafter referred to as "GLY-TA") at 23% and glycerin monoacrylate (hereinafter referred to as "GLY-MA") at 14%. The resulting mixture (a1-1) had a viscosity of 41 mPa·s (25°C) and a hydroxyl value of 240 mgKOH / g. The Mw measured by GPC was 309.

[0105] Furthermore, HPLC, viscosity, hydroxyl value, and GPC were measured according to the following methods. ◆HPLC measurement conditions • Equipment: ACQUITY UPLC manufactured by Waters Co., Ltd. • Detector: UV detector • Detection wavelength: 210nm • Column: Waters Corporation ACQUITY UPLC BEH C18 (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm) Column temperature: 40°C • Eluent composition: Mixture of 0.03 wt% trifluoroacetic acid aqueous solution and methanol. • Eluent flow rate: 0.3 mL / min

[0106] ◆Method for calculating the purity of GLY-DA contained in mixture (a1-1) GLY-DA purity % = [(D / 2) / (M+D / 2+T / 3)]×100...Equation (3) The symbols and terms in formula (1) have the following meanings: • D: Peak area of ​​GLY-DA at 210 nm • Peak area of ​​M:GLY-MA at 210nm • T: Peak area of ​​GLY-TA at 210 nm

[0107] ◆Viscosity measurement conditions The viscosity at 25°C was measured using an E-type viscometer.

[0108] ◆Hydroxyl value measurement conditions The measurement was performed in accordance with JIS K0070-1992. Specifically, the sample was heated in a hot bath with an acetylation reagent added. After cooling, the hydroxyl value was determined by titrating the acid with potassium hydroxide ethanol solution using phenolphthalein solution as an indicator. Furthermore, five times the amount of pyridine used in the method described in JIS K0070-1992 was employed.

[0109] ◆GPC measurement conditions • Equipment: Waters Corporation GPC System Name 1515 2414 717P RI • Detector: RI detector • Columns: Guard column Shodex KFG (8μm 4.6×10mm) manufactured by Showa Denko K.K., and two types of main columns Waters Co., Ltd.: styragel HR 4E THF (7.8×300mm) + styragel HR 1THF (7.8×300mm) manufactured by Waters Co., Ltd. Column temperature: 40°C • Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min Furthermore, GPC measurements were performed under the same conditions in manufacturing examples 2 to 5.

[0110] 2) Manufacturing Example 2 (Production of mixture (a1)) In a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and condenser, 249.92 parts (1.50 mol) of diglycerin [Glycerin 801 (trade name), manufactured by Sakamoto Pharmaceutical Co., Ltd. (hereinafter referred to as "DGLY")], 1410.92 parts (10.84 mol) of MCA, 5.95 parts (0.05 mol) of DABCO as catalyst X, 22.03 parts (0.11 mol) of zinc acrylate as catalyst Y, 0.99 parts (0.01 mol) of MEHQ, and 0.45 parts (0.003 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl were charged, and oxygenated gas (5% oxygen by volume, 95% nitrogen by volume) was bubbled into the liquid. While heating and stirring the reaction mixture at a temperature of 100-130°C, the pressure in the reaction system was adjusted to a range of 150-760 mmHg. The mixture of MCA and MEL, a by-product of the transesterification reaction, was withdrawn from the reaction system via a rectification column and condenser. In addition, MCA containing a polymerization inhibitor was added as needed to balance the weight of the withdrawn liquid. After 20 hours from the start of heating and stirring, the pressure in the reaction system was returned to atmospheric pressure to terminate the withdrawal. The acrylate rate of the hydroxyl group in DGLY was determined to be 82 mol% from the amount of MEL produced. After cooling the reaction mixture to room temperature and filtering out the precipitate, 25.0 parts of aluminum silicate (700SEN-S) were added to the filtrate to adsorb and remove catalysts X and Y, and the mixture was stirred. The mixture was then heated and stirred at a temperature of 70-100°C for 1 hour. Subsequently, 3.7 parts of calcium hydroxide were added at an internal temperature of 20-40°C, and the mixture was stirred at atmospheric pressure for 1 hour. Insoluble materials were then separated by pressure filtration. 2.0 parts of aluminum silicate (700SEN-S) were added to the obtained filtrate, and the mixture was placed in a flask connected to a stirrer, thermometer, gas inlet tube, distillation condenser, and vacuum tube. Vacuum distillation was performed for 10 hours at a temperature of 70-100°C and a pressure of 0.001-100 mmHg while bubbling dry air, and the distillate containing unreacted MCA was separated. 0.33 parts of DEHA were added to the obtained kettle liquid, and the mixture was stirred for 3 hours under atmospheric pressure at an internal temperature of 70-90°C. Then, 5.0 parts of diatomaceous earth (radiolite) were added to the kettle liquid, and pressure filtration was performed to obtain the filtrate. The obtained filtrate was designated as mixture (a1). The yield of mixture (a1) was 502 parts. Hereafter, this will be referred to as mixture (a1-2). Using an HPLC equipped with a UV detector, the purity of diglycerin triacrylate (hereinafter referred to as "DGLY-TA") contained in mixture (a1-2) was calculated using the following formula (4), and the result was 41%. The resulting mixture (a1-2) had a viscosity of 223 mPa·s (25℃) and a hydroxyl value of 80 mgKOH / g.

[0111] ◆Method for calculating the purity of DGLY-TA contained in mixture (a1-2) Purity % of DGLY-TA = [(Tri / 3) / (M+D / 2+Tri / 3+Tetra / 4)]×100 ...Equation (4) The symbols and terms in formula (1) have the following meanings: • Peak area of ​​Tri:DGLY-TA at 210nm • M: Peak area of ​​diglycerin monoacrylate at 210 nm • D: Peak area of ​​diglycerin diacrylate at 210 nm • Tetra: Peak area of ​​diglycerin tetraacrylate at 210 nm

[0112] 3) Manufacturing Example 3 [(A) Manufacturing] In a 1L flask equipped with a stirrer, thermometer, and piping for a 5% oxygen / nitrogen mixed gas (hereinafter referred to as 5%ON), 93.52g of mixture (a1-1), 0.064g of 2,6-di-t-butyl-4-methylphenol (hereinafter referred to as BHT), and 0.064g of di-n-butyltin dilaurate [a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; hereinafter referred to as DBTDL] were charged. The contents were stirred while blowing in 5% ON to bring the temperature inside the flask to 70°C. Then, hexamethylene diisocyanate (hereinafter referred to as HDI) was gradually added until a total of 33.6 g of HDI was added (a ratio of 0.98 moles of isocyanate groups to 1 mole of total hydroxyl groups in mixture (a1-1)). After that, the temperature inside the flask was raised to 90°C and held there for 5 hours to complete the reaction. Subsequent IR measurements confirmed the disappearance of the isocyanate group, and the synthesis was terminated. The resulting reaction mixture was a tetrafunctional urethane acrylate adduct with a GPC Mw of 0.4 million (hereinafter referred to as "A-1").

[0113] 4) Manufacturing Example 4 [(A) Manufacturing] In a 1L flask equipped with a stirrer, thermometer, and 5% ON piping, 112.22g of mixture (a1-2), 0.063g of BHT, and 0.064g of DBTDL were charged. The contents were stirred while blowing in 5% ON to bring the temperature inside the flask to 70°C. Then, HDI was gradually added until a total of 13.5g of HDI was added (0.98 moles of isocyanate groups for every 1 mole of hydroxyl groups in mixture (a1-2)). The temperature inside the flask was then raised to 90°C and held there for 5 hours to complete the reaction. Subsequent IR measurements confirmed the disappearance of the isocyanate group, and the synthesis was terminated. The resulting reaction mixture was a hexafunctional urethane acrylate adduct with a GPC Mw of 0.4 million (hereinafter referred to as "A-2").

[0114] 5) Manufacturing Example 5 [(A) Manufacturing] In a 1L flask equipped with a stirrer, thermometer, and 5% ON piping, 278.3g of mixture (a1-1), 0.50g of BHT, and 0.10g of DBTDL were charged. The contents were stirred while blowing in 5% ON to bring the temperature inside the flask to 70°C. Then, TPA-100 (an isocyanate manufactured by Asahi Kasei Chemicals Corporation; hereinafter referred to as TPA-100) was gradually added, and finally 221.7g of TPA-100 (a ratio of 0.98 moles of isocyanate groups to 1 mole of total hydroxyl groups in mixture (a1-1)) was charged. After that, the temperature inside the flask was raised to 90°C and held for 5 hours to complete the reaction. Subsequent IR measurements confirmed the disappearance of the isocyanate group, thus terminating the synthesis. The resulting reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter referred to as "A-3") with a Mw of 0.6 million as determined by GPC.

[0115] 6) Comparative Manufacturing Example 1 [Manufacturing of urethane acrylate duct bodies other than component (A)] In a 1L flask equipped with a stirrer, thermometer, and 5% ON piping, 599.4g of Arronix M-305 (pentaerythritol tri / tetraacrylate, manufactured by Toagosei Co., Ltd., hydroxyl value 115 mg KOH / g; hereinafter referred to as M-305), 0.50g of BHT, and 0.10g of DBTDL were charged. The contents were stirred while blowing in 5% ON to bring the temperature inside the flask to 70°C. Then, TPA-100 was gradually added until a total of 221.7g of TPA-100 was charged (0.98 moles of isocyanate groups for every 1 mole of hydroxyl groups of M-305). After that, the temperature inside the flask was raised to 90°C and held there for 5 hours to complete the reaction. Subsequent IR measurements confirmed the disappearance of the isocyanate group, and the synthesis was terminated. The resulting reaction mixture was a 9-functional urethane acrylate adduct with a Mw of 0.8 million determined by GPC (hereinafter referred to as "A'-1").

[0116] 2. Examples and Comparative Examples 1) Production of activated energy ray curable compositions The compounds shown in Table 1 below were stirred and mixed in the proportions shown in Table 1 to produce an active energy ray curable composition. The obtained compositions were used for the evaluations described below. The results are shown in Table 2.

[0117] [Table 1]

[0118] In Table 1, the numbers represent the number of copies, and the abbreviations have the following meanings. • M-930: Glycerin triacrylate, manufactured by Toagosei Co., Ltd. as "Aronics M-930" • ACMO: Acryloylmorpholine, manufactured by KJ Chemicals, "ACMO" • UA306H: A tetrafunctional urethane acrylate adduct composed of pentaerythritol triacrylate and hexamethylene diisocyanate, manufactured by Kyoeisha Chemical Co., Ltd., "UA-306H" • HCl: 1-Hydroxycyclohexyl phenyl ketone, manufactured by IGM Resins, Omnirad 184

[0119] 2) Method for evaluating the composition (1) Viscosity The viscosity of the compositions obtained in Table 1 was measured at 25°C using an E-type viscometer. The results are shown in Table 2.

[0120] 3) Physical properties of cured film In the following evaluation, UV-A intensity of 500 mW / cm² was used. 2 At this rate, 800 mJ / cm² per pass. 2 Samples of the composition were cured under the same conditions as the curing test, except that the irradiation energy was adjusted to the specified value.

[0121] (2) Pencil hardness The evaluation was performed under a 750g load in accordance with JIS K5600-5-4.

[0122] (3) Scratch resistance After 100 cycles with a load of 500g using steel wool #0000, the following two levels of evaluation were performed. ○: No scratches are visible on the hardened film, ×: Scratches are visible on the hardened film

[0123] (4) Flexibility In accordance with the mandrel test (JIS K5600-5-1), PET film with a cured film formed on it was wrapped around a core rod with a diameter of 2 mm, 4 mm, or 6 mm, and evaluated at the following two levels. ○: No cracks or peeling of the hardened film, ×: Cracks or peeling of the hardened film were observed.

[0124] (5) Curl The sample was cut into 6cm x 6cm sections, and the height of the raised corners was measured and evaluated using the average value. A smaller value indicates less deformation.

[0125] [Table 2]

[0126] As is clear from the results of Examples 1 and 2, these compositions had low viscosity, and their cured films exhibited excellent hardness, scratch resistance, flexibility, and curlability. In contrast, Comparative Example 1 is a composition mainly composed of a hexafunctional urethane acrylate adduct body that does not contain component (A), but it had high viscosity and poor flexibility and curlability. Furthermore, Example 3 is a composition mainly composed of A-3, a polyfunctional urethane acrylate adduct synthesized from TPA-100, a trifunctional isocyanate. It had lower viscosity and superior flexibility and curlability compared to Comparative Example 2, which mainly composed of A'-1, a polyfunctional urethane acrylate adduct also synthesized from TPA-100. [Industrial applicability]

[0127] The present invention relates to a curable composition, which can be preferably used as an active energy ray curable composition. Furthermore, the composition of the present invention can be used in various applications, such as coating agents for hard coats and inks for offset printing. In particular, because it has low viscosity and the resulting cured film can simultaneously satisfy hardness, scratch resistance, flexibility, and curlability, it is preferably used as a coating agent composition.

Claims

1. An active energy ray curable composition comprising the following components (A), (B), and (C). (A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, having a hydroxyl value of 20 to 300 mg KOH / g (a1), and a reaction product of an aliphatic polyisocyanate. (B) Components: Monofunctional (meth)acrylates having heterocyclic rings, and polyol poly(meth)acrylates (C) Component: Photopolymerization initiator

2. The aliphatic polyisocyanate is hexamethylene diisocyanate. The activated energy ray curable composition according to claim 1.

3. The monofunctional (meth)acrylate having a heterocycle is acryloylmorpholine, The polyol poly(meth)acrylate is glycerin triacrylate. The activated energy ray curable composition according to claim 1.

4. The photopolymerization initiator is 1-hydroxycyclohexylphenyl ketone. The activated energy ray curable composition according to claim 1.

5. The aliphatic polyisocyanate is hexamethylene diisocyanate, The monofunctional (meth)acrylate having a heterocycle is acryloylmorpholine. The polyol poly(meth)acrylate is glycerin triacrylate. The photopolymerization initiator is 1-hydroxycyclohexylphenyl ketone. The activated energy ray curable composition according to claim 1.

6. (A) The weight-average molecular weight of component is 500 to 10,000. The activated energy ray curable composition according to claim 1.

7. Used as a coating agent, The activated energy ray curable composition according to any one of claims 1 to 6.

Images