JP2000109454A - Vinyl group-containing polyfunctional compound, production method thereof and curable composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide excellent curability and low viscosity, to provide sufficient coating film performance, and to reduce the compounding ratio of low molecular weight compounds having performance problems. An object is to provide a vinyl group-containing polyfunctional compound. A vinyl group-containing polyfunctional compound represented by the following general formula (1), in which two or more are organic residues containing a polymerizable unsaturated group and have two or more tertiary or secondary amino groups: . Embedded image (In the formula, R ¹ is a bonding group, and R ² is an organic residue containing a polymerizable unsaturated group.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent curability and fluidity and is used in a wide range of fields as a film-forming material such as paints and inks, or as a raw material for sealants, molding agents, adhesives and adhesives. The present invention relates to a vinyl group-containing polyfunctional compound capable of obtaining a cured product by heat or active energy rays, a method for producing the same, and a curable composition containing the same.

[0002]

2. Description of the Related Art Conventionally, paints, adhesives, adhesives, inks,
Resin solutions containing organic solvents have been used for fillers and molding materials. These resin solutions scatter a large amount of organic solvent in the coating, filling and curing / drying steps. With increasing interest in the global and working environments, restrictions on the use of such resin solutions have been added. As one of the methods, development of resin materials such as water-soluble resin, powder, and hot melt has been promoted. Aqueous resin compositions require a large amount of heat to evaporate water as a dispersion medium, and often contain a small amount of organic solvent in order to further improve coatability, leaving a problem in terms of waste liquid treatment. I have. Further, in the case of coating and filling of powder or hot melt, a new equipment has to be introduced because the method of coating and filling is greatly different from the conventional coating and filling equipment. In order to solve the above-mentioned problems, high solidification of the resin solution,
Improvements in water-soluble resins are being made, and it is thought that such efforts will tend to further reduce the amount of resin solution used in the future. However, as a fundamental solution, there has been a strong demand for the development of a solventless liquid resin composition that can be widely applied without problems of pollution, safety and health, ignition, explosion, etc., and that can be easily applied and filled. I have.

A typical example of a solventless liquid resin composition is an active energy ray-curable composition. Conventional active energy ray-curable compositions include low-viscosity monomers such as various acrylate monomers, and reactive oligomers such as urethane acrylate, epoxy acrylate, or ester acrylate, and other resin components as necessary. And so on. Low-viscosity monomers are mainly used as reactive diluents for the purpose of controlling the viscosity of the composition, but if they are contained in a large amount, the volume shrinkage during curing is large, and the cured coating film is fragile. Odors and the like due to residual monomers in the coating film have been regarded as a problem. Therefore, improvements such as reduction of the amount of the reactive diluent used and increase in the molecular weight have been desired.

[0004] In order to improve the mechanical performance of the cured product, it is preferable to blend a polyfunctional reactive diluent, a reactive oligomer, and a high-molecular-weight resin material. Therefore, in consideration of the flow characteristics of the composition before curing, a large amount of a reactive diluent must be blended, and the blending amount is limited. Therefore, the cured product obtained by curing the conventional solventless liquid resin composition has poor cured product properties such as hardness, toughness, mechanical properties, and chemical resistance, and is practically a solvent-based or water-based resin composition. It was a property far below. Active energy ray-curable compositions containing high-molecular-weight reactive oligomers and resin materials have also been developed for the purpose of improving coating film performance. At present, it is difficult to say that environmental improvements have been made by using a water-soluble diluent or an organic solvent.

In recent years, with the progress of research on polymers having a highly branched structure such as combs, stars, and dendrimers, dendrimers having a methacrylic group at the end thereof have been studied (Ref. Shi W. et. .al., J Appl Polym Sci, 5
9,12,1945 (1996)., Moszner N.et.al., Macromol chem p.
hys, 197, 2,621 (1996). JP-A-8-231864). However, the known compounds did not provide sufficient curability as a radiation-curable material. Also, the viscosity is certainly lower than that of the linear compound having the same molecular weight, but it cannot be said that the viscosity is sufficiently achieved.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the blending ratio of low molecular weight compounds having excellent curability and low viscosity, having sufficient coating properties, and having problems in performance. It is an object of the present invention to provide a vinyl group-containing polyfunctional compound that enables the following.

[0007]

[Means for Solving the Problems]

The present inventor has conducted intensive studies on the correlation between the structure and the viscosity of various resin systems in order to solve the above-mentioned problems. As a result, general linear polymers were replaced with comb polymers, and moreover, multi-branched polymers. By changing the molecular structure of the polymer, it was found that the viscosity was low even though the molecular weight was high, and that many terminal functional groups such as polymerizable vinyl groups could be introduced into one molecule. Furthermore, the inventors have found that a tertiary amino group-containing branched site in the molecule enables curing at a high speed without impairing the performance of the coating film, and the present invention has been accomplished. That is, the present invention relates to a vinyl group-containing polyfunctional compound represented by the following general formula (1) and containing two or more polymerizable unsaturated groups.

[0009]

Embedded image

(In the formula (1), R1 is an organic residue represented by the following general formula (2-1), and R2 is the following general formulas (3-1a) to (3-1e)
Or an organic residue containing a branch site represented by (5-1a) to (5-1c). )

[0011]

Embedded image

[0012] (In the formula (2-1), n is an organic residue represented by integer of 1 to 10, X is a direct bond or the structural formula (2-2a) ~ (2-2e), R 7 And R ⁷ ′ is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.)

[0013]

Embedded image

(In the formulas (3-1a) to (3-1e), R ³ is a hydrogen atom or an organic residue having a polymerizable unsaturated group represented by the following general formulas (4-1a) to (4-1c). Group, R ⁴ is a hydrogen atom or the following general formula (4
Each of the organic residues having a polymerizable unsaturated group represented by -1 d) to (4-1f) is shown. In the formulas (3-1a) to (3-1e), p is 2 to 2.
0 is an integer, s is an integer from 1 to 20, q is an integer from 2 to 15, t is 0 to 10
Integers, r and r 'are integers of 1 to 16, u is an integer of 1 to 10, X is a direct bond or an organic residue represented by the above structural formulas (2-2a) to (2-2e), Y is The organic residues represented by the following formulas (6-1a) to (6-1h) are respectively shown. )

[0015]

Embedded image

(In the formulas (4-1a) to (4-1f), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkylene group having 1 to 20 carbon atoms.)

[0017]

Embedded image

(In the formulas (5-1a) to (5-1c), R ⁸ has 1 to 20 carbon atoms.
Alkylene group or -CH ₂ CH ₂ CONH-R ^1- , R ¹ is represented by the above formula (2
-1), R ² ′ is an organic residue represented by the above general formulas (3-1a) to (3
-1e) represents an organic residue. )

[0019]

Embedded image

(In the formulas (6-1a) to (6-1h), R ⁷ and R ⁷ ′ are a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.) A core obtained by Michael addition of a hydroxyl-containing acrylic compound (b-1) or a carboxyl-containing acrylic compound (b-2) to a polyamino compound (a) having at least one primary or secondary amine The present invention relates to a method for producing the above vinyl group-containing polyfunctional compound obtained by reacting a compound with a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group contained in a polymerizable unsaturated group and a core compound.

The present invention also relates to the above vinyl group-containing polyfunctional compound wherein the polyamino compound (a) is a compound represented by the following formulas (i) to (ii).

[0022]

Embedded image

In the present invention, the number average molecular weight is 200 to 200.
The present invention relates to the above vinyl-functional polyfunctional compound which is a liquid having a viscosity of 100,000 cps (30 ° C.) or less at 100,000. The present invention also relates to the above-mentioned vinyl group-containing polyfunctional compound which is an active energy ray-curable type. The present invention also relates to a curable composition containing the vinyl group-containing polyfunctional compound (A) and another polymerizable unsaturated group-containing compound (B). Further, the present invention provides a vinyl group-containing polyfunctional compound (A)
And the other curable composition having a compounding ratio of the polymerizable unsaturated group-containing compound (B) of 10:90 to 95: 5 (weight ratio).

The present invention also relates to the above curable composition wherein the other polymerizable unsaturated group-containing compound (B) is a (meth) acrylic compound or a vinyl ether compound.
The present invention also relates to another polymerizable unsaturated group-containing compound (B).
Has a viscosity of 10,000 cps (30 ° C.) or less and a number average molecular weight of 2000 or less. The present invention also relates to the above-mentioned curable composition used for printing ink. The present invention also relates to the above-mentioned curable composition for use in paints. The present invention also relates to the curable composition described above, which is curable by active energy rays.

The present invention also relates to a cured product obtained by curing the above curable composition.

The vinyl group-containing polyfunctional compound obtained in the present invention is a compound represented by the above general formula (1) and having two or more polymerizable unsaturated groups as a terminal site of R2. In the present invention, R ¹ in the above formula (1) is an organic residue represented by the above general formula (2-1). In the above formula (2-1), n is 1 to 10
X, preferably an integer of 1 to 4, X is a direct bond or an organic residue represented by the above structural formulas (2-2a) to (2-2e),
R ⁷ is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms. Further, R ² in the above formula (1)
Is a linear organic residue represented by the above formulas (3-1a) to (3-1e).
And an organic residue containing a branch site represented by the above formulas (5-1a) to (5-1c).

In the above formulas (3-1a) to (3-1e), p is an integer of 2 to 20, preferably 2 to 10, and more preferably an integer of 2 to 6; Decrease. s is 1
-20, preferably an integer of 1 to 5, and in this case too, the reactivity is reduced if it is too large. q is an integer of 2 to 15, preferably 4 to 7 in view of the versatility and physical properties of the raw material. t is 0 (direct bond) or 1 to 10, preferably 1
Is an integer of from 5 to 5, and in this case too, the reactivity is reduced if it is too large. r and r 'are integers of 1 to 16, preferably 1 to 6, more preferably 1 to 4 from the viewpoint of reactivity. u is 1 ~
It is an integer of 10 and preferably an integer of 1 to 5. In this case, too large a value lowers the reactivity. X represents a direct bond or an organic residue represented by the above structural formulas (2-2a) to (2-2e), and Y represents an organic residue represented by the above formulas (6-1a) to (6-1h), respectively. .

In the present invention, in order to further improve the reactivity, fluidity, physical properties of the coating film and the like by multifunctionalization,
R ² is preferably a structure containing a branch site by a nitrogen atom represented by the above formulas (5-1a) to (5-1c). The above formulas (5-1a) to (5-1
In c), R ⁸ is an alkylene group having 1 to 20 carbon atoms, preferably 1 to 9 carbon atoms, or —CH ₂ CH ₂ CONH-R ¹ —, wherein R ¹
Is an organic residue represented by the above formula (2-1), wherein, in the above formula (2-1), X is a direct bond, and n is an alkylene group having 2 to 8 carbon atoms having 1 to 4. More preferred. R ² ′ represents an organic residue represented by the above general formulas (3-1a) to (3-1e). In the formulas (3-1a) to (3-1e), R ³ is a hydrogen atom or an organic residue having a polymerizable unsaturated group represented by the general formulas (4-1a) to (4-1c). , R ⁴ is a hydrogen atom or the above general formula (4-1d)
And organic residues having a polymerizable unsaturated group represented by (4-1f). In the above formulas (4-1a) to (4-1f), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkylene group having 1 to 20 carbon atoms, preferably 1 to 9 carbon atoms.

In the present invention, the vinyl group-containing polyfunctional compound contains a hydroxyl group or a carboxyl group in the polyamino compound (a) having two or more primary or secondary amines.
Acrylic compound (b-1) Core compound obtained by Michael addition of (b-2) and compound (c) having a polymerizable unsaturated group and a functional group capable of reacting with a hydroxyl group or a carboxyl group contained in the core compound And can be produced by a reaction with Polyamino compound (a) used in the present invention
Is a compound having two or more primary or secondary amines in a molecule used as a starting material for polyfunctionalizing the compound, and includes a linear / branched aliphatic polyamino compound, a cyclic aliphatic polyamino compound, and a fatty acid. Aromatic polyamino compounds, terminal amino-based multibranched compounds, and the like.

The straight-chain / branched aliphatic amine used in the present invention includes hydrazine compounds such as hydrazine and adipic dihydrazide;
Diamino compounds represented by the following general formula (1) such as propanediamine, butanediamine, propanediamine, pentanediamine, hexanediamine, diaminooctane, diaminodecane, diaminododecane, and 2,5-dimethyl-2,5hexamethylenediamine; Examples include polyoxypropylene diamine, diethylene triamine, tetraethylene tetramine, and the like. Examples of the cycloaliphatic polyamino compound include mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) 2,
4,8,10-tetraoxaspiro (5,5) undecane, 1,4-bis (2-amino-2-methylpropyl)
Piperazine, 1,3-bis (aminomethyl)) cyclohexane, polycyclohexylpolyamine, bis (aminomethyl) -bicyclo [2,2,1] heptane, methylenebis (furanmethanamine) and the like.

Further, examples of the aliphatic aromatic polyamino compound include meta-xylene diamine and para-xylene diamine. Further, among the vinyl group-containing polyfunctional compounds obtained in the present invention, those containing a tertiary amino group at a high density in one molecule are effective for lowering the viscosity of the multi-branched compound, increasing the polyfunctionality, and improving the reactivity. . In order to satisfy this object, it is preferable to use a low molecular weight diamine such as ethylenediamine as the polyamino compound (a) in the present invention. Further, as the terminal amino-based multibranched compound, the reaction of reacting butylenediamine and acrylonitrile shown in the above formulas (i) and (ii) to reduce the terminal nitrile group to amine is defined as one step, and this reaction is performed in one step. Propyleneimine dendrimer obtained by repeating (WO09
3/14147, US5530092, Japanese Patent Publication 7-330631), Michael addition of methyl acrylate to ammonia or ethylenediamine, and furthermore, introduction of secondary amino group at the terminal by ester amide exchange reaction as one step, repeated as necessary The following structural formula obtained by reacting
Amidoamine-based dendrimer shown in (iii) (WO84 / 02
705, Japanese Patent Publication No. 6-70132) or an intermediate product thereof. Since these compounds have many branches, 1
A large number of terminal functional groups can be introduced into the molecule, and because of the spherical shape, the entangled molecular weight is very high, and is 1/10 to 1/10 of that of a linear or comb polymer having the same molecular weight.
Because of the viscosity of 00, the reactivity at higher molecular weight,
It is preferable when the purpose is to improve the fluidity and the physical properties of the coating film.

[0032]

Embedded image

The hydroxyl-containing acrylic compound (b-1) used in the present invention is represented by the following general formula (7-1)
a) or a compound represented by (7-1b), and an acrylic compound having a carboxyl group (b-2) is represented by the following general formula
Compounds represented by (7-1c) to (7-1e).

[0034]

Embedded image

Here, the above formulas (3-1a) to (3-1e) are obtained by the above formula (7)
-1a) to acrylic compound (b-1) containing a hydroxyl or carboxyl group shown in (7-1e) (b-1)
Since it is an organic residue obtained by a Michael addition reaction with the lamino compound (a), the above-mentioned formula (7-
The ranges of p, s, q, t, r, r ', u, X, and Y in (1a) to (7-1e) are (3-1a) to (3
-1e). When a hard cured product is required, it is preferable to use one having a short chain length, and to improve flexibility, use one having a long chain length. Within the above range, the bulk viscosity tends to decrease despite an increase in the molecular weight as the chain length increases.

Acrylic compound containing hydroxyl group (b-1)
Examples include hydroxyalkyl acrylate compounds when s = 1 and t = 0, alkylene glycol monoacrylate compounds when t = 0, and polylactone monoacrylate compounds when s = 1. More specifically, examples of hydroxyalkyl acrylate compounds include 2-hydroxyethyl acrylate, 2-hydroxypropyl) acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, and 1,6-hexanediol monoacrylate. .

Specific examples of the alkylene glycol monoacrylate compounds include diethylene glycol monoacrylate, triethylene glycol monoacrylate, tetraethylene glycol monoacrylate,
Examples include dipropylene glycol monoacrylate, tripropylene glycol monoacrylate, tetrapropylene glycol monoacrylate, and polytetramethylene glycol monoacrylate. Examples of the polylactone monoacrylate-based compound include 2-acryloyloxyethyl hydrogencaprolactonate, 2-acryloyloxyethylhydrogendicaprolactonate, and 2-acryloyloxyethylhydrogenpoly (degree of polymerization: 3 to 5). And 2-acryloyloxyethyl-2-hydroxy-6 hexanolactonate.

Examples of the acrylic compound (b-2) having a carboxyl group include ω-carboxypolycaprolactam (n = 2 to 7) monoacrylate, acrylic acid dimer β-carboxyethyl acrylate, and β-acryloxy succinate. Examples include, but are not necessarily limited to, ethyl monoester, β-carboxyethyl acrylate, β-acryloyloxyethyl hydrogen succinate, acrylic acid, and the like.

In the present invention, the acrylic compound (b-2) having a carboxyl group may be a cyclic acid anhydride and an acrylic compound (b-1) having a hydroxyl group in addition to the above exemplified compounds.
Can be synthesized by the reaction with The above cyclic acid anhydrides are roughly classified into aliphatic, alicyclic and aromatic compounds, and as the aliphatic cyclic anhydride, succinic anhydride,
Butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, succinic anhydride, glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, heptyl glutaric anhydride Glutaric acid anhydrides such as octyl glutaric anhydride, decyl glutaric anhydride, dodecyl glutaric anhydride, maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride And maleic acid anhydrides such as octylmaleic anhydride, decylmaleic anhydride and dodecylmaleic anhydride, and itaconic anhydride. Examples of the alicyclic cyclic acid anhydride include 1,2-cyclohexanedicarboxylic anhydride, 4-n-butylcyclohexanedicarboxylic anhydride, 4-n-dodecylcyclohexanedicarboxylic anhydride, and hexadecylcyclohexanedicarboxylic anhydride. And 5-norbonane-2,3 dicarboxylic anhydride.

Examples of the aromatic cyclic acid anhydride include phthalic anhydride, 4-n-butyl phthalic anhydride, hexyl phthalic anhydride, octyl phthalic anhydride, decyl phthalic anhydride, dodecyl phthalic anhydride, and isatoic anhydride. And aromatic cyclic anhydrides such as diphenic anhydride, but are not necessarily limited thereto. In the present invention, in the above formulas (3-1c) and (3-1d), Y, that is, the above formulas (6-1a) to (6-1h)
The organic residue represented by is derived from the cyclic anhydride used.

In the present invention, the acrylic compound (b-2) containing a carboxyl group can be synthesized by a known method. In the synthesis, a tertiary amine such as dimethylbenzylamine and triethylamine can be used as a catalyst. The catalyst is added in an amount of 0.01 to 3 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the starting compound.
5% by weight. The reaction temperature is preferably from 50 to 120 ° C. The reaction can be performed in a solventless system, but a general-purpose organic solvent such as ethyl acetate, toluene, and methyl ethyl ketone can be used to control the reaction. In this case, the concentration of the active ingredient is preferably 20 to 95% by weight, more preferably 30 to 90%. If the concentration is lower than this, the reactivity decreases, which is not preferable.

In the present invention, the core compound is a Michael addition reaction of the above polyamino compound (a) with an acrylic compound (b-1) (b-2) having a hydroxyl group or a carboxyl group.
In response, they are synthesized. The synthesis can be carried out according to the conventional method, but when an alcohol such as methanol or ethanol is used as a reaction solvent, a side reaction hardly occurs. When a solvent is used, it is preferably used in an amount of 1 to 100 times the compounding weight of the polyamino compound (a). Heating is not particularly necessary, but when the molecular weight of the polyamino compound (a) or the (meth) acrylic compound (b-1) (b-2) is large, the heating is performed in the range of 30 ° C to 70 ° C. Is preferred. The reaction time varies depending on the type of amino compound to be used and the reaction temperature, but is 30 minutes to 72 hours, generally about 1 day and night at room temperature, and 1 to 50 to 100 ° C when heated.
It ends within 10 hours.

In the present invention, the polymerizable unsaturated group at the terminal of the vinyl group-containing polyfunctional compound includes a hydroxyl group or a carboxyl group of the core compound and a hydroxyl group of the compound (c).
Alternatively, it can be introduced by a reaction of a functional group capable of reacting with a carboxyl group.

In the present invention, the polymerizable unsaturated group at the terminal of the vinyl group-containing polyfunctional compound is represented by the general formula (4-1a)
Among them are (meth) acrylic group, vinyl ether group and allyl group shown in (4-1f), and among these, (meth) acrylic group is preferable from the viewpoint of reactivity at the time of radiation curing.
Further, from the viewpoint of improving the reactivity, it is preferable to use a (meth) acryl group and a vinyl ether group in combination.

In the present invention, the method for introducing a polymerizable vinyl group into the core compound is based on the type of the core compound terminal functional group contained in the core compound and the polymerizable unsaturated group contained in the compound (c).
Selected by. When a (meth) acrylic group is introduced into a core compound whose terminal functional group is a hydroxyl group, (meth) acrylic halides such as (meth) acrylic chloride and (meth) acrylic bromide are esterified as compound (c). A low molecular weight acrylate such as methyl (meth) acrylate or ethyl (meth) acrylate is used in the transesterification reaction as the compound (c). Also, acrylonitrile is compound (c)
Alcohol decomposition method used as a method, direct oxidation method of propylene, ACH (acetone cyanohydrin sulfate method), direct oxidation method of isobutylene, etc. (meth)
A (meth) acryl group can be introduced by an acrylic ester production method. When a vinyl ether group is introduced, an ω-halogenated alkyl vinyl ether such as chloroethyl vinyl ether is used as the compound (c) in the etherification reaction. When introducing an allyl group
Is used in the etherification reaction of allyl chloride as compound (c).

When the terminal functional group is a carboxyl group, it is difficult to introduce a vinyl ether group because a side reaction occurs. In the case of introducing a (meth) acryl group, the compound (c) is used as an esterification reaction with an acrylate containing a hydroxyl group or an alkoxide at the terminal. When an allyl group is introduced, allyl alcohol or an alkoxide compound thereof can be used. Also,
When the terminal functional group is a carboxyl group, the esterification reaction proceeds under milder conditions if the carboxyl group is subjected to an acid halogenation treatment with thionyl chloride or the like.

In the present invention, the vinyl group-containing polyfunctional compound is not particularly limited as long as it contains at least two polymerizable unsaturated groups, but is a terminal site represented by the above formula.
Preferably at least 50% of R3 or R4, more preferably 90%
% Or more is preferably a polymerizable unsaturated group represented by the above formulas (4-1a) to (4-1f). If the number of polymerizable unsaturated groups is small, sufficient reactivity may not be obtained.

In the present invention, other than the structural formulas represented by the above formulas (3-1a) to (3-1e) and (5-1a) to (5-1c) as R ² or R ² ′, other organic compounds may be used. Residues can also be introduced. These other organic residues have a role of controlling the viscosity and solubility of the vinyl group-containing polyfunctional compound. Such other organic residues are introduced by the same method as above by Michael addition of a monofunctional acrylic compound other than those represented by the above formulas (7-1a) to (7-1e) and the polyamino compound (a). can do. The introduction ratio of other organic residues that can be introduced in the present invention is as follows.
There is no particular limitation as long as there are two or more polymerizable unsaturated groups, but preferably 30% of R ² or R ² ′ contained in the molecule.
The content is more preferably 20% or less.

Here, specific examples of other organic residues that can be used include: alkyl acrylate compounds such as methyl acrylate, ethyl acrylate, butyl acrylate, pentyl acrylate, heptyl acrylate, hexyl acrylate, octyl acrylate, -Ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, icosyl acrylate, Henikosyl acrylate, docosyl acrylate and the like.

Examples of the alkylene glycol acrylate compound include methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxydiethylene glycol acrylate, phenoxyethylene glycol acrylate, methoxytriethylene guchicol acrylate, methoxytetraethylene glycol acrylate, and ethoxytetraethylene glycol. Acrylate, propoxytetraethylene glycol acrylate, n-butoxytetraethylene glycol acrylate, n-pentaxytetraethylene glycol acrylate, tripropylene glycol acrylate, tetrapropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxytetrap Propylene glycol acrylate, ethoxytetrapropylene glycol acrylate, propoxytetrapropylene glycol acrylate, n-butoxytetrapropylene glycol acrylate, n-pentaxytetrapropylene glycol acrylate, polytetramethylene glycol acrylate, methoxypolytetramethylene glycol acrylate, methoxypolyethylene glycol acrylate Ethoxy polyethylene glycol acrylate or phenoxy triethylene glycol acrylate, phenoxy tetraethylene glycol acrylate, phenoxy hexaethylene glycol acrylate, phenoxy polyethylene glycol acrylate, phenoxy tetrapropylene glycol acrylate, etc. Kokishi groups are those containing a phenoxy group.

Further, as the polylactone acrylic compound, 2-acryloyloxyethyl hydrogen methoxycaprolactonate, 2-acryloyloxyethyl
Lehydrogen methoxy dicaprolactone, 2-
Acryloyloxyethyl hydrogen hydrogen methoxy poly (degree of polymerization: 3 to 5) caprolactonate, 2-acryloyloxyethyl-2-methoxy-6 hexanolactonate and the like can be mentioned.

The vinyl group-containing polyfunctional compound obtained by the present invention is not particularly limited in molecular weight or viscosity, but has a number average molecular weight of 200 to 100,000, preferably 250 to 1000.
A value of 0 is preferred in terms of compatibility with other components such as other polymerizable unsaturated compounds (A) and viscosity. The viscosity is not particularly limited as long as the composition containing the vinyl group-containing polyfunctional compound is in a viscosity range in which a film can be formed.
Viscosity of less than 00 cps, preferably 5000 cps (3
(0 ° C.).

The vinyl group-containing polyfunctional compound obtained in the present invention shows curability by active energy rays as it is, and is used as a curable resin material as a film-forming material such as paints and inks, a molding material, an adhesive and the like. Although it is possible, even when blended with another polymerizable unsaturated compound (B), a film-forming material such as paint, ink, etc.
It can be used for raw materials such as molding materials and adhesives.

As the other polymerizable unsaturated group-containing compound (B), other monofunctional or polyfunctional (meth) acrylic compounds, vinyl ether compounds, other vinyl compounds, diene compounds, styrene compounds, An unsaturated aliphatic compound or the like can be used. Among these, it is desirable to use a (meth) acrylic compound or a vinyl ether compound from the viewpoint of availability.

The monofunctional (meth) acrylate compounds to be incorporated in the composition include methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate.
Acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate,
n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, n-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, benzyl ( (Meth) acrylate, (meth) acryloyloxyethyl hydrogen succinate, (meth) acryloyloxypropyl hydrogen phthalate, (meth) acyl Loyloxypropyl tetrahydrohydrogen phthalate, (meth) acryloyloxypropyl hexahydrohydrogen phthalate, (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) Acid phosphate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Examples include 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, glycerol mono (meth) acrylate, and 2-hydroxysiloxy-3-acryloyloxypropyl (meth) acrylate. However, the present invention is not necessarily limited to these.

The polyfunctional (meth) acrylate compounds include 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di ( Meth) acrylate, neopentyl glycol di (meth) acrylate,
Ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, ester acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) A) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, Pentaerythritol tetra (meth) acrylate, although dipentaerythritol penta (meth) acrylate and the like, not necessarily limited thereto. Use of a trifunctional or higher (meth) acrylate compound among the above polyfunctional compounds increases the reactivity.

The vinyl ether compounds to be blended in the present invention include monofunctional vinyl ether compounds such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether,
Examples include, but are not necessarily limited to, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, and the like. As the polyfunctional vinyl ether compound, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether,
Tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediele divinyl ether, 1,6-hexanediol divinyl ether, glycerol divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether Divinyl ether compounds such as 1,4-dihydroxymethylcyclohexane divinyl ether, hydroquinone divinyl ether, hydroquinone diethoxy divinyl ether, resorcin diethoxy divinyl ether, bisfenol A diethoxy divinyl ether, bisfenol S diethoxy divinyl ether , Glycerol trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane Trivinyl ether compounds such as trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, and ditrimethylolpropane polyvinyl ether; and the like. However, the present invention is not necessarily limited to these.

Other vinyl compounds include vinyl pyrrolidone, vinyl caprolactam, vinyl carbazole, vinyl-1-imidazole, divinyl ethylene urea, N-
Examples include, but are not necessarily limited to, vinyl formamide, N-vinyl formalin, allyl glycidyl ether, allyl chloride, and the like.

In the present invention, the compounding ratio of the vinyl group-containing polyfunctional compound to the other polymerizable unsaturated group-containing compound (B) is preferably 10:90 to 95: 5 (weight ratio), more preferably 30:90. : 70 to 95: 5 (weight ratio).

The curable composition of the present invention contains an amino resin, a phenol resin, a polyamide resin, a cellulose derivative, a vinyl resin, a polyolefin, a natural resin in order to adjust the viscosity, the film forming property and the film performance. Rubber derivatives,
General-purpose resin materials such as acrylic resin, epoxy resin, polyester, polystyrene, alkyd resin, rosin-modified alkyd resin, and linseed oil-modified alkyd resin, and drying oils such as linseed oil, tung oil, and soybean oil may be blended. However,
The amount of each of these is preferably 60% by weight or less, more preferably 40% by weight or less, based on the total amount of the composition. Further, water, an organic solvent, a compatibilizer, a surfactant, a lubricant and the like may be added for the purpose of controlling the fluidity.
The amount of these components is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the composition.

When the curable composition of the present invention is cured by heat or ultraviolet rays, known initiators and sensitizers can be used. The active energy ray-curable composition of the present invention contains a dye or a coloring agent composed of a pigment such as carbon black, titanium white, phthalocyanine, an azo dye, or quinacridone, or an inorganic filler such as Si-based fine particles, mica, or calcium carbonate in an appropriate amount. By being added, it can be used as various printing inks, coloring paints, and the like.

The curable composition of the present invention comprises various metals, plastics, papers, ceramics or composites.
A coating method such as a roll coater, a bar coater, or a knife coater, or a printing method such as offset printing, gravure printing, letterpress printing, or silk screen printing on a plate, sheet, or film-like substrate, and a film thickness of 0.1 to 500 μm. To form or fill. The film filled or formed by the above method can be cured by heat or active energy rays such as electron beam, ultraviolet ray, visible light ray and infrared ray.

When an electron beam is used as a curing trigger in the present invention, the acceleration voltage is not particularly limited, and a cured film can be formed by irradiating an electron beam with an acceleration voltage of 30 to 500 kV. When electron beam irradiation at a voltage is performed, electron beams are intensively absorbed on the coating film / printing surface where curing is likely to be inhibited by oxygen, and thus the curability can be improved.

The electron beam irradiation dose (DOSE) is
Preferably 1 to 1000 kGy, more preferably 5 to 2 kGy
The range is 00 kGy. If the amount is less than this, it is difficult to obtain a sufficiently cured product, and if it is more than this, damage to a coating film or a substrate is large, which is not preferable.

[0065]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. ◎ Structural analysis, measurement method of number average molecular weight and viscosity 1) Structural analysis The structure of the vinyl group-containing dendrimer synthesized here is ¹ H
-Confirmed by NMR. 2) Number average molecular weight: Gel permeation chromatography (Tosoh SC-8020) A calibration curve of gel permeation chromatography (GPC) was independently prepared from several types of dendrimers having a known structure analyzed by ¹ H-NMR, GPC based on this
The result measured in was adopted. In addition, the molecular weight distribution (Mw /
For Mn), the value obtained with the same measuring instrument was adopted. 3) Viscosity: Rheometer (Rheometrics: RDS-)
II, RFS-II) Rheometer RDS-II (high viscosity type) or RFS-II manufactured by Rheometrics Co., Ltd. according to the viscosity of the sample.
(Low viscosity type) steady viscosity (shear speed = 1 ~
(Value of 100 / sec). ◎ Activated energy beam irradiation device and irradiation conditions 1) Area beam type electron beam irradiation device Curetron EBC-200-20-30 (Nissin High Voltage) Electron beam acceleration; 150 kV Absorbed dose (Dose); Current amount in the range of 5 to 20 kGy And the transport speed.

Irradiation atmosphere; nitrogen 2) Low-acceleration voltage type electron beam irradiator Lyocure (irradiation tube; manufactured by MIN-EB AIT) Electron beam acceleration; 50 kV output; 10 W, 30 W Absorbed dose (Dose): 5 to 20 kGy Was adjusted at the transport speed. Irradiation atmosphere; nitrogen 3) ultraviolet irradiation apparatus Tosukyua KUVM-30251-1WA-DMF (Toshiba Lighting & Technology Corp.) UV irradiation; a metal halide lamp 120 W / cm 1 lamp dose; 80 mJ / cm ² irradiation atmosphere; air

◎ Abbreviations of the following compounds used in the examples are described. 1) Polyamino compound (a) meta-xylylenediamine; MXDA ethylenediamine; ED DAB4: described in structural formula (i) 4-Cascade: 1,4-diaminobuta
ne [4]: propylamine DAB8: described in structural formula (ii) 8-Cascade: 1,4-diaminobuta
ne [4]: (1-azabutylidene) 4
propylamine 2) Acrylic compound having hydroxyl group or carboxyl group HEA: 2-hydroxyethyl acrylate HBA: 4-hydroxybutyl acrylate FA2: 2-acryloyloxyethyl hydrogen dicaprolactonate (n = 2) 3) hydroxyl or carboxyl group AcCl; acrylic acid chloride ClEVE; chloroethyl vinyl ether 5) Other polymerizable unsaturated compounds (B) HDDA; 1,6-hexanediol diacrylate TPGDA; Propylene glycol diacrylate DPHA; ethylene oxide-modified trimethylolpropane triacrylate (Example 1) (ED / HBA = 1/4) /AcCl=1/1.1 500 equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser Milliliter four mouth ED to bottom flask
A20.1 g, HBA: 192.2 g, ethyl acetate: 71 g, methanol: 20 g were blended, and the mixture was refluxed for 3 hours in a hot water bath set at 75 ° C., and then partially sampled to measure ¹ H-NMR. The proton peak derived from the acrylic group almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, the solvent was distilled off while continuing to heat and stir at normal pressure in a water bath at 80 ° C., and a vacuum line was connected from the top of the condenser to 70 ° C. 4 in the bath
When the pressure was reduced to 0 mmHg or less, ethyl acetate and methanol were completely distilled off, whereby a viscous liquid core compound was obtained (yield 98%).

A 300 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, a dropping funnel and a condenser was prepared, and 9.05 g of AcCl, 20.2 g of triethylamine and 21.12 g of methylene chloride were charged. A methylene chloride solution (NV = 30%) of 14.47 g of the previously obtained core compound charged in the dropping funnel was added dropwise. After dripping,
The water bath temperature was set at 50 ° C., and the heating and stirring were continued for another 3 hours. After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, washed and separated twice with a saturated aqueous solution of sodium hydrogen carbonate, and the oil phase was recovered.The methylene chloride used as the reaction solvent was removed by an evaporator. As a result, a desired vinyl group-containing polyfunctional compound was obtained. The ¹ H-NMR chart of the obtained vinyl group-containing polyfunctional compound is shown in FIG. 1, and its assignment is shown in the following figure. The average number of acrylic groups introduced from the chart was 2.6 per molecule. Table 2 shows the physical property values.

[0069]

Embedded image

Example 2 (DAB4 / HBA = 1/8) /AcCl=1/1.1 D was placed in a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser.
AB4: 31.6 g, HBA: 115 g, ethyl acetate:
63 g and methanol: 30 g were mixed and refluxed in a hot water bath set at 75 ° C. for 3 hours.
^{When 1} H-NMR was measured, the proton peak derived from the acryl group had almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, the solvent was distilled off while continuing to heat and stir at normal pressure in a water bath at 80 ° C., and a vacuum line was connected from the top of the condenser to 70 ° C. When the pressure was reduced to 40 mmHg or less in a hot water bath, ethyl acetate and methanol were completely distilled off to obtain a viscous liquid core compound (96% yield).

A 300 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, a dropping funnel and a condenser was prepared, and 9.05 g of AcCl, 20.2 g of triethylamine and 21.12 g of methylene chloride were charged. A methylene chloride solution (NV = 30%) of 13.7 g of the previously obtained core compound charged into the dropping funnel was added dropwise. After dropping,
The water bath temperature was set at 50 ° C., and the heating and stirring were continued for another 3 hours. After the completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, and further washed with a saturated aqueous solution of sodium hydrogen carbonate.
After multiple washings and liquid separation, the oil phase was recovered, dehydrated with anhydrous magnesium sulfate, and the methylene chloride used as the reaction solvent was further removed by an evaporator to obtain the desired vinyl group-containing polyfunctional compound. . The ¹ H-NMR chart of the obtained vinyl group-containing polyfunctional compound is shown in FIG. 2, and its assignment is shown in the following figure. The average number of acryl groups introduced from the chart was 4.9 per molecule. Table 2 shows the physical property values.

[0072]

Embedded image

(Example 3) (DAB4 / HBA = 1/8) / ClEVE Core compound obtained in Example 2; 5.0 g of sodium hydride in 14.8 g of a tetrahydrofuran (THF) solution (NV = 50%)
Is added little by little while cooling and stirring so that the inside of the reaction system becomes 25 to 40 degrees.
E: 9.33 g and hydroquinone 0.01 g were added, and the mixture was further refluxed for 5 hours to carry out an etherification reaction. Filtering out the precipitated salt and removing THF used as the reaction solvent
As a result, a polyfunctional compound having a vinyl ether group was obtained.
The measured hydroxyl value was 81.92 mgKOH / g. (Average number of introduced vinyl ether groups: 5.3 / molecule) (Examples 4 to 22) By applying the above method, various vinyl group-containing polyfunctional compounds as listed in Table 1 can be obtained.

[0074]

[Table 1]

(Examples 1 to 11, Comparative Examples 1 to 4) The vinyl group-containing polyfunctional compound obtained in Examples 1 to 3 and the curable composition prepared with the composition shown in Table 2 were used as # 6 It was applied on four types of films (size of substrate for evaluation → thickness: 20 μm, width: 5 cm, length: 20 cm) with a bar coater, and was irradiated with electron beams by various DOSE (3, 5, 20 kGy). . Table 2 shows the types of the vinyl group-containing polyfunctional compound used and the other polymerizable unsaturated group-containing compounds and the curing characteristics of the coating film obtained by electron beam irradiation (touch test → ×: tacked, Δ: No tack but scratches on nails, ○: no scratches due to no tacks, and solvent resistance (ratio of soluble components by THF extraction test), curl (evaluated by sensory test of substrate film deformability → ○) : No curl, Δ: degree of warpage, ×: film rolls up), and evaluation results of abrasion resistance are shown. In Table 2, dipentaerythritol hexaacrylate (DPHA) and the other polymerizable unsaturated group-containing compounds used in the examples, 1,6-hexanediol diacrylate (HDDA) and tripropylene, were used as Comparative Examples 1-4. The evaluation results of glycol diacrylate (TPGDA) are also shown.

[0076]

[Table 2]

[0077]

Industrial Applicability According to the present invention, vinyl having excellent curability and low viscosity, having sufficient coating film performance, and capable of reducing the blending ratio of low molecular weight compounds having problems in performance. A group-containing polyfunctional compound can be provided.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of a vinyl group-containing polyfunctional compound obtained in Example 1.

FIG. 2 is a ¹ H-NMR chart of a vinyl group-containing polyfunctional compound obtained in Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 4J038 C08G 63/685 C08G 63/685 4J039 C09D 4/02 C09D 4/02 4J043 5/00 5/00 C 4J100 11/00 11/00 171/00 171/00 B // C08G 63/06 C08G 63/06 65/26 65/26 69/28 69/28 73/02 73/02 ( 72) Inventor Hiroaki Tanaka 2-3-13 Kyobashi, Chuo-ku, Tokyo F-term in Toyo Ink Manufacturing Co., Ltd. 4H006 AA01 AA03 AB76 AB90 AB99 AC48 AC52 BT12 BU32 4J001 DA01 DA04 DB08 DB10 DC03 DC05 DC06 DC13 DD02 JA17 JA20 JB50 4J005 AA11 BD02 BD05 4J027 AB03 AB10 AB28 AB32 AC03 AC04 AC06 AC07 AC09 AD02 AG01 AH02 AJ01 AJ03 AJ08 BA01 BA04 BA06 BA07 BA08 BA09 BA10 BA11 BA13 BA14 BA15 BA16 BA17 BA19 BA23 BA24 BA26 BA27 CA02 CA03 CA06 CA07 CA09 CA10 CA12 CA14 CA18 CA25 CA34 CA36 CC04 CC05 CC06 CD08 4J029 AA02 AC03 AE11 BF25 EG08 EG09 JE182 4J038 CG141 CH031 CH041 CH071 CH081 CH121 CH131 CH161 CH201 CJ081 CJ131 GA01 MA02 GA09 NA14 MA09 AE13 AF03 CA04 EA03 EA06 EA07 EA08 EA10 EA48 FA01 FA02 FA06 GA01 GA02 GA03 GA10 4J043 PA13 QC02 RA08 SA06 SA07 SA08 SA09 SB01 TA02 TA11 TA72 TB01 UA121 UA761 ZB01 ZB02 ZB03 ZB22 4J100 AE02 AE02 AE02 AE02 AE02 AE02 AL08Q AL09Q AL10Q AL62Q AL63Q AL66Q AL67P AL67Q AN04Q AN13Q AQ08Q BA02P BA02Q BA03Q BA04Q BA05Q BA08P BA08Q BA12Q BA15P BA15Q BA16Q BA27P BA64Q BC04P BC04Q BC07Q BC08P BC23P BC23Q BC27PBC43J

Claims (13)

[Claims] 1. A vinyl group-containing polyfunctional compound represented by the following general formula (1) and containing two or more polymerizable unsaturated groups. Embedded image (In the formula (1), R ¹ is an organic residue represented by the following general formula (2-1), and R ² is an organic residue represented by the following general formulas (3-1a) to (3-1e) Or an organic residue containing a branch site represented by (5-1a) to (5-1c).) (In the formula (2-1), n is an integer of 1 to 10, X is a direct bond or an organic residue represented by the above structural formulas (2-2a) to (2-2e), and R ⁷
And R ⁷ ′ are a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. ) (In the formulas (3-1a) to (3-1e), R ³ is a hydrogen atom or an organic residue having a polymerizable unsaturated group represented by the following general formulas (4-1a) to (4-1c), ⁴ is a hydrogen atom or the following general formulas (4-1d) to (4-1f)
The organic residue which has a polymerizable unsaturated group shown by each is shown. In the formulas (3-1a) to (3-1e), p is an integer of 2 to 20, and s is 1.
An integer from ~ 20, q is an integer from 2 to 15, t is an integer from 0 to 10, r,
r 'is an integer of 1 to 16, u is an integer of 1 to 10, X is a direct bond or an organic residue represented by the above structural formulas (2-2a) to (2-2e), Y is the following formula (6- The organic residues represented by 1a) to (6-1h) are shown, respectively. ) (In the formulas (4-1a) to (4-1f), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkylene group having 1 to 20 carbon atoms.) (In the formulas (5-1a) to (5-1c), R ⁸ is an alkylene group having 1 to 20 carbon atoms or -CH ₂ CH ₂ CONH-R ^1- ; R ¹ is represented by the above formula (2-1) R ² ′ represents an organic residue represented by the above general formulas (3-1a) to (3-1e).) (In the formulas (6-1a) to (6-1h), R ⁷ and R ⁷ ′ are a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.) 2. A polyamino compound (a) having two or more primary or secondary amines, wherein an acrylic compound (b-1) containing a hydroxyl group or an acrylic compound (b-2) containing a carboxyl group is converted into Michael. A core compound to be added;
2. The method for producing a vinyl group-containing polyfunctional compound according to claim 1, which is obtained by reacting a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group contained in the polymerizable unsaturated group and the core compound. 3. The polyamino compound (a) has the following formula (i) to (ii):
3. The vinyl group-containing polyfunctional compound according to claim 2, which is a compound represented by the formula: Embedded image 4. A compound having a number average molecular weight of 200 to 100,000,
4. The vinyl group-containing polyfunctional compound according to claim 1, which is a liquid having a viscosity of 100,000 cps (30 ° C.) or less. 5. The vinyl group-containing polyfunctional compound according to claim 1, which is an active energy ray-curable type. 6. A curable composition comprising the vinyl group-containing polyfunctional compound (A) according to any one of claims 1 to 4 and another polymerizable unsaturated group-containing compound (B). 7. The compounding ratio of the vinyl group-containing polyfunctional compound (A) to another polymerizable unsaturated group-containing compound (B) is 10: 9.
The curable composition according to claim 6, wherein the curable composition is 0 to 95: 5 (weight ratio). 8. The curable composition according to claim 6, wherein the other polymerizable unsaturated group-containing compound (B) is a (meth) acrylic compound or a vinyl ether compound. 9. The curable composition according to claim 6, wherein the other polymerizable unsaturated group-containing compound (B) has a viscosity of 10,000 cps (30 ° C.) or less and a number average molecular weight of 2000 or less. Composition. 10. A printing ink application according to claim 6 to 9.
The curable composition according to claim 1. 11. The curable composition according to claim 6, which is used for coating. 12. An active energy ray-curable composition.
12. The curable composition according to any one of claims 11 to 11. 13. A cured product obtained by curing the curable composition according to any one of claims 6 to 12.