JP2002338644A - Polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polymerizable resin composition which is cured with little bad odor and little volatilization loss of a polymerizable monomer and can give a cured product that is excellent in heat resistance and weather resistance (especially, long-term weather resistance), has no brittleness and is good in impact resistance, bendability, extensibility and process ability workability. SOLUTION: The polymerizable resin composition comprises a polymer and polymerizable monomers, wherein the polymerizable monomers contain indispensably a polymerizable monomer having a specific structure, that is, cyclohexyl (meth)acrylate (the cyclohexyl group may have a substituent group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various molding materials such as fiber reinforced plastics, press molding materials and casting materials, and coating materials such as paints, coated floors, linings, coatings and gel coats, and the like. The present invention relates to a polymerizable resin composition that can be used for various uses such as resin concrete, putty, and an adhesive.

[0002]

2. Description of the Related Art Conventionally, a curable resin composition containing a polymer and a polymerizable monomer, which is called a curable resin, is easy to handle in a liquid state, and is prepared by mixing a polymerization initiator. Since it can be cured at room temperature, under heating, or under irradiation of radiation, and can be a tough cured product, it is used for various purposes. These effects, in the curable resin composition, for the purpose of lowering the viscosity to enhance its workability and moldability,
Due to the fact that polymerizable monomers (reactive monomers) such as styrene and methyl methacrylate are mixed and used as reactive diluents, and that the polymer is reactive and forms a crosslinked product are doing. Thus, a curable resin composition having a desired viscosity is obtained by adding these reactive monomers as a reactive diluent to a resin solid content of an oligomer or a polymer.

[0003] Among such curable resin compositions,
In particular, when styrene, methyl methacrylate, and cyclohexyl (meth) acrylate are used as the polymerizable monomer, problems such as boiling and evaporation of the polymerizable monomer during molding, heat resistance after curing, and weather resistance are observed. It is generally well known that any of the problems of sex and the like can be solved.

However, when styrene is used as the polymerizable monomer, it is inexpensive and has excellent diluting ability, but it has problems of effects as environmental hormones and carcinogenicity, as well as the resulting cured product. However, there is still a problem that the weather resistance is not sufficient even when the weather resistance is high, and the color is easily discolored. On the other hand, when methyl methacrylate is used, it is inexpensive,
Although the cured product is excellent in weather resistance and heat resistance and is not easily discolored, it cannot be said that it is sufficient when it has long-term weather resistance. At the time of molding, a low boiling point and high shrinkage of methyl methacrylate cause a problem of molding failure. When cyclohexyl (meth) acrylate is used, the obtained cured product has a hard and brittle property, and has poor impact resistance, flexibility, elongation, and workability, and also has poor weather resistance. There is also a problem that the cyclohexyl group which improves the properties and the like is easily eliminated by hydrolysis or the like.

[0005]

The problem to be solved by the present invention is to reduce the odor and volatilization loss of the polymerizable monomer at the time of curing, and to obtain heat resistance and weather resistance (particularly long term) after curing. To provide a novel polymerizable resin composition for obtaining a cured product which is excellent in weather resistance), hard and not brittle, and has good impact resistance, flexibility, elongation and processability. is there.

[0006]

Means for Solving the Problems The present inventor has made intensive studies in order to solve the above problems. As a result, in a curable polymerizable resin composition containing a polymer and a polymerizable monomer as a reactive diluent, the polymerizable monomer has a cyclohexylmethyl group as an essential component (meth) acrylic. If it contains an acid ester, it has been found that it becomes a novel polymerizable resin composition that solves the above problems at once,
The present invention has been completed.

The cyclohexylmethyl (meth) acrylate, which is a (meth) acrylic ester having a cyclohexylmethyl group, has a cyclohexyl ring structure having good weather resistance, and has a polymerizable (meth) acryloyl with the cyclohexyl ring structure. It has a methylene structure between the base structure. Due to the presence of this methylene structure, the obtained cured product can be made excellent in the above-mentioned various properties such as improvement in hard brittleness as compared with the case where cyclohexyl (meth) acrylate having no such structure is used. Also, the balance between the strength and the elongation of the cured product can be made very excellent.

That is, the polymerizable resin composition according to the present invention is a composition containing a polymer and a polymerizable monomer,
The polymerizable monomer is a polymerizable monomer having a specific structure, cyclohexylmethyl (meth) acrylate (however,
(A cyclohexyl group may have a substituent)) as an essential component.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polymerizable resin composition of the present invention will be specifically described.

The polymerizable resin composition according to the present invention is a curable polymerizable resin composition containing a polymer and a polymerizable monomer, wherein the polymerizable monomer is cyclohexylmethyl (meth). It is characterized by containing acrylate, that is, cyclohexylmethyl ester of (meth) acrylic acid (however, the cyclohexyl group may have a substituent).

[Polymerizable monomer] The polymerizable monomer component contained in the polymerizable resin composition according to the present invention is cyclohexylmethyl (meth) acrylate (provided that the cyclohexyl group has a substituent. Good).

The above cyclohexylmethyl (meth) acrylate (the cyclohexyl group may have a substituent), that is, cyclohexylmethyl ester of (meth) acrylic acid (the cyclohexyl group has a substituent) May be represented by the following general formula (1):

[0013]

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It is preferred that

In the specific polymerizable unsaturated monomer represented by the general formula (1), R ¹ is a hydrogen atom or a methyl group.

In the specific polymerizable unsaturated monomer represented by the general formula (1), R ² represents an organic residue on a cyclohexyl group. Further, m represents an integer from 0 to 2, and when m is 0, it is unsubstituted, when m is 1, it is 1-substituted,
When m is 2, it represents 2-substitution. In this case, R ² may be a substituent at any position on the cyclohexyl group, one or more substituents may be present at one or more positions, or two or more substituents may be present. The group may be present at one or more places. When R ² is an organic residue,
For example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxyalkyl group having 1 to 5 carbon atoms And a halogenated (for example, chlorinated, brominated or fluorinated) alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 4 carbon atoms,
A hydroxyalkyl group having 1 to 2 carbon atoms, an alkoxyalkyl group having 1 to 2 carbon atoms, and an acetoxyalkyl group having 1 to 2 carbon atoms are preferably used. The R ² is as described above.
The substituent may be at any position on the cyclohexyl group, but is preferably at the 3- or 4-position. It is also preferable that there is no substituent on the cyclohexyl group. However, R ² does not include the substituent structure of the epoxy group, which is found in, for example, 3,4-epoxycyclohexylmethyl (meth) acrylate and 3,4-epoxycyclohexylethyl (meth) acrylate. . That is, the cyclohexyl group structure in the general formula (1) of the present application does not include an alicyclic epoxy ring structure.

The cyclohexylmethyl (meth) acrylate represented by the general formula (1) is not particularly limited, but specific examples include cyclohexylmethyl (meth) acrylate and 4-methylcyclohexylmethyl (meth). A) acrylate, 4-ethylcyclohexylmethyl (meth) acrylate, 4-propylcyclohexylmethyl (meth) acrylate, 4-butylcyclohexylmethyl (meth) acrylate, 4-methoxycyclohexylmethyl (meth) acrylate, 4-ethoxycyclohexylmethyl (meth) ) Acrylate, 4-acetoxymethylcyclohexylmethyl (meth) acrylate, 4-acetoxyethylcyclohexylmethyl (meth) acrylate, 3-methylcyclohexylmethyl (meth) acrylate, -Ethylcyclohexylmethyl (meth) acrylate, 3-propylcyclohexylmethyl (meth) acrylate, 3-butylcyclohexylmethyl (meth) acrylate, 3-methoxycyclohexylmethyl (meth) acrylate, 3-ethoxycyclohexylmethyl (meth) acrylate, 3 -Acetoxymethylcyclohexylmethyl (meth) acrylate,
Preferable examples include 3-acetoxyethylcyclohexylmethyl (meth) acrylate and 3-hydroxymethylcyclohexylmethyl (meth) acrylate. Of these, those containing isomers include the isomers alone and / or
Alternatively, it may be a mixture of isomers. Also, among those listed above, 4-methylcyclohexylmethyl (meth) acrylate, 4-ethylcyclohexylmethyl (meth) acrylate, 4-methoxycyclohexylmethyl (meth) acrylate, 4-acetoxymethylcyclohexylmethyl (meth) acrylate, 3-Methylcyclohexylmethyl (meth) acrylate, 3-ethylcyclohexylmethyl (meth) acrylate, 3-acetoxyethylcyclohexylmethyl (meth) acrylate, and 3-hydroxymethylcyclohexylmethyl (meth) acrylate are more preferably used. These may be used alone or in combination of two or more.
It is even more preferred to use methylcyclohexylmethyl (meth) acrylate.

The content of the cyclohexylmethyl (meth) acrylate contained in the polymerizable monomer in the present invention is preferably 5 to 100% by weight, more preferably 10 to 90% by weight, and still more preferably. 15-8
5% by weight. If the content is less than 5% by weight, it is not preferable because there is a possibility that the effect of preventing hard brittleness and improving weather resistance and heat resistance may not be exhibited.

As a method for producing cyclohexylmethyl (meth) acrylate represented by the above general formula (1), specifically, for example, (meth) acrylic acid and an alcohol represented by the following general formula (2) are used. A production method by the reaction of
A production method by reacting a halide of (meth) acrylic acid with an alcohol represented by the following general formula (2),
Production method by reacting an acid anhydride of (meth) acrylic acid with an alcohol represented by the following general formula (2), alkyl (meth) acrylates and the following general formula (2)
Preferred examples include a production method based on a reaction with an alcohol represented by the following formula, and a production method based on a reaction between a (meth) acrylic acid and a carboxylic acid ester represented by the following general formula (3). It is not done. Among these, the above and the above production methods are particularly preferable from the viewpoint of economy and the like.

[0020]

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[0021]

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(Wherein, R ² represents an organic residue on a cyclohexyl group, R ³ represents a hydrogen atom or an organic residue, m represents an integer from 0 to 2, and n represents an integer from 1 to 4. However, as the R ^2, for example, 3,4-epoxy seen in such cyclohexylmethyl (meth) acrylate, and does not include a substituent epoxy group.) containing the polymerizable monomer in the present invention Other polymerizable monomers other than the above cyclohexylmethyl (meth) acrylate that can be used are not particularly limited, but specifically include vinyl monomers such as styrene and vinyl toluene; methyl ( (Meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth)
Acrylate, sec-butyl (meth) acrylate,
n-propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-ethylcyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 4 -Acetoxycyclohexyl (meth) acrylate, 3-ethylcyclohexyl (meth) acrylate,
3-methylcyclohexyl (meth) acrylate, 3-
Methoxycyclohexyl (meth) acrylate, 3-acetoxycyclohexyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, cyclohexylbutyl (meth) acrylate, 4-ethylcyclohexylmethyl (meth) acrylate, 4-methyl Cyclohexylethyl (meth) acrylate, 3-methylcyclohexylethyl (meth) acrylate, 4-methylcyclohexylpropyl (meth) acrylate, 3-methylcyclohexylpropyl (meth) acrylate, 4-methylcyclohexylbutyl (meth) acrylate, 3-methyl Cyclohexylbutyl (meth) acrylate, n-lauryl (meth) acrylate, dicyclopentanyl (meth)
Acrylate, n-stearyl (meth) acrylate,
(Meth) acrylic acid alkyl esters such as isostearyl (meth) acrylate, isobornyl (meth) acrylate, and tert-butyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
(Meth) acrylates having a hydroxyl group such as acrylate, caprolactone-modified hydroxy acrylate (trade name: Praxel F series, manufactured by Daicel Chemical Industries, Ltd.), caprolactone-modified hydroxy methacrylate (trade name: Praxel FM series, manufactured by Daicel Chemical Industries, Ltd.) Acrylic acid, (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, itaconic anhydride, acrylic acid anhydride, (meth) acrylic acid, carboxyl-terminated caprolactone-modified acrylate (product) (Meth) acrylates having an acidic functional group, such as name PLAXEL FA series (manufactured by Daicel Chemical Industries, Ltd.) and carboxyl group-terminated caprolactone-modified methacrylate (brand name PLAXEL FMA series, manufactured by Daicel Chemical Industries, Ltd.) Various tertiary substances such as 2-dimethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate (Meth) acrylates having an amino group, acrolein, diacetone acrylamide, diacetone (meth) acrylamide, N-
[2- (dimethylamino) ethyl] (meth) acrylamide, N- [2- (di-n-propylamino) ethyl]
(Meth) acrylamide, N- [3- (dimethylamino) propyl] (meth) acrylamide, N- [4-
(Dimethylamino) butyl] (meth) acrylamide,
Polymerizable monomers having a formyl group or an oxo group such as N, N-dimethyl (meth) acrylamide and N- (meth) acryloylmorpholine; allyl esters such as allyl acetate and allyl benzoate; allyl ethyl ether and allyl Allyl ethers such as glycidyl ether and allylphenyl ether; vinyl compounds such as ethylene, propylene, isobutylene, 1-butene, 1-hexene, styrene, α-methylstyrene, vinyltoluene, divinylbenzene, and vinylpyridine; Acrylamide, N, N-dimethylaminopropylacrylamide,
N-isopropylacrylamide, t-butylacrylamide, N, N'-dimethylaminoethyl (meth) acrylate, N, N'-diethylaminoethyl (meth) acrylate, N-methyl-N-vinylformamide, dimethylaminoethyl methacrylate sulfate , N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinylpyrrolidone, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, 2-isopropenyl Nitrogen atom-containing polymerizable monomers such as -2-oxazoline; vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl n-propyl ether, vinyl isobutyl ether, vinyl - butyl ether, cyclohexyl vinyl ether, 4-methylcyclohexyl vinyl ether, hydroxyethyl vinyl ether and hydroxypropyl vinyl ether; (meth) polymerizable monomers having a cyano group such as acrylonitrile may be a preferably exemplified. These other polymerizable monomers may be used alone or in combination of two or more.

[Polymer] The polymer contained in the polymerizable resin composition according to the present invention may be a polymer having a generally known linear or branched molecular structure, and is not particularly limited. is not. Further, the polymer referred to in the present invention is 1
It may include only one type of polymer, but is not limited thereto, and may include two or more types.

The polymer contained in the polymer according to the present invention is not particularly limited, but includes polyalkyl (meth) acrylate, polystyrene, polyvinyl acetate, polycyclohexylalkyl (meth) acrylate, polyethylene, and polypropylene. , ABS, polyvinyl chloride, styrene photopolymer of methyl (meth) acrylate, polyamide, polycarbonate, polyacetal,
Preferably, polyester, polyphenyl ether, polyphenyl sulfide, polyether ethyl ketone, polyallyl ether ketone, polyamide imide, polyimide, polyether imide, polysulfone, polyether sulfone, etc., and at least one selected from the group consisting of these However, among them, polyalkyl (meth) acrylate and / or polystyrene is more preferable because compatibility with the polymerizable monomer is improved. The polymer referred to in the present invention may be a homopolymer composed of only one of the above-mentioned various polymers, or a copolymer composed of two or more.

The above various polymers are preferably contained in the polymer of the present invention in an amount of 10 to 100% by weight, more preferably 20 to 100% by weight, even more preferably 50 to 100% by weight. . The above content rate is 10
If the amount is less than 10% by weight, the polymer and the polymerizable monomer undergo phase separation, and the resulting cured product of the polymerizable resin composition has a low degree of polymerization and is non-uniform, exhibiting desired physical properties. It is not preferable because it may not be possible.

The above-mentioned various polymers preferably have a weight average molecular weight of 1,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 250,000. It is. If the weight-average molecular weight is less than 1,000, the desired physical properties tend not to be exhibited, which is not preferable.
If it exceeds 500,000, the viscosity becomes high, which tends to have an adverse effect on molding processability, workability, and the like, which is not preferable.

In the polyalkyl (meth) acrylate, the content of the structural unit derived from the alkyl (meth) acrylate in the polyalkyl (meth) acrylate is 1
To 100% by weight, more preferably 20 to 100% by weight, even more preferably 50 to 10% by weight.
0% by weight. If the content is less than the above range, the polymer and the polymerizable monomer will phase-separate, the cured product of the resulting polymerizable resin composition has a low degree of polymerization and becomes non-uniform, It is not preferable because desired physical properties may not be exhibited.

In polystyrene, the content of structural units derived from styrene in polystyrene is 1 to 100% by weight.
Is more preferably 20 to 100% by weight, even more preferably 50 to 100% by weight. If the content is less than the above range, the polymer and the polymerizable monomer will phase-separate, the cured product of the resulting polymerizable resin composition has a low degree of polymerization and becomes non-uniform, It is not preferable because desired physical properties may not be exhibited.

The polymer in the present invention is a polymer having a polymerizable unsaturated group in a molecule (hereinafter, for convenience, the polymer having a polymerizable unsaturated group is referred to as a polymer (A)).
It is preferable to include The polymer (A) may be a polymer having an unsaturated group having polymerization reactivity in a molecule.
There is no particular limitation.

The polymer (A) is preferably contained in the polymer of the present invention in an amount of 10 to 100% by weight, more preferably 20 to 100% by weight, even more preferably 50 to 100% by weight. . If the content is less than 10% by weight, the polymer and the polymerizable monomer undergo phase separation, and the resulting cured product of the polymerizable resin composition has a low degree of polymerization and is non-uniform, It is not preferable because desired physical properties may not be exhibited.

The polymer (A) is an epoxy (meth) acrylate polymer, a urethane (meth) acrylate polymer,
It is preferable to include at least one selected from the group consisting of polyester (meth) acrylates and unsaturated polyesters, and the content is preferably 10 to 100% by weight based on the total amount of the polymer (A). It is more preferably 20 to 100% by weight, and even more preferably 50 to 100% by weight. The above content ratio is 10% by weight.
If it is smaller, the degree of polymerization of the polymerizable resin composition to be obtained is low, and the desired physical properties may not be exhibited.

The epoxy (meth) acrylate polymer has a (meth) acryloyl group at a molecular terminal, and is not particularly limited. For example, an epoxy compound having two or more epoxy groups in a molecule; A polymer containing an oligomer obtained by subjecting (meth) acrylic acid to an addition reaction with a polybasic acid, if necessary, is preferred.

The epoxy compound is not particularly restricted but includes, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, hydrogenated bisphenol type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound and the like. Can be Examples of the epoxy compound include glycidyl ethers of polyhydric alcohols such as neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; diglycidyl ether of phthalic acid and diglycidyl ether of dimer; Glycidyl esters of polybasic acids are preferred. These may be used alone or in combination of two or more.

The polybasic acid is not particularly restricted but includes, for example, pyromellitic acid, trimellitic acid, trimer acid and carboxyl group in addition to the above-mentioned α, β-unsaturated dibasic acids and saturated dibasic acids. , Polybutadiene having carboxyl group, butadiene-acrylonitrile copolymer having carboxyl group, compound having terminal carboxyl group obtained by esterification of α, β-unsaturated dibasic acid and / or saturated dibasic acid and polyhydric alcohol, etc. Are preferably mentioned,
These may be used alone or in combination of two or more. When two or more of the above polybasic acids are used in combination, a vinyl ester compound having high flexibility can be obtained.

In order to carry out an addition reaction between an epoxy compound having two or more epoxy groups in the molecule, (meth) acrylic acid and, if necessary, a polybasic acid, usually, in the presence of an addition reaction catalyst, It is preferable to heat in the range of 50 to 150 ° C. As the addition reaction catalyst, for example, a known synthesis catalyst of an epoxy (meth) acrylate polymer can be preferably used, and among them, tertiary amines, onium salts, metal soaps, and the like are more preferable.

The urethane (meth) acrylate polymer is not particularly limited. For example, a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound,
Further, a polymer containing an oligomer as a component, which can be obtained by a urethanation reaction with a polyol compound, if necessary, is preferable.

As the polyisocyanate compound,
Although not particularly limited, for example, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate,
And isophorone diisocyanate. As the hydroxyl group-containing (meth) acrylate compound, any (meth) acrylate compound having at least one hydroxyl group in the molecule may be used. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono ( Preferred are, for example, (meth) acrylate and polypropylene glycol mono (meth) acrylate.

The polyol compound is not particularly limited. For example, in addition to the above polyhydric alcohol,
Polyethylene glycol, polypropylene glycol,
Alkylene oxide adduct of trimethylolpropane,
Polyether polyols such as alkylene oxide adducts of phenol novolak; alcohols having an allyl ether group such as trimethylolpropane monoallyl ether and pentaerythritol diallyl ether;
Preferable examples include polyester polyols obtained by an esterification reaction of a polyol with a polybasic acid such as maleic acid, adipic acid, and phthalic acid. Further, monohydric alcohols such as allyl alcohol and trimethylolpropane diallyl ether; ethylene oxide Oxirane compounds such as propylene oxide, butylene oxide, glycidyl (meth) acrylate, and allyl glycidyl ether can also be used in combination.

As described above, in order to make the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound and, if necessary, the urethanation reaction with the polyol compound, the equivalent ratio of the hydroxyl group to the isocyanate group becomes approximately one. It is preferable to adjust the amount to be used and to heat in the range of 40 to 140 ° C. In order to promote the urethanization reaction, known urethanization catalysts can be preferably used, and among them, tin compounds such as tertiary amines, dibutyltin dilaurate and tin chloride are more preferable.

The polyester (meth) acrylate is not particularly limited, but includes (meth) acrylic acid and
A polymer containing an oligomer obtained by an esterification reaction with a polyhydric alcohol and, if necessary, a basic acid other than (meth) acrylic acids is preferred.

The (meth) acrylic acid is not particularly limited, but examples thereof include (meth) acrylic acid and (meth) acrylic acid.
Can form an ester bond with a hydroxyl group, such as alkyl acrylate and (meth) acrylic halide (meth)
Preference is given to acrylic acid and its derivatives.

The polyhydric alcohol is not particularly limited, but preferably includes, for example, the polyhydric alcohols exemplified as the raw materials for the unsaturated polyester.

The basic acid other than the (meth) acrylic acids is not particularly limited, but, for example, α, β-unsaturated dibasic acids, saturated dibasic acids, etc. exemplified as the raw materials for the unsaturated polyester are preferable. No.

An oligomer obtained by reacting the above polybasic acid with an unsaturated epoxy compound can also be used as an oligomer of the polyester (meth) acrylate resin. The unsaturated epoxy compound is not particularly limited, but preferably includes an unsaturated glycidyl compound and the like, and more preferably glycidyl (meth) acrylate. The conditions for the reaction between the polybasic acid and the unsaturated epoxy compound are preferably the same as the above-described conditions for the addition reaction of the epoxy (meth) acrylate polymer.

The unsaturated polyester is not particularly limited. For example, a dibasic acid and a polyhydric alcohol may be used.
A polymer containing an oligomer as a component obtained by performing dehydration condensation by heating at 0 to 250 ° C. is preferable.

The dibasic acid is not particularly restricted but specifically includes α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and citraconic acid. Basic acids and their anhydrides; phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Cyclohexanedicarboxylic acid, succinic acid, succinic anhydride, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,12-dodecane diacid, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene Dicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
Saturated dibasic acids and anhydrides thereof, such as 2,3-naphthalenedicarboxylic anhydride and 4,4′-biphenyldicarboxylic acid, are preferred.
It preferably contains an α, β-unsaturated dibasic acid and / or an anhydride thereof. α, β-unsaturated dibasic acids and their anhydrides (hereinafter referred to as α, β-unsaturated dibasic acids)
One type may be used alone, or two or more types may be used in combination.
Saturated dibasic acids and anhydrides thereof (hereinafter, referred to as saturated dibasic acids) are preferably used in combination with α, β-unsaturated dibasic acids as required. When a saturated dibasic acid is used in combination, even if the saturated dibasic acid is used alone,
Two or more kinds may be used in combination, and α, β-
The content of unsaturated dibasic acids is preferably more than 0 and less than 100 mol%, more preferably 15 mol% or more and 10 mol% or more.
Less than 0 mol%.

The polyhydric alcohol is not particularly limited, but specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 1,3-butane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-cyclohexanediol, 1,3
-Cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methylpropane-1,3-diol, trimethylolpropane, hydrogenated bisphenol A, alkylene oxides of bisphenol A (for example, ethylene oxide, propylene oxide And the like). These may be used alone or in combination of two or more.

The mixing ratio of the polyhydric alcohol to the dibasic acid is not particularly limited, but the molar ratio of the carboxyl group to the hydroxyl group is preferably 1.5 / 1 to 1 / 1.5, more preferably. Is from 1.2 / 1 to 1 / 1.2, still more preferably from 1.1 / 1 to 1 / 1.1.

The reaction method and reaction conditions for the condensation reaction between the dibasic acid and the polyhydric alcohol are not particularly limited, but are preferably set so that the condensation reaction is completed. In this reaction, if necessary, a catalyst for accelerating the condensation reaction and additives such as an antifoaming agent can be added to the reaction system. The amounts of these catalysts and additives are not particularly limited, but are preferably 0.001 to 10% by weight, more preferably 0.005 to 5% by weight, based on 100% by weight of the whole resin composition. And still more preferably 0.005 to 2% by weight. The order of mixing the dibasic acid, the polyhydric alcohol, the additives, and the like is not particularly limited. Also,
The condensation reaction is more preferably performed in an atmosphere of an inert gas such as nitrogen or helium.

The number average molecular weight (Mn) of the oligomer of the unsaturated polyester is preferably in the range of 500 to 30,000, more preferably 700 to 20,000, and still more preferably 1,000 to 10,000. is there.
When the number average molecular weight is larger than 30,000,
It is not preferable because the viscosity is increased, and the handleability of the unsaturated polyester or the polymerizable resin composition containing the same may be reduced.

Further, unsaturated polyesters other than those described above may be used, for example, in JP-A-8-73577, JP-A-56-150044 and JP-A-57-5983.
Unsaturated oligoesters and the like, which are radical polymerizable oligomers described in Japanese Unexamined Patent Publication (Kokai) No. 4 (Kokai) No. 4 and the like, may be preferably used.

The unsaturated oligoester that is the radical polymerizable oligomer is not particularly limited, but specifically, is preferably an unsaturated oligoester having at least one (meth) acryloyl group at a molecular terminal. . More preferably, it comprises (meth) acrylic acid, (meth) acrylate having an alcoholic hydroxyl group, (meth) acrylate having a carboxylic acid group, (meth) acrylate having an amino group, and (meth) acrylate having a phosphoric acid group. An unsaturated oligoester obtained by reacting an alkylene oxide with an unsaturated polybasic anhydride using at least one compound selected from the group as a reaction starting material. Further, if necessary, a low molecular weight oligoester having a structure in which a saturated polybasic acid anhydride is successively ring-opened and added may be used.

Further, when a saturated dibasic acid and a polyhydric alcohol are reacted under the above-mentioned reaction conditions for an unsaturated polyester, a saturated polyester can be produced. When a radical polymerizable monomer such as styrene is blended with this saturated polyester, it can be used as a radical polymerizable polymer, similarly to the unsaturated polyester. Therefore, a polymerizable resin composition containing a saturated polyester can also be a preferred embodiment of the present invention.

The epoxy (meth) acrylate polymer, urethane (meth) acrylate polymer, polyester (meth) acrylate and unsaturated polyester which can be preferably contained in the polymer (A) are as follows:
The weight average molecular weight is preferably from 500 to 30,000, more preferably from 700 to 20,000,
Even more preferably, it is 1,000 to 10,000. If the weight average molecular weight is smaller than 500, the desired physical properties tend not to be exhibited, which is not preferable.
If it exceeds 000, the viscosity becomes high, which tends to have an adverse effect on molding processability, workability and the like, which is not preferable.

The polymer (A) contained in the polymerizable resin composition of the present invention preferably contains a (meth) acrylic polymer having a double bond.

The (meth) acrylic polymer having a polymerizable double bond as used herein refers to a component having a polymerizable double bond in a molecule and derived from a monomer constituting the polymer. It is preferable that 50 to 100% by weight thereof is a component derived from a (meth) acrylic monomer.

As a method for introducing the polymerizable double bond into the (meth) acrylic polymer, an unsaturated monomer having a functional group is copolymerized at the time of synthesizing the polymer so that the functional group is incorporated into the molecule. Can be obtained by first synthesizing a polymer having the following formula, followed by reacting an unsaturated monomer having another functional group reactive with the functional group. Further, the polymer having a functional group in the molecule and the unsaturated monomer having another functional group may be reacted stepwise as described above, or both may be simultaneously reacted. Well, it is not particularly limited to these.

Examples of the combination of the two reactive functional groups include, for example, carboxyl and glycidyl, hydroxyl and isocyanate, carboxyl and hydroxyl, carboxyl and amino, carboxyl and oxazolinyl, and carboxyl and oxazolinyl. Preferable examples include a group and an aziridinyl group, and a hydroxyl group and an acid anhydride, but are not particularly limited thereto. Among these, a combination of a carboxyl group and a glycidyl group is particularly preferable in terms of high reactivity, low coloration, and the like. In each of these combinations, the unsaturated monomer having one of the functional groups in the combination may be copolymerized with the other unsaturated monomer and introduced into the polymer. It is not limited. Specifically, a method in which a carboxyl group is introduced using an unsaturated monomer having a carboxyl group in a (meth) acrylic polymer and glycidyl methacrylate which is an unsaturated epoxy group compound is reacted, Double bonds can be easily and reliably introduced into the polymer. However, the method is not particularly limited as long as it is a method capable of introducing a double bond into the polymer, and raw materials and the like may be appropriately selected so that the above-described functional group is used as a reaction site.

As the unsaturated monomer having a carboxyl group (hereinafter, referred to as a carboxyl group-containing monomer),
The compound is not particularly limited as long as it has a polymerizable double bond and a carboxyl group in one molecule. Specifically, for example, acrylic acid, methacrylic acid,
Unsaturated monocarboxylic acids such as crotonic acid and vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; monoesters of these unsaturated dicarboxylic acids; Is mentioned. Examples of the monoester of the unsaturated dicarboxylic acid include monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid, and the like. Preferred are mentioned.

Examples of the long-chain carboxyl group-containing monomer include a monoester of an acid anhydride obtained by monoesterifying an acid anhydride with a (meth) acrylic acid ester having a hydroxyl group. Examples of the (meth) acrylate having a hydroxyl group include 2-
Examples thereof include ring-opening adducts of ε-caprolactone to hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate and ring-opening adducts of γ-butyrolactone to 2-hydroxyethyl (meth) acrylate. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and hexahydrophthalic anhydride. Therefore, as the acid anhydride monoester, specifically, for example, succinic acid monoester, phthalic acid monoester,
Hexaphthalic acid monoester is preferred.
These carboxyl group-containing monomers may be used alone, or two or more kinds may be appropriately mixed and used.

Specific examples of the unsaturated epoxy compound preferably include allyl glycidyl ether; glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate; and mono (meth) acrylate of epoxy resin. These compounds may be used alone or in a combination of two or more.

The amount of the unsaturated epoxy compound to be used may be determined according to the combination with the carboxyl group-containing polymer, and is not particularly limited. It is preferably in the range of 0.5 to 2 moles, more preferably in the range of 0.8 to 1.5 moles with respect to the group-containing monomer.

The reaction between the carboxyl group-containing polymer and the unsaturated epoxy compound is desirably performed in the presence of a catalyst. The catalyst may be any one capable of promoting the above reaction, and may be an inorganic metal compound, an oxo acid metal salt, a polyoxo acid metal salt, an organic metal compound, an organic acid metal salt, a metal complex salt, a tertiary amine, Quaternary ammonium salts,
A quaternary phosphonium salt or the like can be used.

As the catalyst, a metal compound containing at least one element selected from the group consisting of Zn, Sn and Zr (hereinafter, simply referred to as “metal compound”) and a quaternary phosphonium salt are particularly preferable.

Examples of the quaternary phosphonium salts include, for example, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, Preferable examples include benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, and tetrabutylphosphonium hydroxide. Among the quaternary phosphonium salts, a tetraphenylphosphonium salt is more preferred, and tetraphenylphosphonium bromide is particularly preferred, in that the time required for the esterification reaction can be reduced.

The amount of the catalyst to be used may be determined according to the type thereof, the combination with the carboxyl group-containing polymer, and the like, and is not particularly limited. 0.01 parts by weight
It is preferably within the range of 5 parts by weight, more preferably within the range of 0.1 to 3 parts by weight.

In carrying out the esterification reaction, a polymerization inhibitor may be present. As the polymerization inhibitor, hydroquinone, methylhydroquinone, methoxyhydroquinone, tert-butylhydroquinone and the like can be used. When performing the esterification reaction, a solvent can be used. Water and / or an organic solvent can be used as the solvent.

In the above esterification reaction, the order and method of mixing the carboxyl group-containing polymer, unsaturated epoxy compound, catalyst and the like are not particularly limited.

When a polymer having a functional group is obtained by polymerizing the unsaturated monomer component, a polymerization initiator can be used. As the above polymerization initiator, specifically,
For example, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, ter
t-butylperoxy-2-ethylhexanoate, t
organic peroxides such as tert-butyl peroxy octoate, tert-butyl peroxy benzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate; ,
Azo compounds such as 2'-azobisisobutyronitrile and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile are preferably exemplified, but are not particularly limited. These polymerization initiators may be used alone, or two or more of them may be used as an appropriate mixture. The amount of the polymerization initiator to be added to the monomer component is not particularly limited.

In obtaining a polymer having a functional group by polymerizing the above unsaturated monomer component, it is necessary to control the polymerization reaction of the unsaturated monomer component to adjust the weight average molecular weight of the polymer. More preferably, a chain transfer agent is added. As the chain transfer agent, a thiol compound is particularly preferably used because the polymerization reaction of the unsaturated monomer component can be very easily controlled, but is not particularly limited, and α-methylstyrene dimer, tetrachloride Carbon or the like can also be used. Specific examples of the thiol compound include alkyl mercaptans such as tert-butyl mercaptan, n-octyl mercaptan and n-dodecyl mercaptan; aromatic mercaptans such as thiophenol and thionaphthol; thioglycolic acid; thioglycolic acid Octyl, ethylene glycol dithioglycolate, trimethylolpropane tris- (thioglycolate), pentaerythritol tetrakis- (thioglycolate)
Thioglycolic acid alkyl esters such as β-mercaptopropionic acid; octyl β-mercaptopropionate, 1,4-butanediol di (β-thiopropionate), trimethylolpropane tris- (β-thiopropionate) , Pentaerythritol tetrakis- (β
Β-mercaptopropionic acid alkyl ester such as -thiopropionate) and the like, but are not particularly limited thereto. One of these chain transfer agents may be used alone, or two or more thereof may be appropriately mixed and used.

The amount of the chain transfer agent to be used may be appropriately adjusted according to the average molecular weight in view of the obtained polymer, and is not particularly limited. A range from about 15% by weight to about 15% by weight is preferred.

The method for polymerizing the unsaturated monomer component is not particularly limited, but a method for terminating the polymerization of the unsaturated monomer component, that is, a partial polymerization is preferable. As a result, a mixture of the polymer and the unreacted unsaturated monomer component is obtained. The above mixture utilizes an unreacted unsaturated monomer component as the polymerizable monomer of the present invention, that is, it can be used as it is as a polymerizable resin composition of a polymer and a polymerizable monomer. . Further, the polymer can be isolated by removing the unreacted unsaturated monomer component from the mixture.

Examples of the method for obtaining a polymer having a functional group by polymerizing the unsaturated monomer component include known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. However, bulk polymerization is particularly preferred from the viewpoint of simplicity of production. When suspension polymerization is employed, it may be suspended in a dispersion medium such as water using a dispersion stabilizer such as polyvinyl alcohol. Reaction conditions such as reaction temperature and reaction time when performing the polymerization are not particularly limited,
For example, known reaction conditions can be adopted. still,
The polymerization is preferably performed under a nitrogen atmosphere.

When the unsaturated monomer component is polymerized by adding a thiol compound as the chain transfer agent, particularly in the case of bulk polymerization, the remaining thiol compound is added to the reaction mixture after the polymerization. Preferably, a treatment is performed. Thereby, the solvent resistance and heat resistance of the cured product obtained by curing the polymerizable resin composition can be improved.

As a method of treating the thiol compound, a method of adding a vinyl ether compound and / or a vinyl thioether compound to the reaction mixture after completion of the polymerization, or a method of treating the reaction mixture after completion of the polymerization with maleic anhydride and basic A method using a compound or the like can be used, but the method is not limited thereto.

The (meth) acrylate used for obtaining the (meth) acrylic polymer having a double bond is not particularly limited, but specifically, methyl (meth) acrylate, ethyl ( Preferred examples include (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate. The other vinyl monomer used as required is not particularly limited, but specific examples include styrene, α-methylstyrene, vinyl toluene, and vinyl acetate. One of these monomers may be used alone, or two or more of them may be appropriately mixed and used.

In the case where the polymer (A) contains the (meth) acrylic polymer having a double bond, trimethylolpropane tri (meth) acrylate or trimethylolpropane tri (meth) acrylate may be used if necessary. A so-called crosslinkable monomer having two or more polymerizable double bonds such as trimethylolpropane di (meth) acrylate and diethylene glycol di (meth) acrylate can be included.
Further, a polymerizable resin composition containing an acrylic polymer into which a double bond has been introduced may be referred to as a crosslinkable acrylic syrup.

In the (meth) acrylic polymer having a double bond, the molecular weight (double bond equivalent) per polymerizable double bond is preferably from 500 to 100,000, and more preferably. Is between 1,000 and 50,000
0, even more preferably from 20,000 to 500,000.
0. If the double bond equivalent is less than 500, the hard and brittle property may become remarkable after curing the polymerizable resin composition of the present invention, so that it is not preferable. If it exceeds, the strength at the time of heating after curing may be similarly reduced, which is not preferable.

When the polymer (A) contains the (meth) acrylic polymer having a double bond, its content may be 10 to 100% by weight based on the total amount of the polymer (A). Preferably, it is more preferably 20 to 100% by weight, and even more preferably 50 to 100% by weight. If the content is less than 10% by weight, the degree of polymerization of the cured product of the polymerizable resin composition to be obtained is low, and the desired physical properties may not be exhibited.

The weight average molecular weight of the (meth) acrylic polymer having a double bond which can be preferably contained in the polymer (A) is 5,000 to 2,000,000.
00, more preferably 10,000
0 to 1,000,000, even more preferably 20,
000 to 500,000. When the weight average molecular weight is less than 5,000, desired physical properties tend not to be exhibited, which is not preferable. When the weight average molecular weight exceeds 2,000,000, the viscosity becomes high, and the moldability and workability tend to be adversely affected. It is not preferable because there is.

[Polymerizable Resin Composition] The polymerizable resin composition according to the present invention contains a polymer and a polymerizable monomer as described above.
The polymer is 5 to 95 parts of the entire polymerizable resin composition obtained.
%, More preferably from 10 to 9% by weight.
0% by weight, even more preferably 15 to 85% by weight, and the polymerizable monomer is preferably 5 to 95% by weight, more preferably 10 to 90% by weight of the whole polymerizable resin composition to be obtained. Wt%, even more preferably 15-8
5% by weight. When the content ratio of the polymer is less than 5% by weight, desired physical properties derived from the polymer cannot be exhibited, and the curing shrinkage of a cured product of the obtained polymerizable resin composition may increase. When the content exceeds 90% by weight, the viscosity of the resulting polymerizable resin composition becomes too high, resulting in poor workability. When the content of the polymerizable monomer is less than 5% by weight, the viscosity of the resulting polymerizable resin composition becomes too high, resulting in poor workability, weather resistance, impact resistance, and the like. It is not preferable because desired physical properties derived from polymerizable monomers such as flexibility and extensibility may not be exhibited,
When the content exceeds 95% by weight, desired physical properties derived from a polymer cannot be exhibited, and the cured product of the polymerizable resin composition may have a large curing shrinkage, which is not preferable.

The viscosity of the polymerizable resin composition according to the present invention is not particularly limited.
° C) is preferably 5 to 500,000 mPa · s, more preferably 5 to 100,000 mPa
S, even more preferably 5 to 50,000 mPa.
s, most preferably 5 to 10,000 mPa · s. When the viscosity is more than 500,000 mPa · s, it is not preferable because it adversely affects molding workability and workability, and when the viscosity is less than 5 mPa · s, it is not preferable because there is a problem such as dripping.

In the polymerizable resin composition according to the present invention, in addition to the above-mentioned polymer and polymerizable monomer, if necessary, reinforcing fibers such as glass fibers and carbon fibers, inorganic fillers and coloring agents , Low shrinkage agent, polymerization inhibitor, internal release agent, antioxidant, ultraviolet absorber, defoamer, leveling agent, shaking change agent, coupling agent, thickener, curing agent, curing accelerator, etc. Additives can be added.

The method of mixing the constituent components for obtaining the polymerizable resin composition according to the present invention is not particularly limited as long as it is a method capable of efficiently mixing a high-viscosity substance, and examples thereof include a kneader, a mixer, and a roll. And a method using an extruder.

As a method for curing the polymerizable resin composition according to the present invention, a curing method at room temperature, under heating, or irradiation with radiation can be preferably mentioned.

The use of the polymerizable resin composition of the present invention is not particularly limited. However, due to its curability and various characteristics as described above, various uses such as fiber reinforced plastics, press molding materials, and casting materials are possible. Preferable examples include molding materials, coating materials such as paints, painted floors, linings, coatings and gel coats, and various uses such as resin concrete, putty and adhesives.

[0087]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following, “parts by weight” may be simply referred to as “parts” for convenience.

Example 1 A flask equipped with a thermometer, a gas inlet tube, a stirrer, and a cooling tube was charged with 215 g of methacrylic acid, 1135 g of a bisphenol A type epoxy resin (epoxy equivalent 454), 6.8 g of triethylamine, and 0.3 g of hydroquinone. And heated at 110 ° C. for 8 hours while blowing a mixed gas of air and nitrogen adjusted to an oxygen concentration of 7%, thereby obtaining an acid value of 7.0, a weight average molecular weight of 1400, and a number average molecular weight of 110.
No. 0 epoxy methacrylate resin was obtained. 1350 g of this epoxy methacrylate resin and 900 g of cyclohexylmethyl methacrylate were mixed to obtain an epoxy methacrylate resin composition (A-1) having a viscosity at 25 ° C. of 500 mPa · s.

Comparative Example 1 An epoxy methacrylate resin was obtained by the same reaction and operation as in Example 1. 1350 g of this epoxy methacrylate resin and 900 g of styrene were mixed to obtain an epoxy methacrylate resin composition (B-1) having a viscosity at 25 ° C. of 300 mPa · s.

Example 2 In a flask equipped with a thermometer, a gas inlet tube, a stirrer, and a cooling tube, 258 g of methacrylic acid, 561 g of a bisphenol A type epoxy resin (epoxy equivalent: 187), 4.1 g of benzyltriethylammonium chloride, hydroquinone 0.2 g was charged and heated at 110 ° C. for 8 hours while blowing a mixed gas of air and nitrogen adjusted to an oxygen concentration of 7%, so that the acid value was 5.0 and the weight average molecular weight was 65.
An epoxy methacrylate resin having a number average molecular weight of 550 was obtained. 800 g of this epoxy methacrylate resin and 530 g of cyclohexylmethyl methacrylate were mixed to obtain an epoxy acrylate resin composition (A-2) having a viscosity at 25 ° C. of 300 mPa · s.

Example 3 An epoxy acrylate resin was obtained by the same reaction and operation as in Example 2. This epoxy acrylate resin 80
0 g and 530 g of 4-methylcyclohexylmethyl methacrylate to give a viscosity at 25 ° C. of 300 mPa ·
s epoxy acrylate resin composition (A-3) was obtained.

Comparative Example 2 An epoxy acrylate resin was obtained by the same reaction and operation as in Example 2. This epoxy acrylate resin 80
0 g and 530 g of styrene were mixed to obtain an epoxy acrylate resin composition (B-2) having a viscosity at 25 ° C. of 200 mPa · s.

Example 4 A flask equipped with a thermometer, a gas inlet tube, a stirrer, a cooling tube and a dropping funnel was charged with 85 g of diethylene glycol and an ethylene oxide adduct of bisphenol A (having a hydroxyl equivalent of 16).
2) 65 g and 0.3 g of dibutyltin dilaurate were charged, and heated to 60 ° C. while blowing in nitrogen gas.
348 g of toluene diisocyanate were added dropwise over 1 hour. The temperature in the reaction system was kept at 60 ° C. Subsequently, 0.2 g of benzoquinone was charged, and 288 g of 2-hydroxypropyl methacrylate was added dropwise over 1 hour while blowing a mixed gas of air and nitrogen adjusted to an oxygen concentration of 7%. During this time, the temperature in the reaction system was kept at 60 ° C. After dropping,
By heating at 80 ° C. for 2 hours, a weight average molecular weight of 1
A urethane methacrylate resin having 150 and a number average molecular weight of 900 was obtained. 600 g of this urethane methacrylate resin
And 400 g of cyclohexylmethyl methacrylate were mixed to obtain a urethane methacrylate resin composition (A-4) having a viscosity of 1100 mPa · s at 25 ° C.

Example 5 A urethane methacrylate resin was obtained by the same reaction and operation as in Example 4. A mixture of 600 g of this urethane methacrylate resin and 400 g of 4-methylcyclohexylmethyl methacrylate has a viscosity of 1200 m at 25 ° C.
Pa · s urethane methacrylate resin composition (A-
5) was obtained.

Comparative Example 3 A urethane methacrylate resin was obtained by the same reaction and operation as in Example 3. By mixing 600 g of this urethane methacrylate resin and 400 g of methyl methacrylate,
A urethane methacrylate resin composition (B-3) having a viscosity at 25 ° C. of 800 mPa · s was obtained.

Example 6 A flask equipped with a thermometer, a gas inlet tube, a stirrer and a Dean-Stark type separator was charged with diethylene glycol 31.
8 g, 296 g of phthalic anhydride, 172 g of methacrylic acid,
314 g of toluene, 3.1 g of paratoluenesulfonic acid,
0.3 g of hydroquinone was charged and heated to 90 ° C. while blowing a mixed gas of air and nitrogen adjusted to an oxygen concentration of 7% to remove condensed water generated and heated for 6 hours. When the amount of condensed water reaches 65 g (90% of the theoretical amount), 4
Cool to 0 ° C and wash with 5% aqueous sodium hydroxide,
Subsequently, after washing with a 5% aqueous ammonium sulfate solution,
Toluene was removed under reduced pressure at 0 ° C. to obtain a polyester methacrylate resin having an acid value of 17, a weight average molecular weight of 900 and a number average molecular weight of 750. A mixture of 600 g of this polyester polymethacrylate resin, 200 g of cyclohexylmethyl methacrylate, and 200 g of 4-methylcyclohexylmethyl methacrylate was mixed at a viscosity of 25 mPa at 25 ° C.
-The polyester polymethacrylate resin composition (A-6) which was s was obtained.

Comparative Example 4 A polyester polymethacrylate resin was obtained by the same reaction and operation as in Example 4. 600 g of this polyester polymethacrylate resin and 400 g of styrene were mixed to obtain a polyester polymethacrylate resin composition (B-4) having a viscosity at 25 ° C. of 100 mPa · s.

Example 7 A flask equipped with a thermometer, a cooling tube, a stirrer, and a gas introduction tube was charged with 294 g of maleic anhydride, 498 g of isophthalic acid,
532 g of propylene glycol was charged, nitrogen gas was blown in, and at 200 ° C. 9
After heating for an hour, an unsaturated polyester resin having an acid value of 15 and a number average molecular weight of 1700 was obtained. 1000 g of this unsaturated polyester resin and cyclohexylmethyl methacrylate 2
50 g, 250 g of 4-methylcyclohexylmethyl methacrylate and 170 g of styrene were mixed to obtain an unsaturated polyester resin composition (A-7) having a viscosity at 25 ° C of 1200 mPa · s.

Comparative Example 5 An unsaturated polyester resin was obtained by the same reaction and operation as in Example 5. This unsaturated polyester resin 1000
g and 670 g of styrene to give a viscosity of 7 at 25 ° C.
00 mPa · s unsaturated polyester resin composition (B-
5) was obtained.

-Example 8- Commercially available polymethyl methacrylate (PMMA) (SUMIPEX LG-6A, Sumitomo Chemical, Mw = 50,000) 3
00g, cyclohexylmethyl methacrylate 500
g and methyl methacrylate (200 g) were mixed and stirred in a flask to obtain a polymethyl methacrylate resin composition (A-8) having a viscosity of 1300 mPa · s at 25 ° C.

Comparative Example 6 Commercially available polymethyl methacrylate (PMMA) (Sumipex LG-6A, Sumitomo Chemical, Mw = 50,000) 3
00 g and methyl methacrylate 700 g were mixed and stirred in a flask, and the viscosity at 25 ° C. was 1000 mPa · s.
The polymethyl methacrylate resin composition (B-6) was obtained.

-Example 9- Commercially available polystyrene (Stoyostyrol Q manufactured by Denka Corporation)
P2B, Mw = 200,000) 300 g, cyclohexylmethyl methacrylate 350 g, and styrene 3
50 g was mixed and stirred in a flask, and the viscosity at 25 ° C. was 500 mPa · s, a polystyrene resin composition (A-9).
I got

-Comparative Example 7- Commercially available polystyrene (Stoyostyrol Q manufactured by Denka Corporation)
300 g of P2B, Mw = 200,000) and 350 g of styrene were mixed and stirred in a flask, and a polystyrene resin composition (B) having a viscosity of 400 mPa · s at 25 ° C.
-7) was obtained. Here, a curing agent Kayaester CND (Chemical Agent Akzo) was used for 300 g of each of the polymerizable resin compositions A-1 to A-9 and B-1 to B-7 obtained in each of Examples and Comparative Examples. 3g and TMPO-7
0 (manufactured by Kayaku Akzo Co., Ltd.) was added and mixed, and the mixture was poured into a glass casting mold for obtaining molded products having a thickness of 3 mm and 7 mm, and left at room temperature for 16 hours. Cured. Then, after heating at 110 ° C. for 2 hours for post-curing, the mold was removed to obtain a molded plate. From this board,
A test piece was cut out, and the tensile strength, the tensile elongation, and the Izod impact strength were measured according to JIS K7113. The results are shown in Tables 1 and 2.

[0104]

[Table 1]

[0105]

[Table 2]

The additives shown in Table 2 were mixed with each of the polymerizable resin compositions A-1 to A-9 and B-1 to B-7 obtained in each of the examples and comparative examples. Thus, a coating composition was prepared. These polymerizable resin compositions for paints 10
To 0 g, 1 g of curing agent Kayaester CND (manufactured by Kayaku Akzo Co., Ltd.) and 0.5 g of TMPO-70 (manufactured by Kayaku Akzo Co., Ltd.) are added and mixed, and then an epoxy primer is applied in advance. Slate board (100m
(m × 50 mm) at a coating amount of 100 g / m ² , left at room temperature for 16 hours, and then placed in a heating furnace at 40 ° C. for 48 hours and post-cured to obtain a test piece for evaluating weather resistance. Using this test piece, a sunshine weather meter (model WEL-SUN-HC (B), Suga Test Machine Co., Ltd.)
), An accelerated exposure test was performed and the color difference was measured. At this time, the thixotropic agent is R-812 manufactured by Nippon Aerosil Co., Ltd.
And paraffin having a melting point of 130F was used. The results are shown in Table 2.

At this time, as the moldability due to the volatilization of the monomer component, the presence or absence of skinning on the coating film surface due to the volatilization of the monomer and the smoothness of the coating film surface were visually observed. The following criteria evaluated the smoothness of the coating film surface. The results are shown in Tables 3 and 4.

：: Smooth △: Almost smooth ×: Irregularities are observed

[0109]

[Table 3]

[0110]

[Table 4]

[0111]

According to the present invention, monomer odor and loss of volatilization during curing are small, and after curing, heat resistance and weather resistance (especially long-term weather resistance) are excellent, and impact resistance and flexibility are improved. It is possible to provide a novel polymerizable resin composition for obtaining a cured product having good stretchability and processability.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshio Hayashiya 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4J011 AA05 NA03 NA04 PA65 PA69 PC08 4J026 AA17 AA45 BA27 BA50 DA05 DA12 DA13 DA15 DB12 DB13 DB15

Claims (4)

[Claims] 1. A composition comprising a polymer and a polymerizable monomer, wherein the polymerizable monomer is cyclohexylmethyl (meth) acrylate (provided that the cyclohexyl group has a substituent Good) as an essential component,
Polymerizable resin composition. 2. The polymerizable composition according to claim 1, wherein the cyclohexylmethyl (meth) acrylate (the cyclohexyl group may have a substituent) is 4-methylcyclohexylmethyl (meth) acrylate. Resin composition. 3. The method according to claim 1, wherein the polymer comprises a polyalkyl (meth) acrylate and / or polystyrene.
Or the polymerizable resin composition according to 2. 4. The polymerizable resin composition according to claim 1, wherein the polymer includes a polymer having a polymerizable unsaturated group.