JP2011178863A - Active energy ray-curable composition, curable resin composition and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition achieving both of curability and substrate adhesiveness in high level, to provide an active energy ray-curable resin composition containing the composition, and to provide a cured product obtained by curing the composition. <P>SOLUTION: The active energy ray-curable composition containing a (meth)acrylic acid ester of an N-hydroxyalkylated lactam compound includes the specific (meth)acrylic acid ester of the N-hydroxyalkylated lactam compound and a specified N-hydroxyalkylated lactam compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an active energy ray-curable composition, an active energy ray-curable resin composition comprising the same, and a cured product obtained by curing them. More specifically, the present invention relates to an active energy ray-curable composition that can be suitably used as a reactive diluent composition, an active energy ray-curable resin composition comprising the same, and a cured product obtained by curing them. .

The active energy ray-curable composition is a composition that is cured by a curing technique using active energy rays such as ultraviolet rays or electron beams, and active energy ray curing has advantages such as energy saving, space saving, and short-time curing. The range of use is expanding.
An active energy ray-curable resin composition can be obtained by adding a curable resin to the active energy ray-curable composition, but among the components of the active energy ray-curable composition, the curable resin composition has a low content. A polymerizable monomer used for the purpose of increasing viscosity and improving adhesiveness is called a reactive diluent, and a wide variety of polymerizable monomers have been developed.

The polymerizable monomers that have been developed so far include (meth) acrylic acid esters, radical curable reactive diluents typified by vinyl compounds, vinyl ethers, epoxy compounds, and alicyclic ether compounds. Typical examples include cationic curable reactive diluents. Among them, not only is the curable resin composition excellent in reducing the viscosity, but also in reactivity, adhesion to a substrate, etc. N-vinylpyrrolidone has been used very widely. However, since N-vinylpyrrolidone is concerned that there is a problem of toxicity and its use is limited, development of a polymerizable monomer that replaces N-vinylpyrrolidone has been advanced.

As such polymerizable monomers, (2-oxo-1-pyrrolidinyl) alkyl acrylates or methacrylates have been developed so far, and radiation curable compositions comprising (2-oxo-1-pyrrolidinyl) alkyl acrylates or methacrylates Is disclosed (for example, see Patent Document 1). Also, as a method for producing the polymerizable monomer, cyclic N-hydroxyalkylated lactam is esterified with (meth) acrylic acid in the presence of at least one heterogeneous inorganic salt, or at least one ( The method of manufacturing by transesterifying with a meth) acrylic acid ester is disclosed (for example, refer patent document 2).

JP-A-8-41133 (page 1-2) Special table 2009-515835 (page 1-2)

As described above, a radiation curable composition containing N-hydroxyalkylated lactam (meth) acrylate and a method for producing the same have been disclosed. ) Regarding the curability and substrate adhesion of the composition containing an acrylate ester, it is still not industrially sufficient, and there is room for improvement in order to achieve higher performance.

The present invention has been made in view of the above situation, and an active energy ray-curable composition that achieves both a high level of curability and substrate adhesion, and an active energy ray-curable resin composition comprising the same, And it aims at providing the hardened | cured material formed by hardening | curing them.

The present inventors have studied various active energy ray-curable compositions containing a (meth) acrylic acid ester of N-hydroxyalkylated lactam, and have focused on the composition of the composition. And by including the N-hydroxyalkylated lactam compound which has a specific structure, it discovered that both the sclerosis | hardenability and base-material adhesiveness of a composition improved, and this can solve the said subject brilliantly. The present invention has been conceived and reached the present invention.
In addition, although patent document 1 is disclosing the radiation-curable composition containing the (meth) acrylic acid ester of N-hydroxyalkylated lactam, the N-hydroxyalkylated lactam compound which has a specific structure in the composition In addition, in Patent Document 2, in the example, when N-hydroxyethylpyrrolidone-methacrylate is synthesized, N-hydroxyethylpyrrolidone which is a synthesis raw material is used as an impurity. In this document, N-hydroxyethylpyrrolidone-methacrylate containing a synthetic raw material as an impurity, and the relationship between the curability of the active energy ray-curable composition and the substrate adhesion are disclosed. Sex is not mentioned at all and is not expected. That is, by including an N-hydroxyalkylated lactam compound having a specific structure in an active energy ray-curable composition containing a (meth) acrylic acid ester of N-hydroxyalkylated lactam, the curability and group of the composition are included. The improvement in both material adhesion is an effect found for the first time in the present invention, and has industrially important technical significance.

That is, the present invention is an active energy ray-curable composition containing a (meth) acrylic acid ester of an N-hydroxyalkylated lactam compound, wherein the active energy ray-curable composition has the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, or represents an oxygen atom formed by an ether bond. Represents an organic group having 4 to 30 carbon atoms having one or more in the structure of the alkylene skeleton, provided that in R ² , the nitrogen atom constituting the lactam ring skeleton and the (meth) acryloyl skeleton are constituted — (CO) — A carbon atom is bonded to the O- group, R ³ represents an alkylene group having 1 to 5 carbon atoms, or an oxygen atom, a sulfur atom, an imino group, a cycloalkylene group having 5 to 12 carbon atoms, At least one selected from the group consisting of-(CO)-group,-(CO) -O- group, -O- (CO) -O- group, and-(NH)-(CO) -O- group. The end or middle part of the alkylene skeleton Represents an organic group having 2 to 20 carbon atoms, and the group is at least one selected from the group consisting of an aryl group, an alkyl group, an aryloxy group, an alkyloxy group, an atomic group having a hetero atom, and a heterocyclic ring. A hydrogen atom may be substituted by any of the above, provided that, in R ³ , a carbon atom is bonded to a carbon atom of the nitrogen atom and carbonyl group constituting the lactam ring skeleton, provided that R ² and R ³ are At least one hydrogen atom is bonded to at least one carbon atom bonded to the nitrogen atom constituting the lactam ring skeleton among the carbon atoms constituting the N-hydroxyalkylated lactam compound. (Meth) acrylic acid ester of the following general formula (2);

(Wherein R ² and R ³ are the same as those in the general formula (1), but may be the same as or different from the R ² and R ³ in the general formula (1)). An active energy ray-curable composition containing the N-hydroxyalkylated lactam compound.
The present invention is described in detail below.

The active energy ray-curable composition of the present invention has the following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, or represents an oxygen atom formed by an ether bond. Represents an organic group having 4 to 30 carbon atoms having one or more in the structure of the alkylene skeleton, provided that in R ² , the nitrogen atom constituting the lactam ring skeleton and the (meth) acryloyl skeleton are constituted — (CO) — A carbon atom is bonded to the O- group, R ³ represents an alkylene group having 1 to 5 carbon atoms, or an oxygen atom, a sulfur atom, an imino group, a cycloalkylene group having 5 to 12 carbon atoms, At least one selected from the group consisting of-(CO)-group,-(CO) -O- group, -O- (CO) -O- group, and-(NH)-(CO) -O- group. The end or middle part of the alkylene skeleton Represents an organic group having 2 to 20 carbon atoms, and the group is at least one selected from the group consisting of an aryl group, an alkyl group, an aryloxy group, an alkyloxy group, an atomic group having a hetero atom, and a heterocyclic ring. A hydrogen atom may be substituted by any of the above, provided that, in R ³ , a carbon atom is bonded to a carbon atom of the nitrogen atom and carbonyl group constituting the lactam ring skeleton, provided that R ² and R ³ are At least one hydrogen atom is bonded to at least one carbon atom bonded to the nitrogen atom constituting the lactam ring skeleton among the carbon atoms constituting the N-hydroxyalkylated lactam compound. Of (meth) acrylic acid ester. Such (meth) acrylic acid esters of N-hydroxyalkylated lactam compounds may be used alone or in combination of two or more.

R ² in the general formula (1) has one or more oxygen atoms due to an ether bond in the structure of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an alkylene skeleton. Any organic group having 4 to 30 carbon atoms may be used, but the atoms bonded to the nitrogen atom constituting the lactam ring skeleton and the-(CO) -O- (ester) group constituting the (meth) acryloyl skeleton are It is a carbon atom.

Examples of the alkylene group having 1 to 10 carbon atoms include 1,2-ethylene, 1,2-propylene, 1,1-dimethyl-1,2-ethylene, 1-hydroxymethyl-1,2-ethylene, and 2-hydroxy. -1,3-propylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, 2-methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl -1,3-propylene, 2,2-dimethyl-1,4-butylene and the like.
Examples of the cycloalkylene group having 5 to 12 carbon atoms include 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene and the like.
The organic group having 4 to 30 carbon atoms and having one or a plurality of oxygen atoms due to an ether bond in the structure of the alkylene skeleton constitutes a (meth) acryloyl skeleton with a nitrogen atom constituting the lactam ring skeleton. An organic group having a structure in which one or a plurality of oxygen atoms by an ether bond is contained in the main chain of the alkylene skeleton connecting to the —O— (ester) group. For example, a structure in which two oxygen atoms due to an ether bond are included in the main chain of the alkylene skeleton is represented by the following general formula (4);

(In formula, Ar < ¹ >, Ar < ² > and Ar < ³ > are the same or different and represent a linear or branched alkylene group, and the sum total of carbon number of Ar < ¹ >, Ar < ² > and Ar < ³ > is 4-30. p represents a terminal oxygen atom of a-(CO) -O- group constituting the (meth) acryloyl skeleton in the general formula (1), and q represents a nitrogen atom constituting the lactam ring skeleton in the general formula (1). It is expressed as However, the structure of the organic group having 4 to 30 carbon atoms having one or more oxygen atoms due to an ether bond in the structure of the alkylene skeleton is not limited to the structure of the general formula (4). As long as at least one oxygen atom due to an ether bond is contained in the main chain, an oxygen atom may be contained in the side chain portion bonded to the main chain of the alkylene skeleton.

Examples of the organic group having 4 to 30 carbon atoms and having one or more oxygen atoms due to an ether bond in the structure of the alkylene skeleton include 3-oxa-1,5-pentylene, 3,6-dioxa-1,8-octylene. And 3,6,8-trioxa-1,8,11-undecylene and the like.

Among these, R ² is preferably 1,2-ethylene, 1,2-propylene, or 1,3-propylene, more preferably 1,2-ethylene or 1,2-propylene, and still more preferably Is 1,2-ethylene.

R ³ in the general formula (1) represents an alkylene group having 1 to 5 carbon atoms, or an oxygen atom, a sulfur atom, an imino group, a cycloalkylene group having 5 to 12 carbon atoms,-(CO)- At least one selected from the group consisting of a group,-(CO) -O- group, -O- (CO) -O- group, and-(NH)-(CO) -O- group, What is necessary is just to represent either the C2-C20 organic group which has in a terminal part or the middle part, The said C1-C5 alkylene group and C2-C20 organic group are an aryl group, alkyl A hydrogen atom may be substituted with at least one selected from the group consisting of a group, an aryloxy group, an alkyloxy group, a heteroatom-containing atomic group, and a heterocyclic ring, but constitutes a lactam ring skeleton Nitrogen atom and cal An atom bonded to a carbon atom of a bonyl group is a carbon atom.
Of the carbon atoms constituting R ² and R ³ , at least one hydrogen atom is bonded to at least one of the carbon atoms bonded to the nitrogen atom constituting the lactam ring skeleton, Preferably, at least one hydrogen atom is bonded to both of the carbon atoms constituting R ² and R ³ that are bonded to the nitrogen atom constituting the lactam ring skeleton.

As said aryl group, a C6-C15 aryl group is mentioned, Specifically, a phenyl group, a benzyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned.
Examples of the alkyl group include alkyl groups having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, hexyl group. Group, cyclohexyl group, 2-ethylhexyl group, octyl group, decyl group and the like.
As said aryloxy group, a C6-C15 aryloxy group is mentioned, Specifically, a phenoxy group, a benzyloxy group, a tolyloxy group, a xylyloxy group, a naphthoxy group, etc. are mentioned.
Examples of the alkyloxy group include alkyloxy groups having 1 to 12 carbon atoms, and specifically include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, amyloxy group. Group, hexyloxy group, cyclohexyloxy group, 2-ethylhexyloxy group, octyloxy group, decyloxy group and the like.
Examples of the atomic group having a heteroatom include an oxygen atom, a sulfur atom, and an imino group.
Examples of the heterocyclic ring include furan, pyrrole, pyrroline, pyrrolidine, dioxolane, prazole, imidazole, oxazole, pyran, pyridine, piperidine, dioxane, morpholine, pyrazine, and piperazine.

1 to 5 carbon atoms in which a hydrogen atom may be substituted by at least one selected from the group consisting of the aryl group, alkyl group, aryloxy group, alkyloxy group, heteroatom-containing atomic group and heterocyclic ring Examples of the alkylene group include methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,1-dimethyl-1,2-ethylene, -Methyl-1,3-propylene, 2-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,4-butylene, 1-hydroxy-methyl-1 , 2-ethylene, 2-hydroxy-1,3-propylene and the like.

An oxygen atom or sulfur atom in which a hydrogen atom may be substituted by at least one selected from the group consisting of the aryl group, alkyl group, aryloxy group, alkyloxy group, hetero atom-containing atomic group and heterocyclic ring , Imino group, cycloalkylene group having 5 to 12 carbon atoms,-(CO)-group,-(CO) -O- group, -O- (CO) -O- group, and-(NH)-(CO ) As the organic group having 2 to 20 carbon atoms having at least one selected from the group consisting of —O— groups at the terminal portion or midway portion of the alkylene skeleton, 1-oxa-1,3-propylene, 1,4 -Dioxa-1,6-hexylene, 1,4,7-trioxa-1,9-nonylene, 1-oxa-1,4-butylene, 1,5-dioxa-1,8-octylene, 1-oxa-1 , 5-pentylene, -Oxa-1,7-heptylene, 1,6-dioxa-1,10-decylene, 1-oxa-3-methyl-1,3-propylene, 1-oxa-3-methyl-1,4-butylene, -Oxa-3,3-dimethyl-1,4-butylene, 1-oxa-3,3-dimethyl-1,5-pentylene, 1,4-dioxa-3,6-dimethyl-1,6-hexylene, Oxa-2-methyl-1,3-propylene, 1,4-dioxa-2,5-dimethyl-1,6-hexylene, 1-oxa-1,5-pent-3-enylene, 1-oxa-1 , 5-pent-3-inylene, 1,1-, 1,2-, 1,3- or 1,4-cyclohexylene, 1,2- or 1,3-cyclopentylene, 1,2-, 1 , 3- or 1,4-phenylene, 4,4'-biphenylene, 1,4-di The-1,4-butylene, 1-aza-1,3-propylene, 1,4,7-triaza-1,7-heptylene, 1,4-diaza-1,6-hexylene, 1,4-diaza- 7-oxa-1,7-heptylene, 4,7-diaza-1-oxa-1,7-heptylene, 4-aza-1-oxa-1,6-hexylene, 1-aza-4-oxa-1, 4-butylene, 1-aza-1,3-propylene, 4-aza-1-oxa-1,4-butylene, 4-aza-1,7-dioxa-1,7-heptylene, 4-aza-1- Oxa-4-methyl-1,6-hexylene, 4-aza-1,7-dioxa-4-methyl-1,7-heptylene, 4-aza-1,7-dioxa-4- (2'-hydroxyethyl) ) -1,7-heptylene, 4-aza-1-oxa- (2'-hydroxyethyl) ) -1,6-hexylene, 1,4-piperazinylene and the like.

Among these, R ³ is preferably 1,4-butylene, 1,5-pentylene, or 1,3-propylene, and more preferably 1,3-propylene.

As the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1), the (meth) acrylic acid ester of the following compound is suitable.
N- (2-hydroxyethyl) -pyrrolidone, N- (2-hydroxypropyl) -pyrrolidone, N- (2 '-(2-hydroxyethoxy) -ethyl) -pyrrolidone, N- (2-hydroxyethyl) -caprolactam N- (2-hydroxypropyl) -caprolactam and (meth) acrylic acid esters of N- (2 ′-(2-hydroxyethoxy) -ethyl) caprolactam are preferably used. More preferred are N- (2-hydroxyethyl) -pyrrolidone and (meth) acrylic acid ester of N- (2-hydroxypropyl) -pyrrolidone, and still more preferred is N- (2-hydroxyethyl) -pyrrolidone. (Meth) acrylic acid ester.

As the viscosity of the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound, the viscosity at 25 ° C. is preferably 0.1 to 1500 mPa · s. If it is less than 0.1 mPa · s, not only the adjustment of the coating thickness becomes difficult, but generally the volatility becomes high and the working environment may be deteriorated. May be difficult to apply. More preferably, it is 0.2-1000 mPa * s, More preferably, it is 0.5-500 mPa * s.
In addition, the viscosity of the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound can be measured according to JIS K-6901 using, for example, a Brookfield viscometer.

In addition to the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1), the active energy ray-curable composition of the present invention has the following general formula (2);

(Wherein R ² and R ³ are the same as those in the general formula (1), but may be the same as or different from the R ² and R ³ in the general formula (1)). Containing N-hydroxyalkylated lactam compounds. Such N-hydroxyalkylated lactam compounds may be used alone or in combination of two or more.

The active energy ray-curable composition of the present invention contains an N-hydroxyalkylated lactam compound represented by the above general formula (2) in addition to the compound represented by the general formula (1). Excellent adhesion to the substrate. The reason for this is considered as follows.
The (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1) has a radical polymerizable group in the molecule, but is represented by the general formula (2). The N-hydroxyalkylated lactam compound does not have a polymerizable group. However, at least one hydrogen atom is bonded to at least one carbon atom bonded to the nitrogen atom forming the lactam ring skeleton among the carbon atoms forming R ² and R ³ in the general formula (2). Therefore, when a radical polymerization reaction is carried out using the active energy ray-curable composition of the present invention, the hydrogen atom is eliminated and a radical is generated, and N-hydroxyalkylation represented by the general formula (2) It is believed that lactam compounds can also be incorporated into the polymerization. Therefore, even when the N-hydroxyalkylated lactam compound represented by the general formula (2) having no polymerizable group is contained in a high ratio, the active energy ray-curable composition of the present invention is completely It is considered that it can be cured. From these facts, in the general formula (2), among the carbon atoms constituting R ² and R ³ , at least one of the carbon atoms bonded to the nitrogen atom constituting the lactam ring skeleton has at least one hydrogen atom. Must be joined. Preferably, among the carbon atoms constituting R ² and R ³ , both of the carbon atoms bonded to the nitrogen atom constituting the lactam ring skeleton are bonded with at least one hydrogen atom.

In addition, since the N-hydroxyalkylated lactam compound represented by the general formula (2) retains a hydroxyl group even when incorporated into a cured product by a polymerization reaction, as described later, polyethylene The adhesion to a substrate such as terephthalate will be further improved.

^{R 2} and ^{R 3} in the general formula (2) is similar to ^{R 2} and ^{R 3} in the general formula (1) may be the same as ^{R 2} and ^{R 3} in the general formula (1) , May be different. As will be described later, the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1) includes an N-hydroxyalkylated lactam compound represented by the general formula (2), ) Since it can be produced by esterification with acrylic acid or transesterification with (meth) acrylic acid ester, (meth) acrylic acid ester of N-hydroxyalkylated lactam compound and raw material for producing it When the composition containing the N-hydroxyalkylated lactam compound used as the active energy ray-curable composition of the present invention is used, R ² and R ³ in the general formula (2) are each represented by the general formula (1). ) Are the same as R ² and R ³ . On the other hand, after synthesizing and preparing a (meth) acrylic acid ester of an N-hydroxyalkylated lactam compound, an N-hydroxyalkylated lactam compound prepared separately is mixed to prepare the active energy ray-curable composition of the present invention. In this case, R ² and R ³ in general formula (2) may be different from R ² and R ³ in general formula (1).
The active energy ray-curable composition of the present invention may be obtained by any of these methods.

Examples of the N-hydroxyalkylated lactam compound represented by the general formula (2) include N- (2-hydroxyethyl) -pyrrolidone, N- (2-hydroxypropyl) -pyrrolidone, and N- (2′- (2-hydroxyethoxy) -ethyl) -pyrrolidone, N- (2-hydroxyethyl) -caprolactam, N- (2-hydroxypropyl) -caprolactam, N- (2 '-(2-hydroxyethoxy) -ethyl) caprolactam Are preferably used. N- (2-hydroxyethyl) -pyrrolidone and N- (2-hydroxypropyl) -pyrrolidone are more preferable, and N- (2-hydroxyethyl) -pyrrolidone is still more preferable.

The content of the N-hydroxyalkylated lactam compound represented by the general formula (2) is 100% by mass of the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1). On the other hand, it is preferable that it is 0.001-30 mass%. With such a content, the active energy ray-curable composition of the present invention can achieve both curability and substrate adhesion at a higher level. More preferably, it is 0.005-20 mass%, More preferably, it is 0.01-10 mass%.

In the present invention, the content of the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1) in the active energy ray-curable composition is N-hydroxyalkylated. Although it can set suitably with the kind, use, etc. of (meth) acrylic acid ester of a lactam compound, 5-99.999 mass% with respect to 100 mass% of solid content of the active energy ray-curable composition of this invention. It is preferable that With such a content, the active energy ray-curable composition of the present invention can achieve both curability and substrate adhesion at a higher level. More preferably, it is 10-99.995 mass%, More preferably, it is 15-99.99 mass%.

The (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound represented by the general formula (1) is an N-hydroxyalkylated lactam compound represented by the general formula (2), (meth) acrylic acid, Or an ester exchange reaction between the N-hydroxyalkylated lactam compound represented by the general formula (2) and a (meth) acrylic acid ester. That is, it is an active energy ray-curable composition containing a (meth) acrylic acid ester of an N-hydroxyalkylated lactam compound, and the active energy ray-curable composition has the following general formula (2);

(In the formula, R ² represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, or a carbon having one or more oxygen atoms by an ether bond in the structure of the alkylene skeleton. This represents an organic group of formula 4 to 30. However, in R ² , a carbon atom is bonded to the nitrogen atom constituting the lactam ring skeleton and the — (CO) —O— group constituting the (meth) acryloyl skeleton. R ³ represents an alkylene group having 1 to 5 carbon atoms, or an oxygen atom, a sulfur atom, an imino group, a cycloalkylene group having 5 to 12 carbon atoms, a — (CO) — group, or — (CO) —. It has at least one selected from the group consisting of O- group, -O- (CO) -O- group, and-(NH)-(CO) -O- group in the terminal part or middle part of the alkylene skeleton. Represents an organic group having 2 to 20 carbon atoms In the above group, a hydrogen atom may be substituted by at least one selected from the group consisting of an aryl group, an alkyl group, an aryloxy group, an alkyloxy group, an atomic group having a hetero atom, and a heterocyclic ring. , R ³ has a carbon atom bonded to the carbon atom of the nitrogen atom and carbonyl group constituting the lactam ring skeleton, provided that among the carbon atoms constituting R ² and R ³ , the lactam ring skeleton constitutes the lactam ring skeleton. At least one hydrogen atom is bonded to at least one of the carbon atoms bonded to the nitrogen atom.) And an N-hydroxyalkylated lactam compound represented by the following general formula (3);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) (meth) acrylic acid or (meth) acrylic acid An active energy ray-curable composition obtained by reacting with an ester is also one aspect of the present invention.

In the general formula (3), when R ⁴ is a hydrogen atom, the general formula (3) represents (meth) acrylic acid. In the present specification, (meth) acrylic acid includes Acrylic acid and methacrylic acid are included.
Further, when R ⁴ is an alkyl group having 1 to 6 carbon atoms in the above general formula (3), the general formula (3) indicates the (meth) acrylic acid esters. Examples of the (meth) acrylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, methacryl Examples include acid pentyl, hexyl acrylate, and hexyl methacrylate.
Among these, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate are preferable. More preferred are methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, and butyl methacrylate.

In the esterification reaction and transesterification reaction step, it is preferable to use a polymerization inhibitor. When a polymerization inhibitor is not used, simultaneously with the esterification reaction or transesterification reaction, the reaction raw material (meth) acrylic acid or (meth) acrylic acid ester or the reaction product N-hydroxyalkylated lactam compound There is a possibility that the polymerization of (meth) acrylic acid ester proceeds.
Examples of the polymerization inhibitor include hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, chloranil, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-tert-butylmethoxyhydroquinone. Quinone polymerization inhibitors such as 2,5-di-tert-aminohydroquinone; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethyl Phenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, 2,6-tert- Butyl-4-hydroxymethylphenol, 2,6-di-tert Butyl-2-dimethylamino-p-cresol, n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,4-bis (n-octylthio) -6 -(4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, styrinate phenol, α-tocophenol, 2-tert-butyl-6- (3'-tert-butyl) -5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert -Pentylphenyl acrylate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) 6-tert-butylphenol), 2,2'-methylenebis (6-cyclohexyl-4-methylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2 '-Ethylidenebis (2,4-di-tert-butylphenol), 2,2'-butylidenebis (2-tert-butyl-4-methylphenol), 4,4'-methylenebis (2,6-di-tert- Butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate, Triethylene glycol bis [(3-tert-butyl-5-methyl-4hydroxyphenyl)] propione N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [3- (3 ', 5'-di-tert -Butyl-4-hydroxyphenyl) propionyl] hexamethylenediamine, 2,2-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2 , 2-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl-6- (3-tert-butyl-5) -Methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxy) Benzyl) isocyanurate, tris [2- (3 ′, 5′-di-tert-butyl-4′-hydroxyhydro-cinnamoyloxyl) ethyl] isocyanurate, tris (4-tert-butyl-2,6-di) -Methyl-3-hydroxybenzyl) isocyanurate, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, calcium-bis (ethyl-3,5- Di-tert-butyl) -4-hydroxybenzyl phosphate, propyl-3,4,5-trihydroxybenzenecarbo Octyl-3,4,5-trihydroxybenzene carbonate, dodecyl-3,4,5-trihydroxybenzene carbonate, 2,2'-methylenebis (4-m-ethyl-6-tert-butylphenol) 4,4-methylenebis (2,6-di-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert) -Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl -2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetrao Alkylphenol-based polymerization inhibitors such as saspiro [5,5] undecane; alkylated diphenylamine, N, N′-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-1,3-dimethylbutyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, aldol-α- Amine polymerization inhibitors such as naphthylamine, N-phenyl-β-naphthylamine, N, N′-di-2-naphthyl-p-phenylenediamine, 4,4′-dioctyldiphenylamine, phenothiazine; copper dimethyldithiocarbamate, diethyldithiocarbamine Copper acid, copper dipropyldithiocarbamate, Copper dithiocarbamate polymerization inhibitors such as copper butyldithiocarbamate, copper ethylenedithiocarbamate, copper tetramethylenedithiocarbamate, copper pentamethylenedithiocarbamate, copper hexamethylenedithiocarbamate, copper oxydiethylenedithiocarbamate; 2, 2, 6, 6 -Tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, And N-oxyl-based polymerization inhibitors such as esters of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.
Among these, hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, 2-tert-butylhydroquinone, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, α-tocophenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, alkylated diphenylamine, phenothiazine, copper dimethyldithiocarbamate, 2,2,6,6-tetramethylpiperidine-N- Oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2 , 6,6-Tetramethylpiperidine-N-oxyl Le is preferable. More preferably, hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, phenothiazine, 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2, 6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl ester, more preferably hydroquinone, methoxyhydroquinone, 2,6-dioxy Tert-butylphenol, 1,1,3-tris (2-methyl-4-hydroxy- -Tert-butylphenyl) butane, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. These polymerization inhibitors may be used alone or in combination of two or more.

As the usage-amount of the said polymerization inhibitor, it is 0.0001-5 mass% with respect to 100 mass% of (meth) acrylic acid or (meth) acrylic acid esters represented by the said General formula (3) to be used. It is preferable. If it is less than 0.0001% by mass, a sufficient polymerization inhibitory effect may not be obtained, and if it exceeds 5% by mass, no further improvement of the polymerization inhibitory effect is observed, and there is a possibility of adverse effects. In some cases, economic efficiency may be impaired. More preferably, it is 0.0002-1 mass%, More preferably, it is 0.001-0.5 mass%, Most preferably, it is 0.005-0.1 mass%.

In the esterification reaction and transesterification reaction step, it is preferable to use a catalyst.
Examples of esterification catalysts include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and partially neutralized salts thereof; heteropolyacids such as tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid, molybdosilicic acid, and Partially neutralized salts; organic sulfonic acids such as methanesulfonic acid and paratoluenesulfonic acid; protonic acids such as organic carboxylic acids such as formic acid, acetic acid, lauric acid, and oleic acid; boron fluoride, boron chloride, aluminum chloride, dichloride A Lewis acid such as tin or tin tetrachloride; a base resin is a phenolic resin or a styrenic resin in any form of a gel type, a porous type, or a macroporous type, and includes a sulfonic acid group and an alkylsulfonic acid group. Acidic ion exchange resins containing at least one ion exchange group selected from the group consisting of: silica, alumina, zeolite , Titania, oxides such as zirconia; and the like.
Among these, hydrochloric acid, sulfuric acid, phosphoric acid, tungstophosphoric acid, paratoluenesulfonic acid, boron fluoride, and acidic ion exchange resin are preferably used. These esterification catalysts may be used alone or in combination of two or more.
The amount of the esterification catalyst used is preferably 0.001 to 20 mol% with respect to the N-hydroxyalkylated lactam compound. If the amount is less than 0.001 mol%, a sufficient reaction promoting effect may not be obtained. If the amount exceeds 20 mol%, no further improvement in the reaction promoting effect is observed, and there is a possibility of adverse effects. In some cases, economic efficiency may be impaired. More preferably, it is 0.005-15 mol%, More preferably, it is 0.01-10 mol%, Most preferably, it is 0.05-5 mol%.
Examples of the transesterification catalyst include oxides such as calcium oxide, barium oxide, lead oxide, zinc oxide, and zirconium oxide; potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, thallium hydroxide, water Hydroxides such as tin oxide, lead hydroxide, nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, nickel chloride; potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, Carbonates such as zinc carbonate and nickel carbonate; bicarbonates such as potassium bicarbonate, rubidium bicarbonate and cesium bicarbonate; sodium phosphate, potassium phosphate, rubidium phosphate, lead phosphate, zinc phosphate and nickel phosphate Phosphate such as lithium nitrate, calcium nitrate, lead nitrate, zinc nitrate, nickel nitrate Nitrate; carboxylates such as lithium acetate, calcium acetate, lead acetate, zinc acetate, nickel acetate; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, calcium methoxide, calcium ethoxide , Alkoxy compounds such as barium methoxide, barium ethoxide, tetraethoxytitanium, tetrabutoxytitanium, tetra (2-ethylhexanoxy) titanium; lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetonate, dibutoxytin Acetylacetonate complexes such as acetylacetonate and dibutoxytitanium acetylacetonate; tetramethylammonium methoxide, tetramethylammonium t-butoxide, trimethylbenzyl Quaternary ammonium alkoxides such as ammonium ethoxide; Dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide and dioctyltin oxide; Distanoxanes such as bis (dibutyltin acetate) oxide and bis (dibutyltin laurate) oxide; And dialkyltin dicarboxylates such as acetate and dibutyltin dilaurate.
Among these, tetraethoxy titanium, tetrabutoxy titanium, tetra (2-ethylhexanoxy) titanium, zirconia acetylacetonate, dibutyltin oxide, dioctyltin oxide, bis (dibutyltin acetate) oxide, bis (dibutyltin laurate) oxide, Dibutyltin diacetate and dibutyltin dilaurate are preferably used. These transesterification catalysts may be used independently and may use 2 or more types together.
The amount of the transesterification catalyst used is preferably 0.001 to 20 mol% with respect to the N-hydroxyalkylated lactam compound. If the amount is less than 0.001 mol%, a sufficient reaction promoting effect may not be obtained. If the amount exceeds 20 mol%, no further improvement in the reaction promoting effect is observed, and there is a possibility of adverse effects. In some cases, economic efficiency may be impaired. More preferably, it is 0.005-15 mol%, More preferably, it is 0.01-10 mol%, Most preferably, it is 0.05-5 mol%.

The molecular oxygen concentration in the gas phase of the reaction system in the esterification reaction and transesterification reaction step is preferably 0.01 to 10% by volume. More preferably, it is 0.02-9 volume%, More preferably, it is 0.05-8 volume%.
The range of the molecular oxygen concentration is effective in terms of yield, polymerization inhibition, explosion avoidance, and economy.
The molecular oxygen concentration can be set by supplying a gas containing molecular oxygen such as molecular oxygen or air and an inert gas such as nitrogen or argon separately to the reactor, or by mixing them in advance. Is done.

The reaction temperature in the esterification reaction and transesterification reaction step is preferably equal to or higher than the boiling point or azeotropic temperature of by-produced water or alcohol, and specifically, preferably 40 to 180 ° C. More preferably, it is 50-170 degreeC, More preferably, it is 60-160 degreeC.
As a method for removing the water or alcohol produced as a by-product, a method of performing a reaction under reduced pressure, a method of performing a reaction using an azeotropic solvent, and a method of performing a reaction in the presence of an adsorbent are suitable. Among these, a method of performing the reaction under reduced pressure and a method of performing the reaction using an azeotropic solvent are preferable.
The azeotropic solvent is not particularly limited as long as it does not inhibit the reaction. For example, ethers such as diethyl ether, diisopropyl ether, and dibutyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; pentane, hexane, heptane, And aliphatic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as chloroform, methylene chloride, 1,2-dichloroethane, and chlorobenzene. These azeotropic solvents may be used alone or in combination of two or more.
The amount of the azeotropic solvent used is that of the N-hydroxyalkylated lactam compound represented by the general formula (2) and the (meth) acrylic acid or (meth) acrylic acid ester represented by the general formula (3). It is preferable that it is 0-300 mass% with respect to the total mass. More preferably, it is 0-200 mass%, More preferably, it is 0-100 mass%. The range of the amount of the azeotropic solvent used is preferable in terms of yield and economy.
In the case of transesterification, excessively used (meth) acrylic acid esters can be used as an azeotropic solvent.
The reaction pressure in the esterification reaction and transesterification reaction step may be any of normal pressure, increased pressure, and reduced pressure. Moreover, what is necessary is just to set reaction time suitably so that the said reaction may be completed.
In the step of removing light boiling components from the reaction system of the esterification reaction and transesterification reaction, examples of the method for removing light boiling components include a method of evaporating at normal pressure and a method of distillation under reduced pressure. Among these, the method of distilling under reduced pressure is preferable.
In addition, a light boiling part is N-- represented by the (meth) acrylic acid ester of N-hydroxyalkylated lactam compound represented by General formula (1) and / or General formula (2) which exist in a reaction system. It means a compound having a boiling point lower than that of the hydroxyalkylated lactam compound, and includes by-product water or alcohol, raw material (meth) acrylic acid or (meth) acrylic acid esters, azeotropic solvent, and the like.
What removed the light boiling part from the reaction system of the said esterification reaction and transesterification reaction may be refine | purified by methods, such as neutralization, filtration, water washing, and vacuum distillation, as needed. These methods may be implemented in combination. Among these, purification by vacuum distillation is preferable.

In the present invention, a polymerizable monomer other than the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound is used together with the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound and the N-hydroxyalkylated lactam compound. May be. As such a polymerizable monomer, any monomer having compatibility with (meth) acrylic acid ester of N-hydroxyalkylated lactam compound and N-hydroxyalkylated lactam compound may be used. Monofunctional or polyfunctional radical polymerization 1 type or 2 types or more can be selected as appropriate. The polymerizable monomer other than the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound is preferably a liquid substance having a viscosity at 25 ° C. of 1000 mPa · s or less.

As the polymerizable monomer other than the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound, the following compounds are suitable.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Acrylate, cyclohexylmethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethyl Monofunctional (meth) acrylates such as ruaminoethyl (meth) acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, butyl α-hydroxymethylacrylate; N, N-dimethyl (meth) acrylamide, N -Monofunctional (meth) acrylamides such as methylol (meth) acrylamide.

Monofunctional N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-N-methylformamide, N-vinylimidazole, N-vinylformamide, N-vinylacetamide; styrene, α-methylstyrene, Monofunctional vinyl compounds such as vinyl toluene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate; maleic anhydride, maleic acid, dimethyl maleate, diethyl maleate, monomethyl maleate, monoethyl maleate, fumaric acid, Dimethyl fumarate, diethyl fumarate, monomethyl fumarate, monoethyl fumarate, itaconic anhydride, itaconic acid, dimethyl itaconate, diethyl itaconate, monomethyl itaconate, monoethyl itaconate, methylenemalonic acid, dimethylmethylenemalonate Methylene malonic acid monomethyl, cinnamic acid, methyl cinnamate, ethyl cinnamate, monofunctional alpha, beta-unsaturated compound such as crotonic acid, methyl crotonate, ethyl crotonate.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide added trimethylolpropane tri (meth) acrylate, ethylene oxide added ditri Multifunctional (meth) acrylates such as methylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate; 2-vinyloxyethyl (meth) acrylate, ( (Meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4-vinyloxybutyrate Vinyl ether group-containing (meth) such as 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate Acrylates.
Among these, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Cold di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane Tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate , Ethylene oxide-added pentaerythritol tetra (meth) acrylate, polyfunctional (meth) acrylates such as ethylene oxide-added dipentaerythritol hexa (meth) acrylate, (meth) acrylic acid 4-vinyloxybutyl, (meth) acrylic acid 2- ( Vinyloxyethoxy) ethyl is preferred.

The active energy ray-curable composition of the present invention comprises a (meth) acrylate ester of an N-hydroxyalkylated lactam compound having a radically polymerizable group in the molecule, so that it can be cured by irradiation with active energy rays. A cured product can be obtained by mixing with a curable resin having at least one radical polymerizable group. Such an active energy ray-curable resin composition comprising the curable resin and the active energy ray-curable composition of the present invention, wherein the curable resin has at least one radical polymerizable group. An active energy ray-curable resin composition having the above is also one aspect of the present invention. Further, the active energy ray-curable composition of the present invention or a cured product obtained by curing the active energy ray-curable resin composition, that is, a cured product obtained by curing the composition of the present invention is also present. It is one of the inventions.

The curable resin is cured by irradiation with an active energy ray, and as such a curable resin, a macromonomer or a prepolymer having at least one radical polymerizable group can be used.

As the viscosity of the curable resin, the lower limit of the viscosity is preferably higher than 1.5 Pa · s at 25 ° C., and the upper limit is preferably 100,000 Pa · s or less at 80 ° C. If it is 1.5 Pa · s or less at 25 ° C, it may be difficult to impart thixotropy necessary to prevent sagging in applications such as paint, and if it exceeds 100,000 Pa · s at 80 ° C, the viscosity is high. It may be difficult to apply. The lower limit is more preferably 10 Pa · s or more at 25 ° C., further preferably 50 Pa · s or more, and the upper limit is more preferably 10,000 Pa · s or less at 80 ° C., further preferably 5000 Pa · s or less.
In addition, the viscosity of curable resin can be measured similarly to the viscosity of the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound mentioned above.

The molecular weight of the curable resin is preferably 300 to 1,000,000. If it is less than 300, not only does the strength physical properties of the cured coating film become brittle, but it may be difficult to impart thixotropy necessary for sagging prevention in applications such as paint, and if it exceeds 1000000, the viscosity is high. It may be difficult to apply. More preferably, it is 350-500000, More preferably, it is 400-100000, Most preferably, it is 450-50000.
In addition, the molecular weight in the said curable resin means a number average molecular weight.
The number average molecular weight can be measured by gel permeation chromatography (GPC) in terms of polystyrene under the following apparatus and measurement conditions.
High-speed GPC apparatus: Measured using HLC-8220 GPC (manufactured by Tosoh Corporation).
Measurement condition:
Developing solvent THF (tetrahydrofuran)
Column TSK-gel GMHXL x 2 eluent flow rate 1 ml / min
Column temperature 40 ° C

Examples of the curable resin include saturated or unsaturated polybasic acids or anhydride acids thereof (for example, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, etc.), saturated or Unsaturated polyhydric alcohols (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, polyethylene glycol, polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol, etc.) and (meth) acrylic acid, a saturated or unsaturated polyester alkyd; a saturated or unsaturated polyhydric alcohol (for example, ethylene glycol, Neopentyl glycol, poly Tramethylene glycol, polyester polyol, polycaprolactone polyol, etc.), organic polyisocyanate (eg, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.), and hydroxyl group-containing (meth) acrylate (eg, 2-hydroxyethyl (meth)) Urethane (meth) acrylate obtained by reaction with acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc .; obtained by reaction of polysiloxane with (meth) acrylic acid Polysiloxane (meth) acrylate; polyamide (meth) acrylate obtained by reaction of polyamide with (meth) acrylic acid; epoxy resin (for example, phenol novolac epoxy resin, Resole novolak epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, polybutanediene modified epoxy resin, alicyclic epoxy resin, brominated phenol novolac epoxy resin, brominated bisphenol A type epoxy Epoxy (meth) acrylate alkyd obtained by reaction of (meth) acrylic acid with resin, amino group-containing epoxy resin, etc .; the above epoxy (meth) acrylate alkyd and polybasic acid anhydride (for example, maleic anhydride, succinic anhydride) Suitable examples include carboxylic acid-modified epoxy (meth) acrylates obtained by reaction with acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like. As said curable resin, 1 type (s) or 2 or more types can be used.

As a mixing ratio of the active energy ray-curable composition containing the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound of the present invention and the curable resin, (meth) acrylic acid of the N-hydroxyalkylated lactam compound is used. Although it will be set as appropriate according to the type and combination of the ester, N-hydroxyalkylated lactam compound and curable resin, the use of the curable resin composition, etc., the active energy with respect to 100 parts by mass of the curable resin. The blending ratio of the linear curable composition is preferably 5 to 100 parts by mass. If it is less than 5 parts by mass, the viscosity of the curable resin composition may be high and it may be difficult to apply. If it exceeds 100 parts by mass, the physical properties of the cured product obtained by curing the curable resin composition are activated. Since there is a possibility that the polymer of the energy ray curable composition may dominate, it is not preferable. More preferably, it is 10-95 mass parts, More preferably, it is 15-90 mass parts, Most preferably, it is 20-85 mass parts.

As a viscosity of the said active energy ray curable resin composition, it is preferable that the viscosity in 25 degreeC is 0.5-100000 mPa * s. If it is less than 0.5 mPa · s, the coating thickness may be uneven, and if it exceeds 100,000 mPa · s, the viscosity may be high and coating may be difficult. More preferably, it is 1-10000 mPa * s, More preferably, it is 2-5000 mPa * s.
In addition, the viscosity of an active energy ray-curable resin composition can be measured similarly to the viscosity of the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound described above.

The active energy ray-curable resin composition of the present invention preferably contains a photopolymerization initiator as necessary. It is also preferable to add a photosensitizer, a photopolymerization accelerator and the like.

As said photoinitiator, the photoradical polymerization initiator which generate | occur | produces a polymerization initiation radical by irradiation of an active energy ray is used suitably.
Examples of the radical photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Acetophenones such as butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. The benzo Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium Benzophenones such as chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy -3 Thioxanthones such as 4-dimethylaminopyridine -9H- thioxanthone-9-Onmesokurorido. Among these, acetophenones, benzophenones, and acyl phosphine oxides are preferable. Particularly preferred are 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one. Used for. As a photoinitiator, these may be used independently and 2 or more types may be used together.

The total amount of the photopolymerization initiator added is preferably 0.05 to 20% by mass with respect to 100% by mass of the active energy ray-curable resin composition. If it is less than 0.05% by mass, sufficient curing may not be obtained, and if it exceeds 20% by mass, no further improvement in the physical properties of the cured product is observed, and there is a possibility that it may adversely affect the economy. Sexuality may be impaired. More preferably, it is 0.1-15 mass%, More preferably, it is 0.2-10 mass%.

As the photosensitizer, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone are preferably used. A photosensitizer may be used independently and may use 2 or more types together.

The total amount of the photosensitizer added is preferably 0.05 to 20% by mass with respect to 100% by mass of the active energy ray-curable resin composition. If it is less than 0.05% by mass, sufficient curing may not be obtained, and if it exceeds 20% by mass, no further improvement in the physical properties of the cured product is observed, and there is a possibility that it may adversely affect the economy. Sexuality may be impaired. More preferably, it is 0.1-15 mass%, More preferably, it is 0.2-10 mass%.

Examples of the photopolymerization accelerator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid- 2-n-butoxyethyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-dimethylaminobenzophenone, and 4,4′-diethylaminobenzophenone are preferred. Among these, triethanolamine, methyldiethanolamine, and triisopropanolamine are preferably used. These may be used alone or in combination of two or more.

The total amount of the photopolymerization accelerator added is preferably 0.05 to 20% by mass with respect to 100% by mass of the active energy ray-curable resin composition. If it is less than 0.05% by mass, sufficient curing may not be obtained, and if it exceeds 20% by mass, no further improvement in the physical properties of the cured product is observed, and there is a possibility that it may adversely affect the economy. Sexuality may be impaired. More preferably, it is 0.1-15 mass%, More preferably, it is 0.2-10 mass%.

When the photopolymerization initiator, photosensitizer, photopolymerization accelerator and the like are added in combination, the total amount is 0.05 to 20 mass with respect to 100 mass% of the active energy ray-curable resin composition. % Is preferred. More preferably, it is 0.1-15 mass%, More preferably, it is 0.2-10 mass%.

The active energy ray curable composition and the active energy ray curable resin composition of the present invention include a reduction in toxicity, viscosity adjustment, coloring with aqueous stain, impregnation into a polar substrate, improvement of wettability to a polar substrate, and curing. Water can be further blended for the purpose of improving the property or improving the economy. The water content is preferably 0.01 to 1000 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition or active energy ray-curable resin composition of the present invention. Below this range, the above-described excellent effects may not be sufficiently exhibited. Moreover, when this range is exceeded, there exists a possibility that the excessive hardening time and energy for evaporating water at the time of hardening may be needed. More preferably, it is 0.02-500 mass parts, More preferably, it is 0.05-200 mass parts. As a method for adding water, water may be added in advance to the active energy ray-curable composition or curable resin, or water is added after preparing the active energy ray-curable resin composition. May be. In addition, the form of water in the composition may be a composition compatible with the composition, a so-called water-soluble composition, or a suspension (dispersion) or emulsification (emulsion) composition.

The active energy ray-curable resin composition of the present invention further includes an inorganic filler, a non-reactive resin (for example, acrylic polymer, polyester, polyurethane, polystyrene, polyvinyl chloride, etc.), an organic solvent as an additive, if necessary. , Color pigments, plasticizers, polymerization inhibitors, basic compounds, UV absorbers, antioxidants, matting agents, dyes, antifoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers Further, a thixotropic agent, a thixotropic agent and the like can be added. The presence or absence of these additives does not particularly affect the effects of the present invention. These may be used alone or in combination of two or more.

The amount of the additive added to the entire active energy ray curable resin composition of the present invention includes the type of additive, the purpose of use of the additive, the use of the active energy ray curable resin composition, and the active energy ray curable resin. It is set as appropriate depending on the method of use of the composition.

For example, the amount of the inorganic filler added is preferably 1 to 800% by mass and more preferably 10 to 600% by mass with respect to 100% by mass of the active energy ray-curable resin composition. Preferably, it is 20-500 mass%.

As said non-reactive resin, an organic solvent, a color pigment, a plasticizer, and an auxiliary | assistant change agent, the addition amount shall be 1-40 mass% with respect to 100 mass% of active energy ray-curable resin compositions. Preferably, it is 5-30 mass%, More preferably, it is 10-25 mass%.

As the UV absorber, antioxidant, matting agent, dye, antifoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, auxiliary agent, the amount added is active. It is preferable that it is 0.0001-5 mass% with respect to 100 mass% of energy-beam curable resin compositions, It is more preferable that it is 0.001-3 mass%, It is 0.01-1 mass%. More preferably.

The active energy ray-curable resin composition of the present invention can be obtained by blending ingredients such as an active energy ray-curable composition, a curable resin, and other additives, and heating, dissolving, and mixing. The obtained active energy ray-curable resin composition of the present invention can be applied by hand, such as brush coating, roll coating, gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, spraying depending on the purpose of use. It can apply | coat to a base material by well-known methods, such as coating and a dipping method. As an application quantity, 0.2-100 g / m < ² > is preferable and 0.5-70 g / m < ² > or more is more preferable.

Examples of the base material include iron, aluminum, steel plate, tin-free steel plate, tin plate, polyethylene terephthalate film laminated steel plate, etc .; concrete; polyethylene, polypropylene, polyacryl, polyethylene terephthalate, polycarbonate, polyamide, polyimide, nylon, Resin moldings and films such as polyvinyl chloride and polyvinylidene chloride; coated papers such as polyethylene-coated paper and polyethylene terephthalate-coated paper; papers such as uncoated paper; wood is preferred.

The active energy ray-curable resin composition of the present invention can be cured by irradiation with active energy rays. Examples of active energy rays used include electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, gamma rays and the like. Can be mentioned. In particular, ultraviolet rays and electron beams are preferable because they can improve the flexibility and work adhesion of the cured product.

In the case of curing with ultraviolet rays, it is preferable to use a light source including light within a wavelength range of 150 to 450 nm. As such a light source, a solar ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like is preferable. Together with these light sources, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

In the case of curing with the electron beam, it is preferable to use an electron beam having an acceleration voltage in the range of 10 to 500 kV. More preferably, it is 20-300 kV, More preferably, it is 30-200 kV. Moreover, as irradiation amount, 2-500 kGy is preferable, 3-300 kGy is more preferable, 5-200 kGy is still more preferable. Along with an electron beam, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

The active energy ray-curable resin composition of the present invention includes an adhesive, an adhesive, a biomaterial, a dental material, an optical member, an information recording material, an optical fiber material, a resist material, an insulator, a sealing material, an ink, and an inkjet ink. , Printing ink, screen printing ink, paint, casting material, decorative board, WPC, coating material, photosensitive resin plate, dry film, lining material, civil engineering and building material, putty, repair material, flooring material, paving material gel coat, over It can be used in a wide range of applications such as coating, hand lay-up, spray-up, pultrusion, filament winding, SMC, BMC, and other molding materials, sheets, plasma display partition walls, and polymer solid electrolytes.
Among these, ink, inkjet ink, printing ink, screen printing ink, paint, optical fiber materials, adhesives, adhesives, sealing materials, photosensitive resin plates, dry films, molding materials, civil engineering and building materials, automobiles, etc. It is suitably used in application fields such as for vehicles.

When the active energy ray-curable resin composition of the present invention is used for coating applications, various fillers such as talc, mica, alumina, silica, and aluminum hydroxide can be added as necessary. In the case of a colored paint, pigments, dyes, dispersants and the like can be added in addition to the filler. The paint thus obtained is one of the preferred embodiments of the present invention. Such a coating material is applied to the above-mentioned various base materials and the like, and can be cured by irradiation with active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, and gamma rays as necessary.

When the active energy ray-curable resin composition of the present invention is used for ink applications, a binder such as a resin, various fillers, pigments, dyes, dispersants and the like can be added as necessary. The ink thus obtained is one of the preferred embodiments of the present invention. Such ink is applied on metal, paper, resin, and other substrates, and irradiated with active energy rays such as electromagnetic energy, ultraviolet rays, visible rays, infrared rays, electron beams, and gamma rays as necessary. Can be cured. It is particularly preferable to cure with light rays such as ultraviolet rays, visible rays, and near infrared rays.

When the active energy ray-curable resin composition of the present invention is used for adhesives or pressure-sensitive adhesives (hereinafter referred to as “adhesives”), it is possible to impart tackiness such as tackifiers as necessary. Agents, various fillers, pigments, dyes, dispersants and the like can be added. The adhesive thus obtained is one of the preferred embodiments of the present invention. Such adhesives are coated on metal, paper, resin, and other substrates, and if necessary, active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, gamma rays, etc. It can be cured by irradiation with energy rays. It is particularly preferable to cure with light rays such as ultraviolet rays, visible rays, and near infrared rays.

When the active energy ray-curable resin composition of the present invention is used for curable molding material applications, various fillers, pigments, dyes, dispersants, and the like can be added as necessary. The curable molding material thus obtained is one of the preferred embodiments of the present invention. Such a curable molding material can be used as it is or impregnated in a reinforcing fiber such as glass fiber, carbon fiber, or aramid fiber, and can be used as required by electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams. It can be cured and shaped by irradiation with active energy rays such as active energy rays such as gamma rays. In particular, it is preferable to cure and shape with a highly transmissive electron beam, visible light, near infrared light or the like.

Since the active energy ray-curable composition and the active energy ray-curable resin composition of the present invention are composed of the above-described configuration and are capable of achieving both high curability and substrate adhesion, It can be used in a wide variety of applications.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
The operations of Examples and Comparative Examples described below were performed as many times as necessary in the Examples and Comparative Examples.

In the following examples and comparative examples, various physical properties were measured as follows.
<UV curability>
Each active energy ray curable composition or active energy ray curable resin composition is applied onto a glass plate (size 150 mm × 100 mm) using a bar coater so as to have a thickness of 100 μm. Company conveyor belt UV irradiation device, trade name “UB031-5BM”, 80 W ultra high pressure mercury lamp, conveyor speed: 15 m / min, distance from light source: 10 cm, irradiation energy amount per pass: 125 mJ / cm ² ) And cured by UV irradiation. The adhesiveness of the coating surface was confirmed by finger touch, and the number of passes until the tackiness disappeared was measured.

<Solvent resistance>
The cured coating film cured with an irradiation energy of 3.5 J / cm ² was rubbed 10 times with gauze soaked with acetone and finally 50 times, and the gloss change of the coating film surface was visually evaluated (gauze). Was counted as one round trip.) The case where the gloss did not change was rated as ◯, the case where the gloss was slightly lowered was marked as Δ, and the case where the gloss was completely lost was marked as x.

<Adhesion>
Each active energy ray curable composition or active energy ray curable resin composition was applied to a thickness of 100 μm using a bar coater on a PET film (size 100 mm × 100 mm), and 3.5 J / cm ² . The cured coating film cured by irradiation energy is cross-cut into 100 squares at 1 mm intervals, and a cellophane tape is applied to the part and adhered sufficiently, and then the cellophane tape is peeled off at 90 degrees. Evaluation was made from the degree of adhesion to the substrate. The evaluation criteria are as follows.
Evaluation criteria A: No peeling.
○: There was peeling of less than 5%.
Δ +: There was peeling of 5% or more and less than 15%.
Δ: There was peeling of 15% or more and less than 35%.
Δ-: There was peeling of 35% or more and less than 65%.
X: There was peeling of 65% or more.

Example 1
N- (2-hydroxyethyl) -pyrrolidone in a 2 L reaction kettle equipped with an Oldershaw rectification column (10 stages) having a stirrer, thermometer holder, liquid input line, gas injection line, thermometer holder and pressure reducing line (HEP) 500 g, methyl acrylate 1166 g, methoxyhydroquinone 5 g and dibutyltin oxide 5 g were added. 7 vol% oxygen gas (nitrogen balance) was stirred and mixed while blowing into the liquid phase, and the temperature was raised. The temperature at the top of the rectifying column is maintained at the azeotropic temperature of methyl acrylate-methanol, and by-produced methanol is removed out of the system as an azeotropic solution of methyl acrylate-methanol. An amount of methyl acrylate was continuously supplied from the liquid charging line. Stirring was carried out for 9 hours from the start of heating. As a result of analysis by GC, the yield of 2-pyrrolidinoethyl acrylate (PEA) was 97%. Under reduced pressure, unreacted methyl acrylate and by-product methanol were removed from the top of the column to the outside of the reaction system. Subsequently, a composition comprising 570 g of 2-pyrrolidinoethyl acrylate and 11 g of N- (2-hydroxyethyl) -pyrrolidone was obtained from the top of the column.

(Preparation Example 1)
100 g of the composition obtained in Example 1 was further treated by silica gel column chromatography using a mixed solvent of hexane / acetone = 98/2 (volume ratio) as an eluent to obtain 64 g of pure 2-pyrrolidinoethyl acrylate. Got.

(Example 2)
Except that methyl acrylate was changed to 1356 g of methyl methacrylate, the same operation as in Example 1 was carried out, and a composition consisting of 577 g of 2-pyrrolidinoethyl methacrylate (PEM) and 9 g of N- (2-hydroxyethyl) -pyrrolidone. The product was obtained from the top of the tower. The temperature at the top of the rectifying column during the reaction was maintained at the methyl methacrylate-methanol azeotropic temperature, and the by-product methanol was removed out of the system as an azeotropic solution of methyl methacrylate-methanol. The same amount of methyl methacrylate as that of methyl methacrylate was continuously supplied from the liquid charging line.

(Preparation Example 2)
100 g of the composition obtained in Example 2 was further treated by silica gel column chromatography using a mixed solvent of hexane / acetone = 98/2 (volume ratio) as an eluent to obtain 71 g of pure 2-pyrrolidinoethyl methacrylate. Got.

<Preparation of active energy ray-curable composition>
(Example 3)
A polymerization inhibitor was added to the composition obtained in Example 1 according to the formulation shown in Table 1 to produce an active energy ray-curable composition a.
Example 4
A polymerization inhibitor was added to the composition obtained in Example 2 according to the formulation shown in Table 1 to produce an active energy ray-curable composition b.
(Examples 5 to 12)
N- (2-hydroxyethyl) -pyrrolidone and a polymerization inhibitor were added to 2-pyrrolidinoethyl acrylate obtained in Preparation Example 1 according to the formulation shown in Table 1, respectively, and active energy ray-curable composition c, d, e, f, g, h, i and j were prepared.
(Examples 13 and 14)
N- (2-hydroxyethyl) -pyrrolidone and a polymerization inhibitor were added to 2-pyrrolidinoethyl methacrylate obtained in Preparation Example 2 according to the formulation shown in Table 1, respectively, and active energy ray-curable composition k and 1 was produced.

(Comparative Example 1)
A polymerization inhibitor was added to the pure 2-pyrrolidinoethyl acrylate obtained in Preparation Example 1 according to the formulation shown in Table 1 to produce a comparative active energy ray-curable composition (Comparative a).
(Comparative Example 2)
A polymerization inhibitor was added to the pure 2-pyrrolidinoethyl methacrylate obtained in Preparation Example 2 according to the formulation shown in Table 1 to produce a comparative active energy ray-curable composition (Comparative b).
The formulations of Examples 3 to 14 and Comparative Examples 1 and 2 are shown in Table 1.
In addition, the symbol in Table 1 is as follows.
PEA: 2-pyrrolidinoethyl acrylate PEM: 2-pyrrolidinoethyl methacrylate HEP: N- (2-hydroxyethyl) -pyrrolidone MHQ: methoxyhydroquinone

<Evaluation of physical properties of active energy ray-curable composition>
(Examples 15 to 26, Comparative Examples 3 and 4)
The active energy ray-curable composition and the photopolymerization initiator were mixed according to the formulation shown in Table 2 to prepare active energy ray-curable compositions, and the curability, solvent resistance, and adhesion of each composition were evaluated. .
Their formulation and evaluation results are shown in Table 2.
In addition, the symbol in Table 2 is as follows.
184: Photoradical polymerization initiator Irgacure 184 (trade name, manufactured by BASF SE); 1-hydroxy-cyclohexyl-phenyl-ketone)
907: Photo radical polymerization initiator Irgacure 907 (trade name, manufactured by BASF SE, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one)

<Preparation and physical property evaluation of active energy ray-curable resin composition>
(Examples 27-35, Comparative Examples 5-7)
An active energy ray-curable composition, a curable resin, and a photopolymerization initiator are mixed according to the formulation shown in Table 3 to prepare an active energy ray-curable resin composition, and the curability, solvent resistance, and Adhesion was evaluated.
Their composition and evaluation results are shown in Table 3.
In addition, the symbol in Table 3 is as follows.
7550B: UV-7550B (trade name, manufactured by Nippon Synthetic Chemical Co., Inc .; urethane acrylate)
G-105: G-105 (trade name, manufactured by Japan Composite; unsaturated polyester alkyd)
RF-711B: RF-711B (trade name, manufactured by Japan Composite; epoxy acrylate alkyd)
184: Photoradical polymerization initiator Irgacure 184 (trade name, manufactured by BASF SE); 1-hydroxy-cyclohexyl-phenyl-ketone)

The following was found from the results of the above Examples and Comparative Examples.
In the active energy ray-curable composition containing the (meth) acrylic acid ester of the N-hydroxyalkylated lactam compound, the N-hydroxyalkylated lactam compound having a specific structure is allowed to coexist, thereby improving the curability and resistance of the composition. It was found that a solvent composition and substrate adhesion could be further improved, and a composition capable of achieving both of these performances at a high level was obtained.
In the above examples, 2-pyrrolidinoethyl acrylate or 2-pyrrolidinoethyl methacrylate is used as the N-hydroxyalkylated lactam compound, and N- (2-hydroxyethyl)-is used as the N-hydroxyalkylated lactam compound. Pyrrolidone is used, but in an active energy ray-curable composition containing a (meth) acrylic acid ester of an N-hydroxyalkylated lactam compound, the presence of the N-hydroxyalkylated lactam compound having a specific structure Since all the mechanisms in which the effects are manifested are the same, the present invention can be applied in various forms disclosed in the present specification based on the results of the above-described Examples and Comparative Examples, and advantageous effects can be exhibited. It can be said.

Claims (4)

An active energy ray-curable composition comprising a (meth) acrylic acid ester of an N-hydroxyalkylated lactam compound,
The active energy ray-curable composition has the following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, or represents an oxygen atom formed by an ether bond. Represents an organic group having 4 to 30 carbon atoms having one or more in the structure of the alkylene skeleton, provided that in R ² , the nitrogen atom constituting the lactam ring skeleton and the (meth) acryloyl skeleton are constituted — (CO) — A carbon atom is bonded to the O- group, R ³ represents an alkylene group having 1 to 5 carbon atoms, or an oxygen atom, a sulfur atom, an imino group, a cycloalkylene group having 5 to 12 carbon atoms, At least one selected from the group consisting of-(CO)-group,-(CO) -O- group, -O- (CO) -O- group, and-(NH)-(CO) -O- group. The end or middle part of the alkylene skeleton Represents an organic group having 2 to 20 carbon atoms, and the group is at least one selected from the group consisting of an aryl group, an alkyl group, an aryloxy group, an alkyloxy group, an atomic group having a hetero atom, and a heterocyclic ring. A hydrogen atom may be substituted by any of the above, provided that, in R ³ , a carbon atom is bonded to a carbon atom of the nitrogen atom and carbonyl group constituting the lactam ring skeleton, provided that R ² and R ³ are At least one hydrogen atom is bonded to at least one carbon atom bonded to the nitrogen atom constituting the lactam ring skeleton among the carbon atoms constituting the N-hydroxyalkylated lactam compound. (Meth) acrylic acid ester of the following general formula (2);

(Wherein R ² and R ³ are the same as those in the general formula (1), but may be the same as or different from the R ² and R ³ in the general formula (1)). An active energy ray-curable composition comprising the N-hydroxyalkylated lactam compound. An active energy ray-curable composition comprising a (meth) acrylic acid ester of an N-hydroxyalkylated lactam compound,
The active energy ray-curable composition has the following general formula (2):

(In the formula, R ² represents an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, or a carbon having one or more oxygen atoms by an ether bond in the structure of the alkylene skeleton. This represents an organic group of formula 4 to 30. However, in R ² , a carbon atom is bonded to the nitrogen atom constituting the lactam ring skeleton and the — (CO) —O— group constituting the (meth) acryloyl skeleton. R ³ represents an alkylene group having 1 to 5 carbon atoms, or an oxygen atom, a sulfur atom, an imino group, a cycloalkylene group having 5 to 12 carbon atoms, a — (CO) — group, or — (CO) —. It has at least one selected from the group consisting of O- group, -O- (CO) -O- group, and-(NH)-(CO) -O- group in the terminal part or middle part of the alkylene skeleton. Represents an organic group having 2 to 20 carbon atoms In the above group, a hydrogen atom may be substituted by at least one selected from the group consisting of an aryl group, an alkyl group, an aryloxy group, an alkyloxy group, an atomic group having a hetero atom, and a heterocyclic ring. , R ³ has a carbon atom bonded to the carbon atom of the nitrogen atom and carbonyl group constituting the lactam ring skeleton, provided that among the carbon atoms constituting R ² and R ³ , the lactam ring skeleton constitutes the lactam ring skeleton. At least one hydrogen atom is bonded to at least one of the carbon atoms bonded to the nitrogen atom.) And an N-hydroxyalkylated lactam compound represented by the following general formula (3);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) (meth) acrylic acid or (meth) acrylic acid An active energy ray-curable composition obtained by reacting with an ester. An active energy ray-curable resin composition comprising the active energy ray-curable composition according to claim 1 or 2 and a curable resin, wherein the curable resin has at least one radical polymerizable group. An active energy ray-curable resin composition. Hardened | cured material formed by hardening | curing the composition of Claim 1, 2 or 3.