JPH101529A - Method for producing active energy ray-curable resin and active energy ray-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin which has excellent reactivity of active energy ray curing, exhibits excellent surface hardness, and can obtain a cured product having appropriate flexibility. And a composition thereof. SOLUTION: An acrylate or methacrylate (A) of an alkylene oxide adduct of sorbitol having a hydroxyl group (A), and a polyisocyanate (B)
And a composition containing the obtained active energy ray-curable resin as an essential component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an active energy ray which can be used for paints, inks, various coating materials, etc., exhibits excellent surface hardness and excellent flexibility. The present invention relates to a method for producing an active energy ray-curable resin and an active energy ray-curable resin composition which provide a cured product having the same.

[0002]

2. Description of the Related Art Photosensitive polymers that are cured by active energy rays such as ultraviolet rays and electron beams were initially used as resists for etching, photosensitive materials for printing plate making, and the like. It is used in a wide range of fields such as coating materials. These photosensitive polymers are very promising from the viewpoints of economical improvement such as productivity improvement, energy saving and space saving, improvement of working environment by reducing the amount of organic solvent used, prevention of pollution, etc., and various applications. Research and development corresponding to are actively conducted.

The photosensitive polymer is mainly composed of an active energy ray-curable resin, and is usually used as an active energy ray-curable resin composition obtained by using a diluting monomer, a solvent, a photopolymerization initiator and the like in combination. The active energy ray-curable resin in the composition affects various physical properties of the photosensitive polymer. Examples of conventionally used resins include epoxy acrylate, polyester acrylate, and urethane acrylate. In the active energy ray-curable resin, those which can complete the polymerization reaction with a small amount of energy and have excellent reactivity, for example, are expected to improve production efficiency, and also have excellent surface physical properties after coating film curing. What can obtain surface hardness, flexibility, etc. is calculated | required.

As a means for increasing the reactivity, a resin is mixed with a polyfunctional (meth) acrylate or the like as a reactive diluent, or the resin is multifunctionalized to thereby polymerize the resin composition. There are ways to increase the number of saturated groups.

[0005] However, simply increasing the number of polymerizable unsaturated groups has a disadvantage that the physical properties after curing are very poor, such as high surface hardness but weakness.

[0006] Therefore, it is conceivable to increase the molecular weight of the active energy ray-curable resin and then introduce a large number of polymerizable unsaturated groups according to the molecular weight. Conventionally, among active energy ray-curable resins, when urethane acrylate is used, the increase in molecular weight is relatively easy, and
The resulting coating film is known to have excellent toughness, hardness, chemical resistance and the like.

[0007]

However, when urethane acrylate is used, the amount of polymerizable unsaturated groups that can be introduced in one molecule is limited in designing the molecule, and the activity of the polymer is excellent in reactivity. There was a problem that it was not possible to obtain an energy ray-curable resin having excellent surface hardness, appropriate flexibility, etc. as the surface physical properties after the cured coating film.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for solving the above-mentioned problems, and as a result, have found that an acrylate or methacrylate (A) of an alkylene oxide adduct of sorbitol having a hydroxyl group.
And the polyisocyanate (B) as an essential component, the obtained active energy ray-curable resin, and the active energy ray-curable resin composition containing the active energy ray-curable resin as an essential component, It has been found that a large number of polymerizable unsaturated groups can be introduced, and the reactivity increases, so that the polymerization reaction can be completed with a small amount of energy, and a cured product having excellent surface hardness and moderate flexibility can be obtained. Thus, the present invention has been completed.

That is, the present invention relates to (1) a (meth) compound of an alkylene oxide adduct of sorbitol having a hydroxyl group.
Acrylic ester (A) and polyisocyanate (B)
And (2) a (meth) acrylate (A) of an alkylene oxide adduct of sorbitol having a hydroxyl group, and a polyisocyanate (B). Together with the compound (C) having an unsaturated group and one or two hydroxyl groups and / or the compound (D) having two hydroxyl groups, the production method according to the above (1),

(3) The method according to the above (1) or (2), wherein the (meth) acrylate (A) of the alkylene oxide adduct of sorbitol having a hydroxyl group is a compound represented by the following general formula (1). Method,

[0011]

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(Wherein R ₁ is a hydrogen atom or a methyl group, R ₂
Represents an ethylene group or a propylene group, m is 0.5 to 5.0 on average, a plurality of m in the same molecule may be the same or different, and q is 3.5 on average. ~ 5.5
Where r is on average 0.5-2.5 and q + r =
6. )

(4) The above (1) to (3), wherein the polyisocyanate (B) is a di- or triisocyanate.
And (5) the active energy ray-curable resin obtained by the production method according to any one of (1) to (4) above as an essential component. The present invention provides an active energy ray-curable resin composition characterized by the following.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION (Meth) of an alkylene oxide adduct of sorbitol having a hydroxyl group used in the present invention.
The acrylate (A) (hereinafter referred to as (meth) acrylate (A)) may be a compound obtained by adding an alkylene oxide to sorbitol, having a structure of (meth) acrylate and having a hydroxyl group. What is necessary is just and the manufacturing method is not limited.

For example, compounds having a structure of (meth) acrylate (A) such as ethylene oxide adduct, propylene oxide adduct and butylene oxide adduct of sorbitol can be used.

Among them, it is particularly preferable to use a (meth) acrylate ester represented by the following general formula (1).

[0017]

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In the general formula (1), R ₁ is a hydrogen atom or a methyl group, and R ₂ is an ethylene group or a propylene group. Further, m is 0.5 to 5.0 on average, and m in a plurality of repeating units in the same molecule may be the same or different.

Furthermore, q is 3.5 to 5.5 on average.
Where r is on average 0.5-2.5 and q + r =
6.

In this case, a (meth) acrylic ester having an average of r of 0.5 or more can provide an active energy ray-curable resin having excellent reactivity, and a (meth) acrylic ester having an average of r of 2.5 or less can be obtained. An acid ester is preferable since an active energy ray-curable resin having good solubility can be obtained.

Further, among them, r is on average 0.8 to 0.8.
When the (meth) acrylate ester of 2.2 is used,
It is particularly preferable because the solubility is particularly good and an active energy ray-curable resin having high reactivity can be obtained.

As for r and q, those having specific integer values may be used alone, or those having different integer values may be used as a mixture. ) When using acrylic acid ester alone,

For example, when a (meth) acrylic ester having one hydroxyl group with r = 1 is used alone,
It can function as a terminal blocking agent for polyisocyanate. In this case, q = 5, and since five side chains contain five unsaturated groups, reactivity can be increased.

For example, when a (meth) acrylic ester having two hydroxyl groups, in which r = 2, is used alone, it can function as a molecular weight regulator. In this case, q = 4. It has good reactivity because it has four unsaturated groups in the side chain.

On the other hand, several kinds of r having different integer values,
When (meth) acrylic acid ester is used as a mixture, usually, when it functions as a terminal blocking agent for polyisocyanate, r is 0.5 to 1.2 on average, preferably 0.8 to 1.2. On the other hand, when functioning as a molecular weight regulator, those having an average r of 1.2 to 2.5, preferably 1.5 to 2.2 are used.

The polyisocyanate (B) used in the present invention
As long as the compound has two or more isocyanate groups, a commercially available one may be used. Among them, a diisocyanate or a triisocyanate is preferably used. It is preferable because a curable resin can be obtained.

For example, 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI)
DI), 4,4-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HD
I), tetramethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, lysine diisocyanate, isophorone diisocyanate (IPD
I) diisocyanates such as methylene bis (4-cyclohexyl) diisocyanate (HMDI) and dimer acid diisocyanate;

An adduct of one equivalent of a hydroxyl group of a low molecular weight polyhydric alcohol represented by trimethylolpropane and two equivalents of the above-mentioned various diisocyanates represented by hexamethylene diisocyanate (HMDI) or toluene diisocyanate (TDI); And triisocyanates such as triphenylmethane triisocyanate, which can be used alone or as a mixture.

Further, among them, when isophorone diisocyanate (IPDI), methylene bis (4-cyclohexyl) diisocyanate (HMDI) or the like is used alone or in combination, an active energy ray-curable resin excellent in non-yellowing and weather resistance is obtained. Is preferred because

The present invention also relates to a compound (C) having an unsaturated group and one or two hydroxyl groups together with a (meth) acrylate (A) and a polyisocyanate (B) and / or having two hydroxyl groups. Compound (D) can be used if necessary.

Among the compounds (C), a compound having one hydroxyl group (hereinafter referred to as compound (C1)) is used as a terminal blocking agent in a concentration of a polymerizable unsaturated group of the obtained active energy ray-curable resin. Can be used to adjust

Among the compounds (C), the compound having two hydroxyl groups (hereinafter referred to as compound (C2)) is further obtained in order to control the molecular weight of the obtained active energy ray-polymerizable resin. It can be used to adjust the concentration of polymerizable unsaturated groups in the resin. That is,
In spite of obtaining a higher molecular weight compound, the concentration of the polymerizable unsaturated group can be maintained because the repeating unit contains an unsaturated group.

Further, since the polymer has an unsaturated group in the side chain, the solubility in the monomer is not reduced irrespective of the high molecular weight, and the toughness is imparted to the cured film. Furthermore, the compound (D) can be used for controlling the molecular weight of the obtained active energy ray-curable resin, controlling mechanical properties such as flexibility and elongation, and the like.

In consideration of the above effects, compound (C) and compound (D) can be used in combination.

As the compound (C1), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) Reaction products of monoglycidyl compounds such as acrylate and butyl glycidyl ether with (meth) acrylic acid, caprolactone-modified 2-hydroxyethyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalic acid, glycerin di (meth) acrylate, 1,6-hexanediol diglycidyl ether Reaction product of polyglycidyl compound and (meth) acrylic acid, hydroxyl-containing (meth) acrylate compound such as pentaerythritol tri (meth) acrylate, hydroxyl-containing (meth) acrylamide compound such as N-methylol (meth) acrylamide, hydroxybutyl Examples thereof include vinyl ether compounds such as vinyl ether, hydroxyethyl vinyl ether, and cyclohexane dimethanol monovinyl ether, but are not limited thereto, and any compound having an unsaturated group and one hydroxyl group can be used.

The compound (C2) includes, for example, condensates of bis (4,4-hydroxyphenyl) -2,2'-propane or bis (4,4-hydroxyphenyl) methane with epichlorohydrin, ethylene glycol diglycidyl Ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, N,
Examples include N-diglycidylaniline or an addition reaction product of N, N-diglycidylaniline with acrylic acid or methacrylic acid, but are not limited thereto.
Any compound having an unsaturated group and two hydroxyl groups can be used.

Among them, when a condensate of bis (4,4-hydroxyphenyl) -2,2'-propane or bis (4,4-hydroxyphenyl) methane and epichlorohydrin is used, more excellent surface hardness can be obtained. Is particularly preferred.

As the compound (D), for example, (poly)
Ethylene glycol, (poly) propylene glycol,
(Poly) alkylene glycols such as (poly) butylene glycol, (poly) tetramethylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran,
A copolymer of ethylene glycol and tetrahydrofuran,
Hydrocarbon polyols such as (poly) isoprene glycol, hydrogenated (poly) isoprene glycol, (poly) butadiene glycol, hydrogenated polybutadiene glycol,
Aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol, and aliphatic (poly) ester polyols which are reaction products; aromatic dicarboxylic acids such as terephthalic acid; and polyols such as neopentyl glycol (Poly) ester polyols such as aromatic (poly) ester polyols, and (poly) carbonate polyols, acrylic polyols, and the like, which are reactants with the above.

When the compounds (C) and (D) each have an average molecular weight of 50 to 5,000, an active energy ray-curable resin having excellent reactivity can be obtained by the production method of the present invention. Is preferred.

Among them, it is particularly preferable to use compounds (C) and (D) each having an average molecular weight of 100 to 1,000, because the curing speed is better.

In the production method of the present invention, a (meth) acrylic ester (A), and if necessary, a hydroxyl group-containing compound comprising a compound (C) and / or a compound (D), and a polyisocyanate (B) are used. For example, there is a method in which a reaction is performed in a temperature range of 20 to 130 ° C. by a one-step reaction or a two-step reaction in the presence of a urethanization catalyst such as a tin compound. There is no problem even if the reaction is carried out in the presence of a solvent or a diluent monomer, and a polymerization inhibitor such as hydroquinone or oxygen may be added to ensure stability during production.

The production method of the present invention is specifically illustrated below. For example, when the reaction is carried out in a one-step reaction, an isocyanate group in the polyisocyanate (B) and a (meth) acrylate (A) having an average of 0.5 to 1.2 hydroxyl groups in one molecule (hereinafter referred to as “A”) (Meth) acrylic acid ester (A1)) and, if necessary, compound (C1)
There is a method in which both are charged and reacted so that the hydroxyl groups in the hydroxyl group-containing compound are equivalent.

On the other hand, when a two-step reaction is carried out, the polyisocyanate (B) is reacted with a hydroxyl group-containing compound,
The first-stage reaction for preparing half-urethane and the second-stage reaction for further reacting a hydroxyl-containing compound with the remaining isocyanate group are separated into two groups. The hydroxyl-containing compound used in the first-stage reaction is usually used in one molecule. (Meth) acrylate (A) having an average of 1.2 to 2.5 hydroxyl groups (hereinafter referred to as (meth) acrylate (A2)), compound (C2), and compound (D)
Selected from the group consisting of

The hydroxyl-containing compound used in the second-stage reaction is usually a (meth) acrylic ester (A
1) or compound (C1).

More specifically, in the two-step reaction, for example, first, in the first step, the isocyanate group in the polyisocyanate (B) and the (meth) acrylate (A2)
In the hydroxyl group, the two are charged so that the isocyanate group becomes excessive, the half urethane is prepared by reacting, and then, in the second stage, the isocyanate group in the half urethane,
The hydroxyl groups in the (meth) acrylate (A1), the hydroxyl groups in the compound (C1), or the hydroxyl groups in the mixture of the (meth) acrylate (A1) and the compound (C1) are equivalent. There is a method to make it react.

For example, first, in the first step, the isocyanate group in the polyisocyanate (B) and the compound (C2)
The hydroxyl group in the compound or the hydroxyl group in the compound (D) is charged with the two so that the isocyanate group becomes excessive and reacted to form a half urethane. Then, in the second stage, the isocyanate group in the half urethane There is also a method in which the hydroxyl groups in the (meth) acrylic ester (A1) or the hydroxyl groups in the mixture of the (meth) acrylic ester (A1) and the compound (C1) are reacted so as to be equivalent.

The active energy ray-curable resin obtained in the present invention can be used alone or, if necessary, by adding other prepolymers, diluting monomers, solvents, photopolymerization initiators and the like. An active energy ray-curable resin composition can also be used.

The diluent monomer or solvent used in the present invention is preferably added in an amount of about 5 to 60% by weight. Examples of the dilutable monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, β-hydroxyethyl (meth) acrylate, trimellilol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentane Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

As the solvent, for example, toluene,
Hydrocarbons such as xylene; cellosolves such as cellosolve and butyl cellosolve; esters such as cellosolve acetate and carbitol acetate; ketones such as methyl ethyl ketone; these diluent monomers or solvents are added alone or as a mixture. It is also possible.

The active energy ray-curable resin and the active energy ray-curable resin composition obtained in the present invention are suitable for curing using an active energy ray such as an electron beam, X-ray, ultraviolet ray, visible light ray or the like. Although it is used, it is particularly preferable to cure using ultraviolet rays.

Hereinafter, the polymerization reaction using ultraviolet rays will be described in detail. Generally, when curing a resin using ultraviolet rays, a photopolymerization initiator is usually used, but the photopolymerization initiator is harmful, causes deterioration of the cured coating film, deteriorates storage stability, and increases costs. There is a problem that. However, the active energy ray-curable resin and the composition obtained by the present invention are excellent in reactivity,
Because the polymerization reaction can be performed with less energy,
When the reaction is performed at a normal reaction rate, the amount of the photopolymerization initiator used can be reduced.

The photopolymerization initiator used for curing the active energy ray-curable resin obtained in the present invention includes:
It can be roughly classified into two types: an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type. Examples of the former include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy)
Phenyl- (2-hydroxy-2-propyl) ketone,
1-hydroxycyclohexyl-phenyl ketone, 2-
Acetophenones such as methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin, benzoin methyl ether, benzoin isopropyl Benzoins such as ethers; acylphosphine oxides such as acylphosphine oxides such as 2,4,6-trimethylbenzoindiphenylphosphine oxide; benzyl and methylphenylglyoxyester.

On the other hand, examples of the latter include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylate Benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-
Benzophenones such as 4-methoxybenzophenone; 2
-Isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4
Thioxanthones such as dichlorothioxanthone; aminobenzophenones such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-
Phenanthrene quinone, camphor quinone and the like can be mentioned.

In the present invention, these photopolymerization initiators are used alone or as a mixture of two or more, and are used in the active energy ray-curable resin composition in an amount of 0.05 to 10.0.
% By weight. When the amount of the photopolymerization initiator is 0.05% by weight or more, the polymerization reaction can be started without any trouble and a cured coating film having an appropriate surface hardness can be obtained, which is preferable. Also, the amount of the photopolymerization initiator is 10.
By using it within 0% by weight, a sufficient polymerization reaction can be carried out, and the cured coating film is hardly deteriorated, has excellent storage stability, and further has a harmful amount of the photopolymerization initiator. This is preferable because it can be suppressed. Further, when curing at a normal reaction rate, the photopolymerization initiator,
0.05 to 5 in the active energy ray-curable resin composition.
It is particularly preferred that the content is 0% by weight.

Further, the active energy ray-curable resin obtained in the present invention can be cured by irradiation with ultraviolet rays only by adding the above-mentioned photopolymerization initiator. It is preferable to use a sensitizer in combination. Such photosensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate And amines such as 2-ethylhexyl acid. The compounding amount of the photosensitizer is 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight in the active energy ray-curable resin composition.

The active energy ray-curable resin composition of the present invention may further contain, if necessary, a filler such as talc and clay, a coloring pigment, an antifoaming agent, a coupling agent, a leveling agent and the like. , Paints, inks, adhesives, coatings, three-dimensional molding, resist inks, etc.

[0057]

The present invention will be described more specifically with reference to the following examples and comparative examples. The parts and percentages in the examples are on a weight basis.

Example 1 Isophorone diisocyanate (B-1) was placed in a 3 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
121.8 parts, 1.6 parts of dibutyltin dilaurate, and 0.1 part of hydroquinone were charged and, while maintaining at 50 ° C.,
878.4 parts of acrylic acid ester (A1-1) of propylene oxide adduct of sorbitol (constituted by m = 1, r = 1, q = 5 in the general formula (1)) was dropped by a dropping funnel. . Thereafter, the mixture was reacted at 50 ° C. for 3 hours and further at 80 ° C. for 2 hours to obtain 1000 parts of an active energy ray-curable resin 1 (urethane acrylate prepolymer).

The obtained active energy ray-curable resin 1
Is dissolved in trimethylolpropane triacrylate (TMPTA) as a diluting monomer, and further, Irgacure 184 (manufactured by Ciba-Geigy, 1
(Hydroxycyclohexyl phenyl ketone) 3% was added and completely dissolved to obtain 1000 parts of an active energy ray-curable resin composition 1.

This solution was applied to an 80 μl
m at a conveyor speed of 20 m / min under a nitrogen atmosphere after application on a glass substrate to a thickness of 120 w / c.
Irradiation was performed using a high-pressure mercury lamp with an m ² output, and the number of irradiations until curing was measured.

For the obtained cured coating film, the pencil hardness (J
ISK5400), abrasion resistance (JISK540)
(Equivalent to 0) was evaluated. Table 1 shows the results.

Example 2 Isophorone diisocyanate (B-1) was placed in a 3 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
76.1 parts, 1.6 parts of dibutyltin dilaurate, and 0.1 part of hydroquinone were charged, and the mixture was kept at 50 ° C. and dropped with a dropping funnel to form an acrylate (A2-1) of propylene oxide adduct of sorbitol (A2-1). 1)
Where m = 2, r = 2, and q = 4)
375.2 parts were added dropwise. 3 hours at 50 ° C, then 80 ° C
After reacting for 2 hours to obtain half urethane, 548.8 parts of acrylate (A1-1) of propylene oxide adduct of sorbitol was added dropwise, and the mixture was reacted at 80 ° C. for 4 hours to obtain active energy ray-curable resin 2. , 1000 parts.

An active energy ray-curable resin composition 2 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 2 was used. , Was evaluated. Table 1 shows the results.

Example 3 A 3 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with hydrogenated xylene diisocyanate (B-
2) 123.6 parts, 1.6 parts of dibutyltin dilaurate,
0.1 parts of 2,6-di-t-butylhydroxytoluene was charged, and a condensate of bis (4,4-hydroxyphenyl) -2,2-propane and epichlorohydrin was added with a dropping funnel while maintaining the temperature at 50 ° C. C2-1) 144.8
Part was dropped. After reacting at 50 ° C. for 3 hours and further at 80 ° C. for 2 hours to obtain half urethane, acrylate of propylene oxide adduct of sorbitol (A1-
2) (In the general formula (1), m = 2, r = 1, q = 5
732.4 parts were added dropwise at 80 ° C.
After reacting for hours, the active energy ray-curable resin 3
0 parts were obtained.

An active energy ray-curable resin composition 3 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 3 was used. , Was evaluated. Table 1 shows the results.

Example 4 192.6 parts of hexamethylene diisocyanate (B-3) instead of isophorone diisocyanate (B-1);
Instead of the acrylate of the propylene oxide adduct of sorbitol (A1-1), the acrylate of the propylene oxide adduct of sorbitol (A1-
1) A mixture of 588 parts and 219 parts of pentaerythritol triacrylate (C1-1) was used in the same manner as in Example 1 to obtain 1000 parts of an active energy ray-curable resin 4.

An active energy ray-curable resin composition 4 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 4 was used. , Was evaluated. Table 1 shows the results.

Example 5 A 3 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with hexamethylene diisocyanate (B-
3) 182.6 parts, 1.6 parts of dibutyltin dilaurate,
0.1 parts of 2,6-di-t-butylhydroxytoluene was charged, and polymethylpentanediol adipate (D-1) (Mw5) was added with a dropping funnel while maintaining the temperature at 50 ° C.
00) 234.5 parts were added dropwise. After reacting at 50 ° C. for 3 hours and further at 80 ° C. for 2 hours to obtain a half urethane, acrylate of an ethylene oxide adduct of sorbitol (A1-3) (in the general formula (1), m = 3,
583.4 parts were dropped, and reacted at 80 ° C. for 4 hours to obtain 1000 parts of an active energy ray-curable resin 5.

An active energy ray-curable resin composition 5 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 5 was used. , Was evaluated. Table 1 shows the results.

Example 6 A 3 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel was charged with hexamethylene diisocyanate (B-
3) 140.7 parts, 1.6 parts of dibutyltin dilaurate,
While charging 0.1 part of 2,6-di-t-butylhydroxytoluene and maintaining the temperature at 50 ° C., an acrylic acid ester of propylene oxide adduct of sorbitol (A2-2) (in the general formula (1)) by a dropping funnel. , M = 1,
(composed of r = 2 and q = 4) 347.6 parts was added dropwise. After reacting at 50 ° C. for 3 hours and further at 80 ° C. for 2 hours to obtain half urethane, acrylate (A1-1) 37 of propylene oxide adduct of sorbitol was used.
2.8 parts and pentaerythritol triacrylate (C
1-1) A mixture with 138.9 parts was added dropwise at 80 ° C.
After reacting for hours, the active energy ray-curable resin 6
0 parts were obtained.

An active energy ray-curable resin composition 6 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 6 was used. , Was evaluated. Table 1 shows the results.

Example 7 Instead of isophorone diisocyanate (B-1), a trimer of an aliphatic diisocyanate (B-4) [trade name: DN9
01S: Dainippon Ink and Chemicals, Inc.] 186 parts;
In place of the acrylate of the propylene oxide adduct of sorbitol (A1-1), the acrylate of the ethylene oxide adduct of sorbitol (A1-
4) (in the general formula (1), m = 1, r = 1, q = 5
813 parts), and the same procedure as in Example 1 was repeated, except that 0.1 parts of 2,6-di-t-butylhydroxytoluene was used instead of hydroquinone. 1000 parts of the line-curable resin 7 was obtained.

An active energy ray-curable resin composition 7 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 7 was used. , Was evaluated. Table 1 shows the results.

Example 8 Isophorone diisocyanate (B-1) was placed in a 3 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel.
228.6 parts, dibutyltin dilaurate 1.6 parts, 2,
20 parts of polypropylene glycol (D-2) [trade name: PPG400: a product of Nippon Oil & Fats Co., Ltd.] was charged with 0.1 part of 6-di-t-butylhydroxytoluene by a dropping funnel while maintaining at 50 ° C. Was added dropwise. 50 ℃
For 3 hours and further at 80 ° C. for 2 hours to obtain half urethane. Then, 412.0 parts of acrylate (A1-1) of propylene oxide adduct of sorbitol and pentaerythritol triacrylate (C1-1) 15
The mixture with 3.5 parts was dropped and reacted at 80 ° C. for 4 hours to obtain 1000 parts of active energy ray-curable resin 8.

An active energy ray-curable resin composition 8 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 8 was used. , Was evaluated. Table 1 shows the results.

Comparative Example 1 The amount of isophorone diisocyanate (B-1) used was 42
3.7 parts, and instead of acrylate (A2-1) of propylene oxide adduct of sorbitol, polyethylene glycol [trade name: PEG400: manufactured by NOF Corporation] 381.6 parts; propylene oxide addition of sorbitol Acrylic acid ester (A1-
1) Instead of hydroxyethyl acrylate 194.
Except for using 6 parts, the same procedure as in Example 2 was carried out to obtain 1000 parts of active energy ray-curable resin 9.

An active energy ray-curable resin composition 9 was obtained in the same manner as in Example 1 except that the obtained active energy ray-curable resin 9 was used. , Was evaluated. Table 1 shows the results.

Comparative Example 2 The amount of isophorone diisocyanate (B-1) used was
7.3 parts, and instead of acrylate (A1-1) of propylene oxide adduct of sorbitol, pentaerythritol triacrylate 347.2
And a mixture of 135.2 parts of hydroxyethyl acrylate was used in the same manner as in Example 1 to obtain 1000 parts of an active energy ray-curable resin 10.

The obtained active energy ray-curable resin 10
Except for using, an active energy ray-curable resin composition 10 was obtained in the same manner as in Example 1, and a cured coating film was prepared and evaluated in the same manner. Table 1 shows the results.

[0080]

[Table 1]

[0081]

The active energy ray-curable resin obtained by the production method of the present invention and the composition thereof are excellent in reactivity, exhibit excellent surface hardness, and have a cured product having an appropriate flexibility. Can be provided.

Claims (5)

[Claims] An active energy ray-curable resin characterized by reacting (meth) acrylic acid ester (A) of an alkylene oxide adduct of sorbitol having a hydroxyl group with polyisocyanate (B) as an essential component 0. Production method. 2. A compound (C) having an unsaturated group and one or two hydroxyl groups together with a (meth) acrylic acid ester (A) of an alkylene oxide adduct of sorbitol having a hydroxyl group and a polyisocyanate (B). The method according to claim 1, wherein the reaction is carried out with a compound (D) having two hydroxyl groups. 3. The method according to claim 1, wherein the (meth) acrylic acid ester (A) of the alkylene oxide adduct of sorbitol having a hydroxyl group is a compound represented by the following general formula (1). Embedded image (In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an ethylene group or a propylene group, and m is 0.5 to 5.0 on average.
Wherein a plurality of m in the same molecule may be the same or different, q is 3.5 to 5.5 on average, r is 0.5 to 2.5 on average, And q + r = 6. ) 4. The method according to claim 1, wherein the polyisocyanate (B) is a di- or tri-isocyanate.
The manufacturing method described in (1). 5. An active energy ray-curable resin composition comprising the active energy ray-curable resin obtained by the production method according to claim 1 as an essential component.