JPH09110948A - Vinyl ester resin composition and cured article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl ester resin composition giving a cured article excellent in heat resistance, corrosion resistance, water resistance, toughness, resistance to boiling, gloss, transparency, etc., by reacting a conventionally known vinyl ester resin with an isocyanate ingredient to increase the mol.wt. SOLUTION: This resin composition comprises a vinyl ester resin which is either a urethane-modified vinyl ester resin A or a urethane-modified acid- added vinyl ester resin A' obtained by adding a polybasic acid anhydride B to a part or all of the hydroxyl groups of the resin A and a reactive monomer C having at least one double bond per molecule. The resin A is obtained by reacting a vinyl ester resin F obtained by adding an unsaturated monobasic acid E to an epoxy resin D and/or a (meth)acrylate G having one hydroxyl group per molecule with a polyisocyanate component H in such a proportion hat the equivalent ratio of the isocyanate groups of the component H to the sum of the hydroxyl groups of the components F and G is 0.01 to 1.2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel vinyl ester resin composition and a cured product thereof, and more specifically to high production efficiency, heat resistance, toughness, corrosion resistance, water resistance, boiling resistance and gloss. , A vinyl ester resin composition excellent in transparency and the like and a cured product thereof.

[0002]

2. Description of the Related Art A cured product of vinyl ester resin has heat resistance,
It has excellent corrosion resistance, toughness, boiling resistance, gloss, transparency, etc., and has been used in various fields in recent years. However, for example, in order to mold the resin composition by the heating and pressing method, first,
Although it is necessary to thicken the resin by some method, since vinyl ester resin does not have a carboxyl group at the terminal, for example, alkaline earth such as magnesium oxide as disclosed in Japanese Patent Publication No. 40-273. A thickening method using a metal oxide cannot be performed. Therefore, a vinyl ester resin having no functional group involved in thickening, and an unsaturated polyester resin having a carboxyl group involved in thickening are mixed to impart thickening to the resin,
A method of heating and pressing is also known (Japanese Patent Laid-Open No. 4-23).
No. 818) has a strong tendency to separate a vinyl ester resin and an unsaturated polyester resin, which are originally poor in compatibility, in this system, and a low molecular weight vinyl ester resin which does not participate in thickening is If a large amount is contained,
Not enough thickening. Furthermore, the above-mentioned characteristics originally possessed by vinyl ester resins are less likely to be exhibited due to the influence of phase separation in the system. Further, vinyl ester resins containing a carboxyl group at the terminal are also known, but vinyl ester resins of this type have insufficient molecular weight and cannot exhibit sufficient thickening properties. For the above reasons, a vinyl ester resin which gives a cured product having the above-mentioned characteristic features of the resin has not yet been obtained by the heat and pressure molding method. On the other hand, in the cast molding method, vinyl ester resins have already been used for some applications, but the number of double bonds contained in one molecule is limited, so the degree of crosslinking is increased too much. Therefore, it takes a long time to cure, which lowers the production efficiency. Furthermore, since the degree of cross-linking is low, the heat resistance, which is a characteristic of vinyl ester resins, is not sufficiently exhibited.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have found that the cast molding method has a low viscosity and a high degree of cross-linking, and the heat and pressure molding method enables thickening with an alkaline earth metal oxide. In all cases, the cured product obtained by curing the resin is a vinyl ester-based resin excellent in heat resistance, corrosion resistance, water resistance, toughness, boiling resistance, gloss, transparency, etc. Layered.

[0004]

The present inventors have overcome the problems at the time of cast molding by reacting a conventionally known vinyl ester resin with an isocyanate component to obtain a higher molecular weight, Furthermore, by adding a polybasic acid to the hydroxyl groups present in the polymerized urethane-modified vinyl ester resin, it has become possible to solve the problems during heat and pressure molding. That is, the present invention provides (1) a urethane-modified acid addition obtained by adding a polybasic acid anhydride (B) to some or all of the hydroxyl groups present in the urethane-modified vinyl ester resin (A) or (A). It contains a vinyl ester resin (A ') and a reactive monomer (C) having at least one double bond in the molecule, and (A) has an average of 1.2 or more in one molecule. Vinyl ester resin (F) obtained by adding unsaturated monobasic acid (E) to epoxy resin (D) having an epoxy group and / or 1 in one molecule
A (meth) acrylate (G) having one hydroxyl group and a polyisocyanate component (H) having an average of 1.5 or more isocyanate groups in one molecule, an isocyanate group in the (H) component, (F) and ( A vinyl ester resin composition, characterized in that it is obtained by reacting so that the equivalent ratio of the total hydroxyl groups in G) is 0.01 to 1.2.
(2) The vinyl ester resin composition according to (1), wherein (D) has 1.5 to 3 epoxy groups in one molecule, and (3) the epoxy group in (D) is a glycidyl group. The vinyl ester resin composition according to (1) above,
(4) The vinyl ester resin composition according to the above (1), wherein (D) is a bisphenol epoxy resin, (5)
The vinyl ester resin composition according to (1) above, wherein (H) has an average of 2 to 3.5 isocyanate groups in one molecule, and (6) above (E) is acrylic acid or methacrylic acid. (1) The vinyl ester resin composition described above, (7) (G) is hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or glycerin di (meth) acrylate. 1) The vinyl ester resin composition described in (1), (8) Further, 0.1 to 5.0 parts by weight of a curing catalyst and 0.01 to 10.0 parts by weight of an internal release agent are added to 100 parts by weight of the vinyl ester resin composition. , 0-400
(1) The vinyl ester resin composition according to the above (1), which comprises an additive such as a filler by weight, and (9) a curing of 0.1 to 5.0 parts by weight per 100 parts by weight of the vinyl ester resin composition. Catalyst, 0.01 to 10.0 parts by weight of internal release agent, 0
A sheet-form obtained by impregnating glass fibers with a vinyl ester resin composition according to claim 1, which comprises ˜400 parts by weight of an additive such as a filler, together with 0.2-10 parts by weight of a thickening agent. Or a bulk resin composition, and (10) a cured product obtained by curing the resin composition according to (8) or (9),
It is.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, first, an epoxy resin (D) having an epoxy group is reacted with an unsaturated monobasic acid (E) to obtain a vinyl ester resin (F).
Examples of the epoxy resin (D) used in this reaction include novolak type epoxy resins represented by bisphenol type epoxy resin, phenol novolac, cresol novolac, etc., aliphatic type, alicyclic, monocyclic epoxy resin, amine type epoxy resin. , A copolymer type epoxy resin or the like can be used. As the bisphenol type epoxy resin, a bisphenol A type epoxy resin having two glycidyl groups in the molecule, for example, Epototo YD128, YD011, YD014, YD0 manufactured by Tohto Kasei Co., Ltd.
17, YD901, YD904, Epicoat 828, 1001, 1004, 1 manufactured by Yuka Shell Epoxy Co., Ltd.
007, ELA128, ESA01 manufactured by Sumitomo Chemical Co., Ltd.
1, ESA014, ESA017, etc., a bisphenol F type epoxy resin having two glycidyl groups in the molecule, for example, Epotote YDF17 manufactured by Tohto Kasei Co., Ltd.
0, YDF 2001, Epicoat 807 manufactured by Yuka Shell Epoxy Co., Ltd., and other bisphenol S type epoxy resins having two glycidyl groups in the molecule, such as EBPS-300 manufactured by Nippon Kayaku Co., Ltd. Brominated bisphenol A type epoxy resin having two glycidyl groups on the base, for example, Epototo YD manufactured by Tohto Kasei Co., Ltd.
B400, YDB406, YDB412, Epicoat 5050, 5051 manufactured by Yuka Shell Epoxy Co., Ltd., Sumiepoxy ELB240, ELB25 manufactured by Sumitomo Chemical Co., Ltd.
0 can be mentioned. Examples of the phenol novolac type epoxy resin include Epotote YDPN 638 manufactured by Tohto Kasei Co., Ltd., Epicoat 152, 154 manufactured by Yuka Shell Epoxy Co., Ltd., Nippon Kayaku Co., Ltd.
EPPN201, BREN, etc. manufactured by Mitsui Chemical Co., Ltd. may be mentioned.

Examples of the cresol novolac type epoxy resin include Epotote YDC manufactured by Tohto Kasei Co., Ltd.
N701, YDCN702, YDCN703, YDCN
704, Sumitomo Chemical Co., Ltd. Sumiepoxy ESCN19
5HH, 220HH etc. can be mentioned. As the aliphatic type epoxy resin, a hydrogenated bisphenol A type epoxy resin having two glycidyl groups in the molecule, for example, Epotote ST-1000, ST manufactured by Tohto Kasei Co., Ltd.
Examples thereof include propylene glycol polyglycidyl ether having 1-2 glycidyl groups in the molecule, and pentaerythritol polyglycidyl ether having 1-4 glycidyl groups in the molecule.
Examples of the alicyclic epoxy resin include alicyclic diepoxy acetal having two epoxy groups in the molecule, dicyclopentadiene dioxide, and vinylhexene dioxide. Further, examples of the epoxy resin having one epoxy group in the molecule include vinylhexene monoxide, glycidyl methacrylate and the like. Examples of the monocyclic epoxy resin include resorcin diglycidyl ether and terephthalic acid diglycidyl ester. As amine type epoxy resin,
One having 4 epoxy groups in the molecule, such as YH-434 manufactured by Tohto Kasei Co., Ltd., can be used. Examples of the copolymerizable epoxy resin include a copolymer of glycidyl methacrylate and styrene. These epoxy resins may be used alone or as a mixture. These epoxy resins may have an average number of epoxy groups contained in one molecule of 1.2 or more, but those having an average of 1.2 to 4 are preferably used, and an average of 1.5 to 3 It is more preferably used as an individual item. Among these various types of epoxy resins, bisphenol type, aliphatic type, whose reaction with polyisocyanate is easy to control,
It is preferable to use monocyclic or alicyclic epoxy resin,
Furthermore, it is particularly preferable to use a bisphenol type epoxy resin having a skeleton with excellent corrosion resistance. Some bisphenol type epoxy resins have different nuclides, but when the number of nuclei is 5 or more, the viscosity of the resin increases, the workability deteriorates, and the double bond density in one molecule decreases. Since the heat resistance of the cured product is affected, it is preferable to use one having 4 or less nuclides.

Next, as the unsaturated monobasic acid (E), for example, unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and dibasic anhydride and at least one in one molecule. And a reaction product with an alcohol having an unsaturated group. Examples of the dibasic acid anhydride used in the reaction product, for example, maleic anhydride,
Examples thereof include aliphatic or aromatic dicarboxylic acid anhydrides such as succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Examples of the alcohol having an unsaturated group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,
Pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, and other acrylic acid, and ester compounds of methacrylic acid and polyhydric alcohol can be mentioned. As the unsaturated monobasic acid (E), it is preferable to use an unsaturated monobasic acid having a structure not containing an ester group having a C number of 6 or less, low heat resistance and high water absorption from the viewpoint of heat resistance, corrosion resistance and the like. . Further, it is preferable to use acrylic acid or methacrylic acid. In the reaction of the epoxy resin (D) with the unsaturated monobasic acid (E), the equivalent ratio of the unsaturated monobasic acid (E) to the epoxy groups of the epoxy resin (D) is 0.1.
The reaction is preferably carried out so as to be 8 to 1.2, and particularly preferably 0.9 to 1.1. At the time of this reaction, it is preferable to add a polymerization inhibitor so as not to gel the vinyl ester resin (F). Examples of the polymerization inhibitor used in the present invention include polymerization inhibitors conventionally used for unsaturated polyester resins such as hydroquinone, parabenzoquinone, methylhydroquinone and catechol, and vinyl ester resins. Further, in order to quantitatively promote the reaction of (D) and (E), it is preferable to use a vinyl esterification catalyst. Examples of the vinyl esterification catalyst include various tertiary amines such as benzyldimethylamine, various quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus-containing compounds such as triphenylphosphine, and various metal salts such as lithium and tin. And the like conventionally used.

Examples of the (meth) acrylate (G) having one hydroxyl group in the molecule which can be used in the production of the vinyl ester resin composition of the present invention include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid. 2-Hydroxyethyl (meth) to which monoepoxy compounds such as ethylene oxide and propylene oxide are added
(Meth) acrylic acid ester such as acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerin di (meth)
Preferred examples include acrylate and pentaerythritol tri (meth) acrylate. In the system of (F) and / or (G), when the ratio of (G) to the vinyl ester resin (F) contained in the system is high, the number of double bonds contained in one molecule is small and the heat resistance is high. Therefore, the amount of (G) contained in the system is 50% by weight.
The content is preferably the following, and particularly in the field where heat resistance is required, it is preferably 30% by weight or less. Next, the polyisocyanate component (H) is reacted with the vinyl ester resin (F) and / or the (meth) acrylate (G) having one hydroxyl group in one molecule to obtain the urethane-modified vinyl ester resin (A). . Examples of the polyisocyanate component (H) include conventionally known aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds containing alicyclic and araliphatic compounds, and mixtures of these polyisocyanate compounds and monoisocyanate compounds. Can be used. Examples of this polyisocyanate compound include, for example, tolylene diisocyanate (TDI),
Aromatic polyisocyanates such as phenylene diisocyanate (PDI), 4,4′-diphenylmethane diisocyanate (MDI), for example hydrogenated xylylene diisocyanate (H ₆ XDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (CHDI), hydrogenated Alicyclic polyisocyanates such as 4,4′-diphenylmethane diisocyanate (H ₁₂ MDI), araliphatic polyisocyanates such as xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI), for example 1,6-hexamethylene Aliphatic polyisocyanates such as diisocyanates (HDI) are mentioned. In addition, allophanates, burettes, trimers and the like of these polyisocyanate compounds are also preferred. Further, as the isocyanate compound having a monoisocyanate group, phenyl isocyanate, isocyanate ethyl methacrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate may be mentioned as a preferred example.

The cured product obtained by the present invention has an appearance, transparency,
It is also suitable for artificial marble applications because of its excellent color tone and boiling resistance. For artificial marble applications where appearance is important, IPDI, XDI, H ₆ XD among polyisocyanates
It is preferable to use so-called non-yellowing polyisocyanates such as I, TMXDI, H ₁₂ MDI and HDI.
The average number of functional groups of the isocyanate contained in one molecule in the polyisocyanate component (H) may be 1.5 or more, preferably 1.5 to 4, and more preferably 2 to
It is 3.5. This vinyl ester resin (F) and /
Alternatively, in the reaction of the (meth) acrylate (G) having one hydroxyl group and the polyisocyanate component (H), the equivalent ratio of the isocyanate group and the hydroxyl group is usually 0.01.
The reaction is carried out in the range of ~ 1.2, preferably 0.1-
The range is 1.2, more preferably 0.3 to 1.1.
A urethanization catalyst can be used to smoothly promote the reaction between the isocyanate group and the hydroxyl group. As the urethanization catalyst, for example, known tertiary amines such as triethylamine, organic acid salts such as tin octoate and dibutyltin dilaurate, and organometallic compounds can be used. The urethane-modified vinyl ester resin (A) may be mixed as it is with the reactive monomer (C), but a polybasic acid anhydride (B) is further added to a part or all of the hydroxyl groups in (A). Then, the urethane-modified acid-added vinyl ester resin (A ′) can be mixed with (C).
When (A) is not thickened with an alkaline earth metal oxide or the like, it is not necessary to modify it with an acid anhydride (B), but when it is sufficiently thickened with an alkaline earth metal oxide or the like ( A)
It is preferable to react 10% or more, preferably 25% or more of the hydroxyl groups therein with an acid anhydride. As (B) used here, anhydrides of saturated and unsaturated dicarboxylic acids such as maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferable. It is effective to use a reaction catalyst for the reaction of (A) and (B). For example, when a tertiary amine or a quaternary ammonium salt is used, the reaction time can be significantly shortened. The reaction temperature is usually 50 to 160 ° C, preferably 80 to 120 ° C. The use of the urethane-modified acid-added vinyl ester resin (A ′) is particularly useful when it is desired to thicken an alkaline earth metal oxide such as magnesium oxide by a heat and pressure molding method. Even in the pressure molding method, it is not always necessary when thickening with an isocyanate or when molding by a casting method.

The thus-obtained (A) or (A ') is mixed with the reactive monomer (C) (hereinafter sometimes referred to as vinyl monomer). Examples of the vinyl monomer include unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate 2
-Ethylhexyl, glycidyl (meth) acrylate,
Unsaturated fatty acid esters such as dodecyl (meth) acrylate, nitriles such as (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, diethylaminoethyl (meth) acrylamide, etc. Aliphatic vinyl compounds such as amides, vinyl chloride, propene, butene,
Styrene, vinyltoluene, divinylbenzene, pt
-Aromatic vinyl compounds such as butylstyrene, butadiene, isoprene, chloroprene, diene compounds such as pentadiene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
Examples thereof include polyfunctional (meth) acrylates such as 6-hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate, and these may be used alone or in combination. The mixing ratio of the urethane-modified vinyl ester resin (A) or the urethane-modified acid-added vinyl ester resin (A ') and the vinyl monomer can be arbitrarily selected, but the vinyl monomer content is preferably in the range of 10 to 80% by weight. , 30-8
The range of 0% by weight is more preferable. In addition to these (A) or (A ') and (C), a vinyl ester resin (F) is added in an amount of 5 to 45% by weight with respect to the entire resin composition, so that the workability of the cured product is not changed. In addition, productivity can be improved.

The vinyl ester resin composition of the present invention can be easily cured by adding an ordinary unsaturated polyester resin, a curing catalyst used for curing the vinyl ester resin, and a curing accelerator if necessary. You can Examples of the curing catalyst used in the present invention include organic peroxides such as methyl ethyl ketone peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide and cumene hydroperoxide. The amount of the curing catalyst used is preferably 0.1 to 5.0 parts by weight, and more preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the vinyl ester resin composition. As the curing accelerator, cobalt naphthenate, cobalt octanoate, dimethylaniline, diethylaniline,
Acetylacetone and the like can be mentioned. The amount of the curing accelerator used is 100 parts by weight of the vinyl ester resin composition,
It is preferably from 0.01 to 3.0 parts by weight. The vinyl ester resin composition of the present invention contains a filler, a shrinkage-reducing agent, a curing agent, an internal release agent, a pigment, a thickener, a polymerization inhibitor, a fiber reinforcement and the like which are usually used in this type of technique. By mixing the agent, it is possible to produce an artificial marble-like molded product and various cured products. Examples of the filler include aluminum hydroxide, glass powder, calcium carbonate, talc, silica, clay, glass balloons and the like. These are usually mixed in an amount of 0 to 400 parts by weight with respect to 100 parts by weight of the resin composition. As the shrinkage reducing agent, saturated polyester, polymethyl methacrylate, polyvinyl acetate, crosslinked polystyrene, styrene-butadiene (block) copolymer and its hydrogenated product, vinyl acetate-styrene (block) copolymer, (meth) acrylate Examples thereof include roux styrene (block) copolymers, and these can usually be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the vinyl ester resin composition. Examples of the internal mold release agent include metal soaps typified by zinc stearate and calcium stearate, silicon and fluorine-based organic compounds, phosphoric acid-based compounds, and the like. These are vinyl ester resin composition 100.
Usually, 0.01 to 10.0 parts by weight is used with respect to parts by weight.
Examples of the pigment include titanium oxide, carbon black, red iron oxide, phthalocyanine blue and the like.

Examples of the thickener include magnesium,
Examples thereof include oxides or hydroxides such as calcium, and usually 0.2 to 10 parts by weight is used with respect to 100 parts by weight of the vinyl ester resin. As the fiber reinforcing material, glass fibers having a diameter of about 8 to 15 μm and a length of 50 mm or less are generally used. Fiber reinforcement is usually 1 for the total amount of molding material.
About 75% by weight is blended. The vinyl ester resin composition of the present invention can be formed into a sheet-shaped molding material such as SMC or TMC or a bulk-shaped molding material such as BMC by kneading and impregnating these components by a known method. When a thickener is used, it is kneaded and impregnated, and then aged at a predetermined temperature for a predetermined time and then subjected to molding. The vinyl ester resin composition of the present invention can be made into a desired cured product by a heating / pressing method or a casting method known per se.

[0013]

EXAMPLES In order to help understanding of the present invention, preferred embodiments will be described below. Example 1 A vinyl ester resin composition (a) was prepared by the following method. In a 2-liter 4-necked Kolben equipped with a reflux tube and a stirrer, in the presence of 1.0 g of hydroquinone and 1.0 g of benzyldimethylamine, an epoxy resin (YD12
8, Toto Kasei Co., Ltd., epoxy equivalent 187) 748g
To the above, 344 g of methacrylic acid (manufactured by Mitsubishi Gas Co., Ltd.) was added, and the epoxy group was completely reacted at 120 ° C. Then, after adjusting the temperature in Kolben to 60 ° C., 0.3 g of dibutyltin dilaurate and 188 g of XDI (manufactured by Takeda Pharmaceutical Co., Ltd.) were added to completely react the isocyanate groups. Next, 98 g of succinic anhydride was added at 100 ° C. to completely react the acid anhydride with styrene 59.
The reaction was terminated by adding 1 g to obtain a vinyl ester resin composition (a). Next, this (a) was molded by the heating and pressing method, and the physical properties were evaluated. The molding conditions are shown below. Vinyl ester resin composition (a) 1 in a 3 liter kneader
00 g, aluminum hydroxide (CWL325B, manufactured by Sumitomo Chemical Co., Ltd.) 300 g, mono t-butyl hydroquinone (MTBHQ) 0.03 g, t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation) 0.5
g, t-butylperoxy 2-ethylhexanoate (Perbutyl O, manufactured by NOF CORPORATION) 0.5 g, zinc stearate (ZNS-P, manufactured by ADEKA FINE CHEMICALS Co., Ltd.) 4 g, and kneaded well . Next, 1 g of magnesium oxide (Magmic, manufactured by Kyowa Chemical Industry Co., Ltd.), 5 g of crosslinked polystyrene (Stafloyroid GS103, manufactured by Takeda Pharmaceutical Co., Ltd.), glass fiber (length: 1.5 m)
m chopped strands) was added and sufficiently kneaded and impregnated. This bulk molding compound (BM
C) was taken out from the kneader, and was thickened and aged at 40 ° C. for 3 days, and then, in a flat mold of 300 × 300 × 8 mm, 12
The plate was kept at 0 ° C. and 10 MPa for 7 minutes to obtain a flat plate for measuring physical properties. The evaluation results are shown in [Table 1].

Example 2 During the production of the vinyl ester resin composition (a) in Example 1, 344 g of methacrylic acid was changed to 288 g of acrylic acid,
A urethane-modified vinyl ester resin composition (b) was prepared in the same manner as in Example 1 except that the amount of styrene was changed to 567 g. A flat plate for evaluating physical properties was obtained in the same manner as in Example 1 except that 300 g of aluminum hydroxide was changed to 350 g. The evaluation results are shown in [Table 1]. Example 3 (a) 100 g in Example 1 (a) 50 g, (b) 5
A flat plate for measuring physical properties was obtained in the same manner as in Example 1 except that the amount was 0 g. The evaluation results are shown in [Table 1]. Example 4 (a) 100 g in Example 1 (a) 30 g, (b) 7
A flat plate for measuring physical properties was obtained in the same manner as in Example 1 except that the amount was 0 g. The evaluation results are shown in [Table 1]. Example 5 (a) 100 g in Example 1 (a) 80 g, (b) 2
A flat plate for measuring physical properties was obtained in the same manner as in Example 1 except that 0 g was used and 300 g of aluminum hydroxide was changed to 400 g.
The evaluation results are shown in [Table 1].

Example 6 A vinyl ester resin composition (c) and a plate for measuring physical properties were obtained in the same manner as in Example 1 except that 98 g of tetrahydrophthalic anhydride was used instead of 98 g of succinic anhydride in Example 1. Got The measurement results are shown in [Table 1]. Example 7 A vinyl ester resin composition (d) and a flat plate for measuring physical properties were obtained in the same manner as in Example 1 except that 98 g of maleic anhydride was used instead of 98 g of succinic anhydride in Example 1. The results are shown in [Table 1]. Comparative Example 1 Example 1 except that 100 g of (a) in Example 1 was replaced with 100 g of an isophthalic acid-based unsaturated polyester resin composition (Polymer 6316, manufactured by Takeda Pharmaceutical Co., Ltd.)
A flat plate for measuring physical properties was obtained in the same manner as in. The evaluation results are shown in [Table 1].

Example 8 An epoxy resin (YD128, manufactured by Tohto Kasei Co., Ltd.) in the presence of 1.0 g of hydroquinone and 1.0 g of benzyldimethylamine in a 2-liter 4-neck Kolben equipped with a reflux tube and a stirrer. To 374 g of epoxy equivalent 187), 172 g of methacrylic acid (manufactured by Mitsubishi Gas Co., Ltd.) was added.
The epoxy group was completely reacted at 0 ° C. Then, hydroxyethyl methacrylate (manufactured by Mitsubishi Gas Co., Ltd.) 260
g and 507 g of styrene monomer were added, the temperature in the Kolben was adjusted to 60 ° C., and then 0.3 g of dibutyltin dilaurate and 376 g of XDI (manufactured by Takeda Pharmaceutical Co., Ltd.) were added and reacted until the isocyanate group disappeared. Then, a vinyl ester resin composition (e) was obtained. Next, this resin composition was molded by a casting method and the physical properties were evaluated. The molding conditions are shown below. (E) For 100 g, aluminum hydroxide (CWL325B, manufactured by Sumitomo Chemical Co., Ltd.) 150
g, t-hexyl peroxy 2-ethylhexanoate (Percure HO, manufactured by NOF CORPORATION) 1.5 g, bis (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16, Kayaku Akzo ( Co., Ltd.)
After 0.5 g was added and kneaded well, vacuum degassing was performed. This resin paste is placed in a 300 × 300 × 8 mm flat mold and
The plate for physical property evaluation was obtained by heating at 0 ° C. for 20 minutes and at 90 ° C. for 60 minutes. The evaluation results are shown in [Table 2]. Example 9 A vinyl ester resin composition (f) was prepared in the same manner as in the preparation method of (e) in Example 8 except that 376 g of XDI was changed to 442 g of IPDI and the amount of styrene monomer was changed to 535 g in Example 8. Then, it carried out similarly to Example 8, and obtained the flat plate for physical-property evaluation. The evaluation results are shown in [Table 2]. Example 10 In Example 8, (e) 100 g, (e) 30 g, (f)
70 g and aluminum hydroxide amount 150 g
A flat plate for evaluating physical properties was obtained in the same manner as in Example 8 except that the amount was 0 g. The evaluation results are shown in [Table 2].

Comparative Example 2 In Example 8, 100 g of (e) was added to an isophthalic acid-based unsaturated polyester resin composition (Polymer 631).
6. A flat plate for evaluating physical properties was obtained in the same manner as in Example 8 except that the amount was 100 g, manufactured by Takeda Pharmaceutical Co., Ltd. The evaluation results are shown in [Table 2].

Example 11 Epoxy resin (YD128, manufactured by Tohto Kasei Co., Ltd.) in the presence of 3.5 g of hydroquinone and 3.0 g of benzyldimethylamine in a 10 liter four-necked Kolben equipped with a reflux tube and a stirrer. To 2244 g of epoxy equivalent 187), 1032 g of methacrylic acid (manufactured by Mitsubishi Gas Co., Ltd.) was added, and the epoxy group was completely reacted at 125 ° C. After adjusting the temperature in the Kolben to 60 ° C., 1.0 g of dibutyltin dilaurate, TDI (Takeda Pharmaceutical Co., Ltd.)
(Manufactured by K.K.) was added to completely react the isocyanate groups. Next, 98 g of maleic anhydride was added and reacted at 100 ° C., and 3616 g of styrene monomer was added to obtain a composition (g). Composition (g) 5 in a 10 liter container
kg, aluminum hydroxide (CWL325B, manufactured by Sumitomo Chemical Co., Ltd.) 7.5 kg, 1 g of parabenzoquinone, 50 g of t-butylperoxybenzoate, zinc stearate (ZNS-P, manufactured by ADEKA Fine Chemical Co., Ltd.) 20
0g, 10% carbon black toner (606BLK,
500 g of Tai Tai Kako Co., Ltd. was weighed and stirred with a high speed mixer for 10 minutes. Further, 300 g of 24% MgO paste (polymeric thickener, manufactured by Takeda Pharmaceutical Co., Ltd.) was added and further stirred for 3 minutes. 1 using this resin composition
Glass fiber (S-30 made by Nippon Electric Glass) cut into inches occupies 30% by weight in SMC.
MC was prepared. After thickening and aging this SMC at 40 ° C. for 3 days, 140 ° C. on a 300 × 300 × 8 mm flat plate,
The plate was held for 7 minutes under the condition of 10 MPa to obtain a flat plate for measuring physical properties. Comparative Example 3 In Example 11, in place of 5 kg of the composition (g), an unsaturated polyester resin (9305Z, bis A unsaturated polyester resin, NV53 (manufactured by Takeda Chemical Industries, Ltd.)) 5
A flat plate was prepared using kg. The evaluation results are shown in [Table 3].

[0018]

[Table 1] Heat and pressure method Unsaturated polyester: Isophthalic acid-based unsaturated polyester resin (styrene content 40% by weight)

[0019]

[Table 2] Casting method Unsaturated polyester resin: iso type unsaturated polyester resin (styrene content 40%)

[0020]

[Table 3] Strength retention rate: Retention rate after 150 ° C x 3000 hours

[0021]

The vinyl ester resin composition of the present invention is
In the case of heat and pressure molding, for example, the viscosity increases due to alkaline earth metal oxides such as magnesium oxide, and also in casting, the degree of crosslinking can be increased while keeping the resin viscosity low, resulting in high production efficiency. Moreover, the obtained cured product exhibits good heat resistance, corrosion resistance, boiling resistance, gloss and thickening property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C08G 18/58 NEK C08G 18/58 NEK 18/67 NFA 18/67 NFA 18/72 NFF 18/72 NFF 59/14 NHB 59/14 NHB C08L 75/14 C08L 75/14 (72) Inventor Kenichi Morita 2-26-1 Muraokahigashi, Fujisawa, Kanagawa Takeda Yakuhin Daiichi Shonan Dormitory (72) Inventor Shibata Koji 2-27-1401 Kajiwara, Kamakura City, Kanagawa Prefecture

Claims (10)

[Claims] 1. A urethane-modified vinyl ester resin (A) or a urethane-modified acid-added vinyl ester resin (A) obtained by adding a polybasic acid anhydride (B) to a part or all of the hydroxyl groups present in (A). A ') and a reactive monomer (C) having at least one double bond in the molecule, and (A) has an average of 1.2 or more epoxy groups in the molecule. Vinyl ester resin (F) obtained by adding unsaturated monobasic acid (E) to epoxy resin (D)
And / or has one hydroxyl group in one molecule (meta)
Acrylate (G) and polyisocyanate component (H) having an average of 1.5 or more isocyanate groups in one molecule
Is obtained by reacting an isocyanate group in the component (H) with an equivalent ratio of the total hydroxyl groups in the components (F) and (G) to be 0.01 to 1.2. Vinyl ester resin composition. 2. The vinyl ester resin composition according to claim 1, wherein (D) has 1.5 to 3 epoxy groups in one molecule. 3. The vinyl ester resin composition according to claim 1, wherein the epoxy group in (D) is a glycidyl group. 4. The vinyl ester resin composition according to claim 1, wherein (D) is a bisphenol epoxy resin. 5. The vinyl ester resin composition according to claim 1, wherein (H) has an average of 2 to 3.5 isocyanate groups in one molecule. 6. The vinyl ester resin composition according to claim 1, wherein (E) is acrylic acid or methacrylic acid. 7. The vinyl ester resin composition according to claim 1, wherein (G) is hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or glycerin di (meth) acrylate. 8. A curing catalyst of 0.1 to 5.0 parts by weight and 0.0 per 100 parts by weight of the vinyl ester resin composition.
The vinyl ester resin composition according to claim 1, comprising 1 to 10.0 parts by weight of an internal release agent and 0 to 400 parts by weight of additives such as a filler. 9. A curing catalyst of 0.1 to 5.0 parts by weight, based on 100 parts by weight of the vinyl ester resin composition, and 0.01 to 5.0 parts by weight.
The vinyl ester resin composition according to claim 1, which comprises 10.0 parts by weight of an internal release agent and 0 to 400 parts by weight of an additive such as a filler together with 0.2 to 10 parts by weight of a thickener. A sheet-like or bulk-like resin composition in which glass fibers are impregnated and thickened. 10. A cured product obtained by curing the resin composition according to claim 8.