JPH05105747A - Polyol, curable resin and composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a polyester (carbonate) polyol having a polycyclic aliphatic dicarboxylate residue and suitable as a photo-setting composition by reacting and oligomerizing a diisocyanate with a (meth)acrylate monomer containing active hydrogen. CONSTITUTION:The objective polyester (carbonate) polyol contains the group of formula ((p) is 0, 1 or 2; R is CH2CH2 or CH=CH) as a structural unit. Preferably, the objective polyol is made to react with a diisocyanate and a (meth)acrylate monomer containing active hydrogen to form a polymerizable oligomer, which is preferably incorporated with a photopolymerization initiator and other polymerizable monomer compound, etc., to obtain a photo-setting composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyester polyol and polyester carbonate polyol, a polymerizable oligomer obtained therefrom, a curable composition containing the polymerizable oligomer and a cured product thereof.

[0002] In recent years, curable resins by ultraviolet rays or electron beams have been widely used for applications such as paints, inks, coatings, adhesives, and electronics, and the range of application thereof is expanding. The reason for this is that these radiation curable resins are quick curable and do not contain a solvent, so they have the advantages of resource saving, energy saving, low pollution, and high productivity as compared with thermosetting resins. is there.

Although the radiation-curable resin has the above-mentioned advantages, it has problems in skin irritation, polymerization inhibition by oxygen, adhesiveness, adhesiveness, mechanical properties, internal stress, weather resistance and the like. It is also known to be doing.

[0004]

As described above, the radiation curable composition has some problems, but the shrinkage upon curing is one of the major problems. For example, in applications such as adhesives, the adhesiveness and adhesion are often inferior due to shrinkage during curing, and in applications where it is used as a structural material, residual stress, deformation, etc. occur, and in severe cases problems such as cracking occur. Therefore, the advent of a radiation curable composition having a low shrinkage ratio is desired.

The object of the present invention is to provide a novel polymerizable oligomer having a low shrinkage ratio, a radiation-curable composition containing the same, a cured product obtained by curing the same, and a polyol which is a raw material of the polymerizable oligomer. To provide.

[0006]

According to the present invention, the above objects are achieved by providing the following items. As a structural unit, the following formula (I)

[0007]

[Chemical 2]

(In the formula, p represents 0, 1 or 2, and R is a group represented by the formula -CH ↓ 2-CH ↓ 2- or the formula -CH.
Represents a group represented by = CH-. ) A polyester polyol or polyester carbonate polyol having a group represented by At least one polyol selected from the group consisting of the above polyester polyols and polyester carbonate polyols and diisocyanate, and active hydrogen-containing acrylic monomer and / or active hydrogen-containing methacrylic monomer [hereinafter, these are referred to as active hydrogen Inclusion (meta)
Collectively referred to as an acrylic monomer] is a polymerizable oligomer obtained by reacting. A curable composition comprising the above-mentioned polymerizable oligomer, a monomer compound having a polymerizable double bond, and a polymerization initiator. A cured product obtained by curing the above curable composition.

The group represented by the formula (I) is derived from the corresponding carboxylic acid or its ester derivative, and its three-dimensional structure may be trans or cis, and the alicyclic structure part is also included. Either the endo form or the exo form may be used. The group represented by formula (I) may be a mixture of these stereoisomers.

The above-mentioned polyol means a polymer having a plurality of hydroxyl groups at the terminals. Its number average molecular weight is 200
It is preferably in the range of -100,000. Polyol is polyurethane other than the polymerizable oligomer of the present invention,
It can be used as a suitable material for melamine resin,
There is an optimal molecular weight range for each application.

When the above-mentioned polyol is used as a raw material for the polymerizable oligomer of the present invention, the higher the molecular weight thereof, the higher the viscosity of the obtained polymerizable oligomer. On the other hand, when the molecular weight of the polyol is too small, the urethane group is too small. Since the concentration increases, the viscosity increases due to the intermolecular interaction of urethane bonds. Therefore, in this case, the number average molecular weight of the polyol is preferably in the above range,
It is more preferably in the range of 0 to 10,000.

The polyester polyol of the present invention is similar to the known method used in the production of polyethylene terephthalate or polybutylene terephthalate from a dicarboxylic acid having a group represented by formula (I) or its derivative and a diol. It can be produced by a method, that is, a transesterification reaction or a direct esterification reaction followed by a melt polycondensation reaction. The polyester carbonate polyol can be produced, for example, by a known production method, that is, an esterification reaction or a transesterification reaction, by simultaneously charging a dicarboxylic acid or a derivative thereof having a group represented by the formula (I), a diol and a carbonate compound. it can. In addition, a polyester polyol or a polycarbonate polyol is previously synthesized, and then a carbonate compound is reacted in the former case, and a diol, a dicarboxylic acid having a group represented by the formula (I) or a derivative thereof is reacted in the latter case. It is also possible to manufacture.

When synthesizing the polyol of the present invention, a dicarboxylic acid having a group represented by the formula (I) or its ester derivative is essential as a dicarboxylic acid component, but one of other dicarboxylic acids as a copolymerization component. Alternatively, two or more kinds can be used. Examples of such dicarboxylic acid include succinic acid, methylmalonic acid, glutaric acid, dimethylmalonic acid, adipic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 3-methylglutaric acid, 3,3. -Aliphatic dicarboxylic acids such as dimethyl glutaric acid, 3-methyl adipic acid, pimelic acid, dimethyl adipic acid, suberic acid, azelaic acid, sebacic acid, undecane dicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2, Aromatic dicarboxylic acids such as 6-dicarboxylic acid and naphthalene-2,7-dicarboxylic acid; and dicarboxylic acids having an alicyclic skeleton such as cyclohexanedicarboxylic acid. When the polymerizable oligomer of the present invention is used for UV curing, aromatic dicarboxylic acids and their derivatives have UV absorbing sites, and therefore, they are used as the dicarboxylic acid component of the above polyester polyol and polyester carbonate polyol. Is not preferable.

In order to realize the characteristics of the present invention, it is preferable to use dicarboxylic acid having a group represented by the formula (I) in an amount of 20 mol% or more based on the total carboxylic acid component.
It is more preferable to use at least mol%.

As the diol component for synthesizing the polyol of the present invention, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, propane diol, 1,4-butane diol, 1,
5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-
1,8-octanediol, 1,9-nonanediol,
1,10-decanediol, norbornane-2,3-dimethanol, 3 (4), 8 (9) -dihydroxymethyl-tricyclo [5.2.1.0 ↑ 2 ↑, ↑ 6] decane,
Hydroquinone, bisphenol A, etc. are used. In addition to these diol components, it is also possible to use trifunctional alcohols such as glycerin, trimethylolethane, trimethylolpropane, and trimethylolheptane. However, if the amount of trifunctional alcohol added is large, gelation is likely to occur. Therefore, it is desirable to adjust the charging ratio so that the trifunctional alcohol copolymerized per one molecule of the polyol has an average of 5 molecules or less. When the polymerizable oligomer of the present invention is used for ultraviolet curing, the compound having an aromatic ring has an ultraviolet absorbing site, and therefore it is not preferable to use it as the diol component of the above polyester polyol and polyester carbonate polyol. ..

Examples of the carbonate compound used when synthesizing the polyester carbonate polyol include diphenyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate.

In producing the polymerizable oligomer of the present invention, the above-mentioned polyol and diisocyanate are reacted,
Next, when the active hydrogen-containing (meth) acrylic monomer is reacted, the reaction is performed under the condition that the isocyanate group is in excess of the hydroxyl group of the polyol (OH / NCO <1). When is close to 1, the molecular weight increases due to chain extension and the viscosity increases. Therefore, the hydroxyl group is 0.5 to 0.75 with respect to 1 mol of the isocyanate group.
It is preferable to adjust the amount to be in the range of mol.
When reacting the obtained polyol of the terminal isocyanate with the active hydrogen-containing (meth) acrylic monomer, it is preferable to adjust so that an equimolar amount of active hydrogen is present with the isocyanate group. Also, when reacting the polyol and the diisocyanate, an appropriate amount of diol, for example,
The amount of diol having 1 to 3 times the amount of hydroxyl groups with respect to the amount of hydroxyl groups contained in the polyol is added to participate in the reaction
By reacting the obtained compound with active hydrogen-containing (meth) acrylate, a polymerizable oligomer having a hard segment can be obtained. Examples of the diol used at this time include 1,4-butanediol,
1,6-hexanediol etc. are mentioned. On the other hand, when chain extension is not necessary, the above method may be used, but first, an equimolar amount of diisocyanate and an active hydrogen-containing (meth) acrylic monomer are reacted to synthesize a (meth) acrylic group-containing monoisocyanate. Then, the desired polymerizable oligomer can be obtained by reacting this with a polyol.

As the diisocyanate, an aromatic, aliphatic or alicyclic diisocyanate commonly used in the polyurethane industry can be used. For example, 4,4'-
Diphenylmethane diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,
1,5-naphthylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,
It is preferable to use 4′-dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane or the like.

Examples of active hydrogen-containing (meth) acrylic monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
1,4-butanediol mono (meth) acrylate,
1,6-hexanediol mono (meth) acrylate,
1,9-nonanediol mono (meth) acrylate, propylene oxide-modified mono (meth) acrylate, caprolactone-modified mono (meth) acrylate and the like can be mentioned.

The curable composition of the present invention comprises the above-mentioned polymerizable oligomer, a monomer compound having a polymerizable double bond, and a polymerization initiator, which are cured to give a cured product. can get. Curing is carried out by a means known per se, for example, a curing means using ultraviolet rays, electron beams, heat, microwaves, high frequencies and the like.

The polymerization initiator is appropriately selected from those used in ordinary polymerization reactions according to the curing means such as ultraviolet rays, electron beams, heat, microwaves and high frequencies. When an electron beam is used as a curing means, it is not necessary to add a polymerization initiator, but when other means is used, a suitable polymerization initiator is usually allowed to coexist to increase the curing rate. You can The amount of the polymerization initiator compounded is generally 0. 1 with respect to 100 parts by weight of the resin-forming component.
01 to 10 parts by weight is preferable, and 1 to 5 parts by weight is more preferable.

As the polymerization initiator, for example, in the case of ultraviolet curing, a photopolymerization initiator that absorbs ultraviolet rays to generate radicals is used. Such photopolymerization initiators are roughly classified into two types: intramolecular bond cleavage type and intermolecular hydrogen abstraction type. Examples of the former include 4-phenoxydichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1. -(4-dodecylphenyl) propan-1-one, 1- (2-hydroxyethoxyphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl-phenyl ketone,
Acetophenone-based compounds such as 2-methyl-2-morpholino-1-thiomethylphenylpropan-1-one; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal. Be done. On the other hand, examples of the latter include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, chlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated benzophenone, 3,
Benzophenone series such as 3′-dimethyl-4-methoxybenzophenone; 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone,
2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,
4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrenequinone, camphorquinone, benzyl, 3,3 ′,
4,4'-Tetra (t-butylperoxycarbonyl)
Thioxanthone compounds such as benzophenone, dibenzosuberone and 2-ethylanthraquinone; Michler's ketone, 4,
4'-diethylaminophenone and the like can be mentioned.

In the case of ultraviolet curing, the above photopolymerization initiator alone cures, but a photosensitizer may be used in combination for further improving the curability. As the photosensitizer, triethanolamine, methyldiethanolamine, dimethylaminoethanol, triisopropanolamine, 4
Examples include amines such as ethyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoic acid. The compounding amount of the photosensitizer is usually preferably 0.01 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin-forming component.

As another polymerization initiator, a usual thermal polymerization initiator is used when the curing method mainly uses heat energy. Specific examples of such a thermal polymerization initiator include:
Acetyl peroxide, p-chlorobenzoyl peroxide, isobutyryl peroxide, bis (3,5,5-
(Trimethylhexanoyl) peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2 , 5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-dit-butylperoxy-3,3,5-trimethylcyclohexane, 1, 1-di-t-butylperoxycyclohexane,
Organic peroxides such as 2,2′-di-t-butyl peroxybutane, t-butyl peracetate, t-butyl perbenzoate, t-butyl peroxyisopropyl carbonate, diisopropyl peroxydicarbonate;
2'-azobis (2,4-dimethylvaleronitrile),
2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2-
Azobis such as cyano-2-propylazoformamide, 2,2'-azobis-1-cyclobutanenitrile, 4,4'-azobis-4-cyanopentanoic acid, 2,2'-azobiscyclopropylpropionitrile Compounds.

In the present invention, the monomer compound having a polymerizable double bond is added in order to make the curable composition have a lower viscosity. Examples of the monomer compound include acrylamide, acrylic acid, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, butyl cellosolve acrylate, n-butyl acrylate, cyclohexyl acrylate, and methacrylic acid. Amide, methacrylic acid,
Methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, lauryl methacrylate, phenyl methacrylate, vinyl acetate, styrene, acrylonitrile, cinnamon Acid, crotonic acid, maleic anhydride, itaconic acid, N-methylmaleimide, N-phenylmaleimide, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A dioxydiethylene glycol diacrylate, tri Methylolpropane triacrylate, pentaerythri Triacrylate, diethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, bisphenol A dioxydiethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, 1,4-butanediol diacrylate , 1,4
Examples include butanediol dimethacrylate and N-vinylpyrrolidone. The blending amount of such a monomer compound is
Up to 50% by weight of the resin-forming component is preferable, and 5 to 30% by weight is more preferable. It is not preferable to use a large amount of a volatile vinyl monomer such as a lower alkyl ester of (meth) acrylic acid, styrene or acrylonitrile because it evaporates during curing to cause problems such as bad odor and toxicity.

The polymerizable oligomer of the present invention or the curable composition containing the same is treated with an ultraviolet ray, an electron beam, heat, a microwave,
A cured product can be obtained by curing by a known means such as high frequency.

By using the polymerizable oligomer of the present invention, a curable composition which gives a resin having a further improved surface curability is obtained. By curing this, a cured product having excellent adhesion to a substrate is obtained. Can be obtained. Formula (I)
Among the groups represented by, R is a surface of a curable composition containing a polymerizable oligomer obtained from a polyol having a group having a group represented by the formula —CH═CH— as a structural unit. A resin having excellent curability can be obtained.
The curable composition of the present invention is a coating agent or surface treatment agent for various materials such as metal, plastic, glass, wood, paper and fiber, a vehicle for printing ink, a binder, a plastic material, a molding material, a laminated plate, etc. It can be applied not only to the more widely used applications, but also to the optics-related and electronics-related applications.

[0028]

EXAMPLES Next, the present invention will be described more specifically by way of Examples and Comparative Examples. The curability and the like were evaluated by the following methods. (1) Surface curability: A cylindrical cell having a depth of 100 μm and a diameter of 3 cm was prepared, the curable composition was poured into the cell, and the weight was measured. This was irradiated with ultraviolet rays for 2 seconds, the uncured portion was wiped off with acetone and dried, and the thickness wiped off was calculated from the weight reduction in consideration of specific gravity. (2) Shrinkability: Calculated from the densities before and after curing measured at room temperature by the helium gas substitution method.

Examples 1 to 3 A reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a water separation tube was charged with a predetermined amount of norbornane-2,3-dicarboxylic acid and 1,6-hexanediol, and these raw materials were used. On the other hand, 10 ppm of titanium tetraisopropoxide was charged, and by-product water was distilled off while stirring at a reaction temperature of 200 to 220 ° C. under a nitrogen atmosphere. The acid value of the product is 0.
When it reached 3, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. The acid value, hydroxyl value (OH value) and polystyrene conversion number average molecular weight of the obtained polyester polyol were measured by gel permeation chromatography. Table 1 shows the charging conditions and the measurement results.

Example 4 In Example 1, 393 was added to 1,6-hexanediol.
Parts by weight, and instead of 528 parts by weight of norbornane-2,3-dicarboxylic acid, perhydro-1,4; 5,8-
A polyester polyol was synthesized by the same method except that 709 parts by weight of dimethanonaphthalene-2,3-dicarboxylic acid was used. The acid value of the obtained polyester polyol,
The hydroxyl value and number average molecular weight were measured. Table 1 shows the charging conditions and the measurement results.

Example 5 In Example 1, 480 was added to 1,6-hexanediol.
A polyester polyol was synthesized in the same manner as above except that 549 parts by weight of 5-norbornene-2,3-dicarboxylic acid was used instead of 528 parts by weight of norbornane-2,3-dicarboxylic acid. The acid value, hydroxyl group and number average molecular weight of the obtained polyester polyol were measured. Table 1 shows the charging conditions and the measurement results.

Example 6 A reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and an outflow tube was equipped with 557 parts by weight of 1,6-hexanediol, 248 parts by weight of norbornane-2,3-dicarboxylic acid, and 296 parts by weight of adipic acid. Parts and diphenyl carbonate 18
0 part by weight was charged, and phenol and water were distilled off at 160 ° C. under a nitrogen atmosphere. When the acid value became 0.3 or less, a vacuum was applied to completely distill off phenol and water. The acid value, the hydroxyl value, and the polystyrene equivalent number average molecular weight of the obtained polyester carbonate polyol were measured by gel permeation chromatography. The measurement results are shown in Table 1.

Comparative Example 1 In Example 1, 546 of 1,6-hexanediol was added.
A polyester polyol was synthesized by the same method except that 603 parts by weight of adipic acid was used instead of 528 parts by weight of norbornane-2,3-dicarboxylic acid. The acid value, hydroxyl group and number average molecular weight of the obtained polyester polyol were measured. Table 1 shows the charging conditions and the measurement results.

[0034]

[Table 1]

Examples 7 to 12 100 parts by weight of the polyols obtained in Examples 1 to 6 were dried under reduced pressure at 110 to 115 ° C. for 30 minutes under a nitrogen atmosphere, to which a predetermined amount of isophorone diisocyanate was added. And reacted at 110 to 115 ° C. The reaction was followed by the concentration of residual isocyanate groups, and when the amount of residual isocyanate in the reaction system reached about 50% of the charged amount, a predetermined amount of 2-hydroxyethyl acrylate and dibutyltin dilaurate (DBTDL) were added as resin forming components. 100 ppm was added to the total charged amount, and 100 ppm of para-methoxyphenol was added to the total charged amount of the resin-forming component. After blowing air, the reaction was carried out at 115 to 120 ° C., and after confirming that the residual isocyanate amount was 1% or less, the reaction was terminated to obtain a polymerizable oligomer. 95 parts by weight of the obtained polymerizable oligomer, and a photopolymerization initiator (Irgacure 651, CIBA-G
5 parts by weight (manufactured by EIGY) was mixed to obtain a composition. The surface curability and shrinkage of this composition were evaluated.
Table 2 shows the charging conditions and the evaluation results.

Example 13 100 parts by weight of the polyester polyol obtained in Example 2 was dried under reduced pressure at 110 to 115 ° C. for 30 minutes under a nitrogen atmosphere, and 33.3 parts by weight of isophorone diisocyanate was added thereto. The reaction was carried out at 110 to 115 ° C. The reaction was followed by the concentration of residual isocyanate groups, and when the amount of residual isocyanate in the reaction system reached about 33% of the charged amount, 2-hydroxyethyl acrylate was added to 5.
8 parts by weight, dibutyltin dilaurate (DBTDL) was added at 100 ppm to the total amount of the resin-forming component, and paramethoxyphenol was added at 100 ppm to the total amount of the resin-forming component. After blowing air, the reaction was carried out at 115 to 120 ° C., and after confirming that the residual isocyanate amount was 1% or less, the reaction was terminated to obtain a polymerizable oligomer. 95 parts by weight of the obtained polymerizable oligomer, and a photopolymerization initiator (Irgacure
651) 5 parts by weight were mixed to obtain a composition. The surface curability and shrinkage of this composition were evaluated. Table 2 shows the charging conditions and the evaluation results.

Example 14 100 parts by weight of the polyester polyol obtained in Example 2 was dried under reduced pressure at 110 to 115 ° C. for 30 minutes under a nitrogen atmosphere, to which isophorone diisocyanate 3 was added.
8.9 parts by weight and 1,6-hexanediol 11.8
Parts by weight were added and the reaction was carried out at 110 to 115 ° C. The reaction was traced by the concentration of residual isocyanate groups, and when the amount of residual isocyanate in the reaction system reached about 14% of the charged amount, 5.8 parts by weight of 2-hydroxyethyl acrylate,
Dibutyltin dilaurate (DBTDL) is 100 ppm with respect to the total amount of the resin-forming component, and paramethoxyphenol is 1 with respect to the total amount of the resin-forming component.
00 ppm was added. 115-1 while blowing air
After reacting at 20 ° C. and confirming that the amount of residual isocyanate was 1% or less, the reaction was terminated to obtain a polymerizable oligomer. 95 parts by weight of the obtained polymerizable oligomer, and a photopolymerization initiator (Irgacure 651)
The composition was obtained by mixing 5 parts by weight. The surface curability and shrinkage of this composition were evaluated. Table 2 shows the charging conditions and the evaluation results.

Example 15 A polymerizable oligomer was synthesized in the same manner as in Example 8 except that 13 parts by weight of 2-hydroxyethyl methacrylate was used instead of 11.6 parts by weight of 2-hydroxyethyl acrylate. Got The surface curability and shrinkage of this composition were evaluated. The evaluation results are shown in Table 2.

Example 16 70 parts by weight of the polymerizable oligomer obtained in Example 8, 25 parts by weight of hexanediol diacrylate, and 5 parts by weight of a photopolymerization initiator (Irgacure 651) were mixed to obtain a composition. The surface curability and shrinkage of this composition were evaluated. The evaluation results are shown in Table 2.

Comparative Example 2 A polymerizable oligomer was prepared in the same manner as in Example 8 except that 100 parts by weight of the polyester polyol obtained in Comparative Example 1 was used instead of 100 parts by weight of the polyester polyol obtained in Example 2. Was synthesized to obtain a composition. The surface curability and shrinkage of this composition were evaluated. The evaluation results are shown in Table 2.

Comparative Example 3 In Example 8, 100 parts by weight of the polyester polyol obtained in Comparative Example 1 was used in place of 100 parts by weight of the polyester polyol obtained in Example 2, and 2-hydroxyethyl acrylate 11.6. A polymerizable oligomer was synthesized by the same method except that 13 parts by weight of 2-hydroxyethyl methacrylate was used instead of parts by weight to obtain a composition. The surface curability and shrinkage of this composition were evaluated. The evaluation results are shown in Table 2.

Comparative Example 4 A composition was prepared in the same manner as in Example 16 except that 70 parts by weight of the polymerizable oligomer obtained in Example 8 was used instead of 70 parts by weight of the polymerizable oligomer obtained in Example 8. I got a thing. The surface curability and shrinkage of this composition were evaluated. The evaluation results are shown in Table 2.

[0043]

[Table 2]

[0044]

By using the polymerizable oligomer of the present invention, it is possible to obtain a curable composition having a small volume shrinkage upon curing and excellent adhesiveness and adhesiveness. Moreover, among the polymerizable oligomers of the present invention, a curable composition using a polymerizable oligomer having an acryloyl group is particularly excellent in air-drying property. The polyol of the present invention not only gives the polymerizable oligomer, but is widely applicable to various uses such as polyurethane and melamine resin.

Claims (4)

[Claims] 1. A structural unit represented by the following formula (I): (In the formula, p represents 0, 1 or 2, and R represents the formula -CH ↓ 2.
Represents a group represented by —CH ↓ 2- or a group represented by the formula —CH═CH—. ) A polyester polyol or polyester carbonate polyol having a group represented by 2. At least one polyol selected from the group consisting of the polyester polyol and the polyester carbonate polyol according to claim 1, and a diisocyanate, and an active hydrogen-containing acrylic monomer and / or an active hydrogen-containing methacrylic unit amount. A polymerizable oligomer obtained by reacting the body. 3. A curable composition comprising the polymerizable oligomer according to claim 2 and a monomer compound having a polymerizable double bond, and a polymerization initiator. 4. A cured product obtained by curing the curable composition according to claim 3.