JPH10120736A - Curable resin composition, FRP molded product and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-odor, low-toxic radical-curable curable resin composition having excellent strength characteristics, water resistance, and chemical resistance without using styrene. With the goal. SOLUTION: The present invention provides (A) a polyurethane polymer containing at least one or more vinyl ether groups by using three components of a polyol, a polyisocyanate and a hydroxyl group-containing vinyl ether compound as essential components, and (B) a low molecular weight unsaturated polymer. The present invention relates to a curable resin composition comprising a polyester compound, (C) one or more diluent monomers selected from a vinyl ether compound, a (meth) acrylic acid derivative, and vinyl carboxylate as required.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition which is excellent in strength, water resistance, chemical resistance and low odor, is liquid, and can be radically cured, and relates to an FRP molded product and a coating material.

[0002]

2. Description of the Related Art As radical-curable resins, unsaturated polyester resins, epoxy (meth) acrylate resins, diallyl phthalate resins and the like are generally known.
In particular, unsaturated polyester resins are produced in large quantities, and FR
It is used for P molded products, coating materials, paints, putties, cast products, etc.

However, since styrene is used as a monomer in the unsaturated polyester resin, environmental pollution due to odor and toxicity is a problem.

[0004] To solve this problem, it has been proposed to use an acrylic derivative having a low volatility, that is, a high molecular weight, instead of styrene (Japanese Patent Application Laid-Open No. Hei 7-216040 and Japanese Patent Application No. Hei 7-245980). However, in these examples, the strength properties, water resistance, and chemical resistance are not sufficient, and the applications are limited.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to cure radically without using styrene, to obtain strength properties, water resistance,
Low-odor, low-toxicity curable resin composition with excellent chemical resistance,
FRP molded products and coating materials.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned conventional disadvantages, and as a result, completed the present invention.

That is, the present invention relates to (A) polyols, polyisocyanates and hydroxyl group-containing vinyl ether compounds.
A polyurethane polymer containing at least one vinyl ether group (hereinafter abbreviated as a vinyl ether urethane polymer), (B) a low molecular weight unsaturated polyester compound, and (C) if necessary, A curable resin composition comprising at least one diluent monomer selected from a vinyl ether compound, a (meth) acrylic acid derivative, and vinyl carboxylate, wherein the component (A) preferably has a content of 10 to 90% by weight. %, The component (B) has a component composition of 10 to 90% by weight, and the component (C) has a component composition of 0 to 70% by weight. More preferably, the polyol of the component (A) is a polyol using a polyalkylene oxide. A curable resin composition, wherein the compound (B) is preferably an unsaturated acid dialkyl ester,
An object of the present invention is to provide an FRP molded product and a coating material using the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol used in (A) of the present invention has two or more hydroxyl groups in one molecule and preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000. Things. The polyol typically includes polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, and the like.

The polyether polyol referred to herein is:
Polyethylene glycol, polypropylene glycol,
In addition to polyalkylene oxides such as polytetramethylene glycol, bisphenol A and bisphenol F
And a polyol having the above-mentioned alkylene oxide added thereto.

[0010] The polyester polyol is a condensation polymer of a dibasic acid and glycol or a ring-opened polymer of a cyclic ester compound such as polycaprolactone. The dibasic acid used here includes, for example, phthalic acid, phthalic anhydride,
Halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, Adipic acid,
Sebacic acid, 1,12-dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
Examples thereof include 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. Glycol is, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-
Methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, an adduct of bisphenol A and propylene oxide or ethylene oxide,
1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4- Examples thereof include cyclohexanedimethanol, para-xylene glycol, bicyclohexyl-4,4′-diol, 2,6-decalin glycol, and 2,7-decalin glycol.

The polyisocyanate (A) includes 2,4-tolylene diisocyanate and its isomer or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate. Isocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like can be mentioned, and these can be used alone or in combination of two or more. Among the above polyisocyanates, diisocyanates, especially T
DI is preferably used.

Examples of the hydroxyl group-containing vinyl ether compound (A) include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxydiethylene glycol monovinyl ether, and hydroxycyclohexanedimethanol monovinyl ether. Further, a part of the vinyl ether compound can be used by substituting it with a hydroxyl group-containing allyl ether compound. In this case, an air-drying function can be imparted to the resin, and typical examples thereof include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, propylene glycol monoallyl ether, and dipropylene glycol. Monoallyl ether, triethylene glycol monoallyl ether, trimethylo-
Examples include lupropane diallyl ether, glycerin diallyl ether, and pentaerythritol triallyl ether.

As an example of a method for producing a urethane polymer having at least one vinyl ether group obtained from the polyol (A) component polyol, polyisocyanate, and hydroxyl group-containing vinyl ether compound, first, the polyisocyanate and the polyol are converted into NCO /OH=1.3 to 2 to form a terminal isocyanate compound, and then react a hydroxyl group-containing vinyl ether compound so that hydroxyl groups are substantially equivalent to isocyanate groups; and a polyisocyanate compound and a hydroxyl group. A method in which a vinyl ether compound is reacted at NCO / OH = 2 or more to form a compound having one terminal isocyanate, and then a polyol is added and reacted.

The low molecular weight unsaturated polyester compound (B) used in the present invention is preferably an ester compound having a number average molecular weight of 1,000 or less and having an unsaturated bond, particularly preferably an unsaturated acid dialkyl ester. is there. Typically, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dioctyl maleate, dicyclohexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate, fumarate Unsaturated alkyl dialkyl esters such as dicyclohexyl acid, and maleic acid, a condensation polymer obtained from fumaric acid and the dibasic acid and glycol used in the production of the polyester polyol, or maleic acid and propylene oxide, butylene oxide and the like. It may be a ring-opened polymer with an alkylene oxide. Particularly, dialkyl maleate is preferable because of high reactivity with a vinyl ether group.

The diluent monomer of component (C) used in the present invention is selected from those which adjust the viscosity of the present composition to a range which is easy to use, and which do not inhibit the high reactivity between the vinyl ether group and the maleic group. Those meeting these requirements are vinyl ether compounds, (meth) acrylic acid derivatives and vinyl carboxylate compounds. Those commercially available can also be used.

As typical examples of the vinyl ether compound, monofunctional vinyl ether compounds such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, and cyclohexyl vinyl ether; Polyfunctional vinyl ether compounds such as ethylene glycol divinyl ether, butylene glycol divinyl ether, hexane glycol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether. is there.

Examples of the (meth) acrylic acid derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and (meth) acrylic acid. T-butyl acid, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, Cyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate,
Ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono Butyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Neopentyl glycol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythrol hexa (meth) acrylate, methoxydiethylene glycol mono (meth) acrylate, methoxydi Propylene glycol mono (meth) acrylate and the like can be used.

The vinyl carboxylate compounds include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl benzoate, vinyl versate (Shell Chemical Products: Veova-9, V
eova-10) and the like.

In order to achieve low odor and non-toxicity, which are one of the objects of the present invention, vinyl ether compounds having a molecular weight of 170 or more, (meth) acrylic derivatives, and vinyl carboxylate compounds are preferred. Of these, methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, Veo
va-9 and Veova-10 can be particularly preferably used.

In the composition ratio of the present invention, the component (A) is preferably 10 to 90% by weight, and the component (B) is preferably 10 to 9% by weight.
0% by weight and the component (C) is 0 to 70% by weight. (A)
If the component is less than 10% by weight, the mechanical strength of the cured product is not sufficient, and if it exceeds 90% by weight, the viscosity of the structure is too high to be used as a liquid resin. When the amount of the component (B) is less than 10% by weight or more than 90% by weight, the curability of the composition is poor, and it takes a long time to obtain a cured product. The component (C) adjusts the viscosity of the present composition so that it can be used easily, and is not necessary if the above components (A) and (B) achieve the purpose. However, in most cases, it is preferable to use it. However, if the content of the component (C) is more than 70% by weight, the mechanical strength of the molded article is deteriorated, which is not preferable.

The composition of the present invention comprises a radical curing agent, a photoradical initiator, a curing accelerator,
Polymerization inhibitors can be used.

Examples of the radical curing agent include organic peroxides. Specific examples include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, kent peroxides, and peroxyketals. Known and publicly used ones, such as an alkyl perester type and a percarbonate type, are used.

The photoradical initiator is a photosensitizer and specifically includes benzoin ethers such as benzoin alkyl ethers, benzophenones such as benzophenone, benzyl and methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2 Acetophenones such as -diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone, 2-chlorothioxanthone,
Thioxanthones such as 2-methylthioxanthone and 2-isopropylthioxanthone are exemplified.

Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, vanadium acetyl acetate, cobalt acetyl acetate and iron acetylacetonate. Metal chelates such as aniline, N, N-dimethylaniline,
N, N-diethylaniline, p-toluidine, N, N-
Dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- (N, N-bis (2-
(Hydroxyethyl) amino) benzaldehyde, 4- (methyldroxyethylamino) benzaldehyde, N, N
-Bis (2-hydroxypropyl) -p-toluidine,
N-ethyl-m-toluidine, triethanolamine m
N, N such as toluidine, diethylenetriamine, pyridine, phenylimorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, etc.
-Substituted aniline, N, N-substituted-p-toluidine, 4-
Amines such as (N, N-substituted amino) benzaldehyde are exemplified.

Examples of the polymerization inhibitor include trihydrobenzene, toluhydroquinone, 14-naphthoquinone,
Examples thereof include parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, and 2,6-di-tert-butyl-4-methylphenol. Preferably, 10 to 1000 ppm can be added to the resin composition.

The addition amount of the curing agent is preferably 0.1 to 6 parts by weight based on 100 parts by weight of the total amount of the curable resin composition. The addition amount of the curing accelerator is 0.1 to 5 parts by weight. In the present invention, amine and metal soap accelerators are preferred. The curing accelerator may be used in a combination of two or more kinds, and may be added to the resin in advance or may be added at the time of use.

In the present invention, various additives such as fillers, ultraviolet absorbers, pigments, thickeners, low-shrinkage agents, antioxidants, plasticizers, aggregates, flame retardants, stabilizers, reinforcing materials, waxes Etc. may be used.

As the filler, for example, a hydraulic silicate material, calcium carbonate powder, clay, alumina powder, silica stone powder,
Examples include talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose, silica sand, river sand, cold water stone, marble chips, crushed stone and the like.

The FRP molded product of the present invention is a product obtained by curing the above-mentioned curable resin composition, a curing agent and a fiber reinforcing material together in a mold or the like. Examples of the fiber reinforcement include various types of organic fibers such as glass fiber, amide fiber, aramid fiber, vinylon fiber, polyester fiber or phenol fiber; carbon fiber, metal, and the like. Fibers or ceramic fibers are used in combination. In consideration of economical aspects, the use of glass fibers or organic fibers is desirable, and the use of glass fibers is particularly desirable.
Examples of the form of these fibers include plain weave, satin weave, non-woven fabric and mat, but it is desirable to use them according to the application. Also, glass roving,
It is also possible to cut it into a length of 20 to 100 mm and use it as a chopped strand as an SMC or BMC molding material.

The coating material of the present invention covers various substrates by adding additives such as a filler, an ultraviolet absorber and a pigment, and adding a curing agent and a curing accelerator. Various substrates are metals, concrete, wood, plastic, fiber,
Any of glass, asphalt, ceramic and the like may be used.

The resin composition of the present invention also has a problem of odor, especially at the time of forming putty, paint, casting, specifically, floor and wall coating material, road marking material, pavement material, lining material and the like. It is useful for civil engineering and building material applications.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, “parts” in the text indicates parts by weight.

Reference Example 1 Synthesis of Vinyl Ether Urethane Polymer [I] Polypropylene glycol (number-average molecular weight) was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 399.3) 599 parts, and 522 parts of tolylene diisocyanate were charged, and 80
C., and reacted for 2 hours. When the NCO equivalent reached 366, the mixture was cooled to 50.degree. C., and then tolhydroquinone 0.11 in a mixed gas stream of nitrogen / air (flow ratio: 1/1).
Parts, 0.056 parts of T-9 and 371 parts of hydroxybutyl vinyl ether, and the temperature is raised again to 90 ° C. 3
The reaction was continued for an hour to obtain a vinyl ether urethane polymer having a residual NCO amount of 0.0447%. This polymer is referred to below as [VE
UI].

Reference Example 2 Synthesis of Vinyl Ether Urethane Polymer [II] Polypropylene glycol (number average molecular weight) was placed in a 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 399.3) Charge 1393 parts, 1035 parts of tolylene diisocyanate, and 234 parts of isophorone diisocyanate, raise the temperature to 80 ° C in a nitrogen atmosphere, react for 3.5 hours, and cool to 50 ° C when the NCO equivalent is 374. And then nitrogen / air (flow ratio 1
/ 1) 0.27 parts of toluhydroquinone under a mixed gas flow,
0.19 parts of T-9 and 433 parts of hydroxybutyl vinyl ether and 887 parts of pentaerythritol triaryl ether were added, and the mixture was heated again to 90 ° C. and reacted for 4 hours to obtain vinyl ether urethane having a residual NCO amount of 0.27%. Was. Furthermore, hydroxybutyl vinyl ether 2
3 parts, T-9 and 0.069 parts were added and reacted for 2 hours to obtain one having a residual NCO amount of 0.115%. This polymer is hereinafter referred to as [VEU-II].

Reference Example 3 Synthesis of Vinyl Ether Urethane Polymer [III] Polypropylene glycol (number average molecular weight) was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 688.3) 792 parts, and 400 parts of tolylene diisocyanate were charged, and 80 parts were placed in a nitrogen atmosphere.
C. and allowed to react for 3.5 hours, NCO equivalent 508
After cooling to 50 ° C., 0.11 part of toluhydroquinone, 0.060 part of T-9, and 286 parts of hydroxybutyl vinyl ether under a mixed gas stream of nitrogen / air / (flow ratio 1/1). , And the mixture was heated again to 90 ° C. and reacted for 3.5 hours.
Of vinyl ether urethane was obtained. This polymer is hereinafter referred to as [VEU-III].

[Reference Example 4] Synthesis of vinyl ether urethane polymer [IV] Polytetramethylene glycol (a few parts) was placed in a two-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. 792 parts of an average molecular weight of 650) and 400 parts of tolylene diisocyanate were charged and 80
C. and allowed to react for 3.5 hours, NCO equivalent 508
After cooling to 50 ° C., 0.11 part of toluhydroquinone, 0.060 part of T-9, and 286 parts of hydroxybutyl vinyl ether were added under a mixed gas stream of nitrogen / air (flow ratio 1/1). In addition, the temperature was raised again to 90 ° C. and reacted for 3.5 hours, and the residual NCO amount was 0.061%.
Of vinyl ether urethane was obtained. This polymer is hereinafter referred to as [VEU-IV].

[Reference Example 5] Synthesis of vinyl ether urethane polymer [V] In a 2-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, butylene glycol and adipic acid were added. 792 parts of the synthesized polyester polyol (number average molecular weight 688.3) and 400 parts of tolylene diisocyanate were charged, the temperature was raised to 80 ° C. in a nitrogen atmosphere, and the mixture was reacted for 3.5 hours. After cooling to 0.1 ° C., toluhydroquinone 0.11 was added under a nitrogen / air (flow ratio 1/1) mixed gas flow.
Parts, 0.060 parts of T-9 and 286 parts of hydroxybutyl vinyl ether were added, and the mixture was heated again to 90 ° C. and reacted for 3.5 hours to obtain a vinyl ether urethane having a residual NCO amount of 0.051%. This polymer is referred to as [VEU
-V].

Reference Example 6 Synthesis of Low Molecular Weight Unsaturated Polyester Compound [I] Maleic anhydride 40 was placed in a two-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser.
8 g was added, and the mixture was heated to 70 ° C. and melted. While stirring and introducing nitrogen gas, 392 g of hexyl alcohol was dropped in about 30 minutes. Next, 180 g of 1.4 butylene glycol was added, the temperature was raised to 215 ° C., and the reaction was carried out for 18 hours until the acid value became 10 (KOH mg / g). A polymer having an average molecular weight of 497 and a viscosity of 21.2 poise was obtained was gotten. This polymer is referred to as [UPE-I].

Reference Example 7 Synthesis of Low Molecular Weight Unsaturated Polyester Compound [II] Maleic anhydride 408 was placed in a two-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser.
g and 1.2 butylene oxide (432 g),
After stirring and dissolving in, the mixture was homogenized, and 12.6 g of zinc chelyl octylate solution (8% zinc content) was added, and the mixture was reacted at 60 ° C. for 8 hours and further at 85 ° C. for 7 hours. A polymer having an average molecular weight of 480 at 17.8 poise was obtained. This polymer is referred to as [UPE-II].

[Examples 1 to 4] VE synthesized in Reference Example 1
As shown in Table 1, diethyl maleate and a diluting monomer were mixed and dissolved in 100 parts of UI to obtain a resin solution.
To 100 parts of the resin composition, 0.3 parts of N, N-bis-2- (hydroxyethyl) -p-toluidine and 2 parts of 50% benzoyl peroxide were added. A casting plate was prepared. After leaving overnight in a greenhouse, 120 ° C x 2
After curing for a time, a tensile test test piece was prepared, and the tensile strength and the tensile elongation were measured.

Comparative Example 1 The resin composition obtained by diluting 100 parts of the vinyl ether urethane polymer obtained in Reference Example 1 with 40 parts of styrene did not cure in the same catalyst system as in Example 1, and was subjected to a tensile test. Could not test.

Comparative Example 2 The resin composition obtained by diluting the vinyl ether urethane polymer obtained in Reference Example 1 with methyl methacrylate instead of styrene of Comparative Example 2 was cured after one hour. The cured product obtained was fragile and could not be subjected to a tensile test.

[0043]

[Table 1]

^{* 1 According to} JISK-6901 room temperature gel time measurement method ^{* 2} Low odor, judgment criteria ○ No odor at 10〓 from nose △ 〃 Slightly feel × 感 じ る Strongly feel

[Examples 5 to 8] Using the vinyl ether urethane polymer synthesized in Reference Example 3, the types of unsaturated polyester compounds and the types of vinyl carboxylate were blended as shown in Table 2, and the same as in Example 1. Cured and measured tensile strength by the method

[0046]

[Table 2]

[Examples 9 to 10] Using the VEU-4 and VEU-5 resins synthesized in Reference Examples 4 and 5, the resin was cured in the same manner as in Example 1, and the tensile strength was measured. Shown in 3

[0048]

[Table 3]

Examples 11 to 12 Using VEU-1 and VEU-2 synthesized in Reference Examples 1 and 2, VEU
100 parts, 35 parts of diethyl maleate, Veo
va9 and 73 parts were added and dissolved. For 100 parts of the resin composition, 0.5 parts of 6% Co-naphthoute, 0.3 parts of N, N-bis- (2-hydroxyethyl) -P-toluidine 0.3
Parts, 130, 135, 140 and 145 ° F. 0.1 part each of F wax and 2 parts of 50% benzoyl peroxide were added, stirred and flowed at 25 ° C. into a glass plate at a thickness of 2 °, Test pieces were prepared. At that time, the time (tack free time) at which the surface was tacky was measured. Table 4 shows the measurement results.

Comparative Example 3 A 5-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with polypropylene glycol (number average molecular weight 39).
9.3) 1393 parts, tolylene diisocyanate 10
35 parts and 234 parts of isophorone diisocyanate were charged, heated to 80 ° C. in a nitrogen atmosphere, reacted for 3.5 hours, and cooled to 50 ° C. when the NCO equivalent reached 379, and then nitrogen / air (flow ratio: 1/1) )
0.27 parts of toluhydroquinone, 0.13 parts of T-9,
Then, 485 parts of hydroxyethyl methacrylate and 887 parts of pentaerythritol triaryl ether were added, and the mixture was heated again to 90 ° C. and reacted for 4 hours.
An amount of 0.26% vinyl urethane was obtained. Further, 22 parts of hydroxyethyl methacrylate, T-9, 0.069
And react for 2 hours, remaining NCO amount, 0.112%
Got something. Hydroquinone, 0.16 parts, methyl methacrylate (MMA) based on 100 parts of this resin
32 parts, 2-ethylhexyl acrylylate (2EH
A) 49 parts were added to obtain a resin solution. This was cured in the same manner as in Example 11 to prepare a test piece. Table 4 shows the results.

[0051]

[Table 4]

Example 13 VEU synthesized in Reference Example 1
1, 29 parts of dimethyl maleate per 100 parts, v
76 parts of eova-9 was added and dissolved. This resin composition 1
N, N-bis- (2-hydroxyethyl) to 00 parts
0.3 parts of -P-toluidine and 2 parts of 50% benzoyl peroxide were added to obtain a resin solution. This resin liquid is impregnated into three glass fibers (chopped strand mat # 450) with an impregnating roll so that the glass content is 30%. After one day, after-curing is performed at 80 ° C. for 6 hours to perform physical properties as FRP. Was measured. Table 5 shows the results.

Comparative Example 4 70 parts of unsaturated polyester and styrene 3 were prepared from 3 mol of propylene glycol, 2 mol of phthalic anhydride and 1 mol of maleic acid, which were synthesized by a usual method.
An FRP board was obtained in the same manner as in Example 13, except that 0.1 part of 6% cobalt-naphthocoat and 1 part of methyl ethyl ketone peroxide were added to 100 parts of the unsaturated polyester resin consisting of 0 parts. Table 5 shows the results.

[0054]

[Table 5] * 1) Height at which 1 mm steel balls are dropped and cracks are generated. * 2) Time when cracks are generated by immersion in hot water at 98 ° C.

[0055]

The resin composition of the present invention relates to a novel resin composition comprising a vinyl ether urethane polymer, a low molecular weight unsaturated compound, and, if necessary, a diluent monomer. Liquid, radical curable, excellent in strength properties, water resistance, chemical resistance, low odor,
It has low toxicity, and is useful for products such as FRP molded products, coating materials, paints, putties, cast products, and construction materials.

Claims (6)

[Claims] 1. A polyurethane polymer containing (A) a polyol, a polyisocyanate and a hydroxyl group-containing vinyl ether compound as essential components and containing at least one or more vinyl ether groups. (B) a low molecular weight unsaturated polyester compound (C) ) If necessary, vinyl ether compound, (meth)
A curable resin composition comprising one or more monomers selected from acrylic acid derivatives and vinyl carboxylate compounds. 2. The curable resin according to claim 1, comprising 10 to 90% by weight of the component (A), 10 to 90% by weight of the component (B) and 0 to 70% by weight of the component (C). Composition. 3. The curable resin composition according to claim 1, wherein the polyol (A) is a polyol using a polyalkylene oxide. 4. The curable resin composition according to claim 1, wherein the compound (B) is a dialkyl unsaturated acid ester. 5. An FRP molded article using the curable resin composition according to claim 1. Description: 6. A coating material comprising the curable resin composition according to claim 1.