JP2009024163A - Unsaturated polyester resin composition, and resin composite composition using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which has the alcohol resistant performance equal to or higher than that of a novolac-type epoxy (meth)acrylate resin and is excellent in the economy. <P>SOLUTION: The unsaturated polyester resin composition which contains an unsaturated polyester that is obtained from a dibasic acid component and a polyhydric alcohol component, and a polymerizable unsaturated monomer, is characterized in that the above dibasic acid component is comprised of 70-100% by mole of an unsaturated dibasic acid and 0-30% by mole of a saturated dibasic acid, and the above polyhydric alcohol component contains 50-100% by mole of a glycol having the main chain with the number of carbons of 1-3 and the side chain with the number of 0 or 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an unsaturated polyester resin composition excellent in alcohol resistance and a resin composite composition using the same.

  In recent years, carbon dioxide emissions have increased on a global scale, and global warming due to the effects has become a serious problem. In other countries, in order to reduce carbon dioxide emissions derived from fossil fuels, the use of alcohol-based fuels, especially ethanol, is advancing. In Japan, nearly 10% ethanol will be mixed with gasoline in the future. Use of automobile fuel is expected.

  The use of reinforced plastic double-shell tanks is considered for storing alcohol-based fuels. The structure of the reinforced plastic double shell tank includes an inner shell of an underground tank body and an FRP outer shell for forming a gap for detecting leakage of dangerous materials. And what uses the steel tank for the inner shell is called SF double shell tank, and what uses FRP for the inner shell is called FF double shell tank.

  Usually, the matrix used for FRP of SF double shell tank and FF double shell tank is various unsaturated polyester resins such as isophthalic acid type, bisphenol type, heptic acid type, bisphenol type, novolak type, brom bisphenol type And various epoxy (meth) acrylate resins, epoxy resins, phenol resins and the like. In particular, it is excellent in corrosion resistance, economic efficiency and room temperature curing, and can be easily molded, so unsaturated polyester resins such as isophthalic acid type, bisphenol type, heptic acid type, bisphenol type epoxy (meth) acrylate resin, and more In applications requiring corrosion resistance, novolak-type and bromobisphenol-type epoxy (meth) acrylate resins have been widely used.

  The non-patent document 1 confirms the usefulness of the alcohol-resistant performance of the novolak-type and bromobisphenol-type epoxy (meth) acrylate resins.

  On the other hand, regarding unsaturated polyester resins, it has been confirmed in Non-Patent Document 2 that degradation to alcohol occurs due to transesterification in a saturated dibasic acid moiety, and sufficient studies are made for applications requiring alcohol resistance performance. Was the required content.

  Therefore, novolak-type and bromobisphenol-type epoxy (meth) acrylate resins are useful for applications that require alcohol-resistant performance, but because they are relatively expensive matrices, they are more economically unsaturated. Development with polyester resin has been desired.

Edited by the Vinyl Ester Resin Study Group, “Vinyl Ester Resin”, published by Chemical Industry Daily, pages 423-424 Journal of the Japan Society of Materials Science, 18, 2 (1992), pp. 66-72

  Accordingly, the present invention has been made in view of the above circumstances, and has an unsaturated polyester resin composition having an alcohol resistance performance equal to or higher than that of a novolak-type epoxy (meth) acrylate resin and excellent in economic efficiency. The purpose is to provide.

Then, as a result of intensive investigations to solve the above problems, the present inventors, as a result, a dibasic acid component composed of 70 to 100 mol% unsaturated dibasic acid and 0 to 30 mol% saturated dibasic acid, Unsaturation blended with an unsaturated polyester obtained by esterifying a polyhydric alcohol component containing 50 to 100 mol% of a glycol having 1 to 3 carbon atoms in the main chain and 0 or 1 side chain The present inventors have found that a polyester resin composition can solve the above problems and have completed the present invention.
That is, the present invention is an unsaturated polyester resin composition comprising an unsaturated polyester obtained from a dibasic acid component and a polyhydric alcohol component, and a polymerizable unsaturated monomer, wherein the dibasic acid component is 70 to 100 mol% unsaturated dibasic acid and 0 to 30 mol% saturated dibasic acid, wherein the polyhydric alcohol component has 1 to 3 carbon atoms in the main chain and 0 side chains. Or it is an unsaturated polyester resin composition which contains 50-100 mol% of glycol which is 1.

  According to the present invention, it is possible to provide an unsaturated polyester resin composition having an alcohol resistance performance equal to or higher than that of a novolac-type epoxy (meth) acrylate resin and excellent in economic efficiency.

Hereinafter, the unsaturated polyester resin composition according to the present invention will be described in detail.
<Unsaturated polyester>
The unsaturated polyester resin composition of the present invention comprises, as essential components, a dibasic acid component composed of 70 to 100 mol% unsaturated dibasic acid and 0 to 30 mol% saturated dibasic acid, preferably unsaturated dibasic acid. Esterification reaction of a dibasic acid component consisting only of a basic acid and a polyhydric alcohol component containing 50 to 100 mol% of a glycol having 1 to 3 carbon atoms in the main chain and 0 or 1 side chain It contains the unsaturated polyester obtained by this, and a polymerizable unsaturated monomer.

The unsaturated polyester used in the present invention comprises an esterification reaction between a dibasic acid component containing an unsaturated dibasic acid and optionally containing a saturated dibasic acid and a polyhydric alcohol component containing a specific glycol. It is obtained and preferably has a number average molecular weight in the range of 400 to 5,000.
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. These may be used alone or in combination. You may use combining more than a kind. Examples of the saturated dibasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, Aromatic dibasic acids such as 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof, halogen A saturated saturated dibasic acid can be used, and these may be used alone or in combination of two or more.
The dibasic acid component used in the present invention must contain 70 to 100 mol% of unsaturated dibasic acid (0 to 30 mol% of saturated dibasic acid), and the dibasic acid component must be unsaturated dibasic. It preferably consists of only a basic acid. When the ratio of the unsaturated dibasic acid in the dibasic acid component is less than 70 mol%, sufficient alcohol resistance cannot be obtained.
Furthermore, it is preferable that fumaric acid is contained in the unsaturated dibasic acid component of the unsaturated polyester in an amount of 75 mol% or more, and more preferably 80 mol% or more. If the proportion of fumaric acid in the unsaturated dibasic acid component is less than 75 mol%, ethanol resistance may be lowered. In addition, maleic acid and maleic anhydride are known to transfer to fumaric acid during the esterification reaction, and fumaric acid can be used as a reaction raw material as long as the obtained unsaturated polyester satisfies the above-mentioned content ratio of fumaric acid. May not be used. The analysis method can be easily calculated from the integration ratio of the fumaric acid peak and the other unsaturated dibasic acid peak by a nuclear magnetic resonance analyzer (NMR).

The polyhydric alcohol component used in the present invention needs to contain 50 to 100 mol% of glycol having 1 to 3 carbon atoms in the main chain and 0 or 1 side chain. If the proportion of the glycol in the polyhydric alcohol component is less than 50 mol%, sufficient alcohol resistance cannot be obtained. Examples of the glycol having 1 to 3 carbon atoms in the main chain and 0 or 1 side chain include, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 2 -Methyl-1,3-propanediol and the like. In particular, since glycols containing side chains tend to lower alcohol resistance compared to glycols containing no side chains, the polyhydric alcohol component has 1 to 3 carbon atoms in the main chain. It is preferable to contain only the glycol which does not contain.
Other polyhydric alcohol components include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-butanediol, neopentyl glycol, 2-methyl-1,4- Butanediol, 2-ethyl-1,4-butanediol, 2,2,4-trimethyl-1,3-pentanediol 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5- Pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S Divalent phenols such as tetrabromobisphenol A and propylene oxide Or adducts with alkylene oxides typified by ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, pentaerythritol, 1,2-cyclohexane glycol, 1,3-cyclohexaneglycol 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2 , 7-decalin glycol and the like.

  As the unsaturated polyester used in the present invention, a polyester modified with a dicyclopentadiene compound can be used as long as the effects of the present invention are not impaired. Various known methods can be used for the modification with dicyclopentadiene compounds. For example, dicyclopentadiene and a maleic acid addition product (sidecanol monomaleate) are obtained and used as a monobasic acid. And a method of introducing a dicyclopentadiene skeleton.

<Polymerizable unsaturated monomer>
Examples of the polymerizable unsaturated monomer used in the present invention include unsaturated monomers capable of crosslinking with unsaturated polyester. As such a polymerizable unsaturated monomer, those having a vinyl group or a (meth) acryloyl group are preferable. Specific examples of the monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diarylphthalate, and triaryl. Examples include cyanurate.

  Examples of the monomer having a (meth) acryloyl group include acrylic acid esters and methacrylic acid esters; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) I-butyl acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid Stearyl, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glyco R-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 monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether ( (Meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethacrylate of PTMG, 1,3-butylene glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy , 3 Dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- ( Methacryloxy / polyethoxy) phenyl] propane, tetraethylene glycol diacrylate, bisphenol AEO modified (n = 2) diacrylate, isocyanuric acid EO modified (n = 3) diacrylate, pentaerythritol diacrylate monostearate, dicyclopentadiene, dicyclodecane Or various derivatives such as triazine, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate or tris (2-hydroxyethyl) ) Isocyanuric acrylate and the like.

  Furthermore, as polyfunctional (meth) acrylic acid esters, for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 -Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, alkanediol di- (meth) acrylate such as 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene Polyoxyalkylene-glycol di (meth) acrylates such as glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol (meth) acrylate Rate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, and diallyl fumarate. These may be used alone or in combination of two or more.

<Other ingredients>
In the unsaturated polyester resin composition of the present invention, an epoxy (meth) acrylate and / or an unsaturated polyester other than those described above may be blended within a range not impairing the effects of the present invention. It is 0-50 mass% of unsaturated polyester other than an epoxy (meth) acrylate and / or the above with respect to 50-100 mass% of polyester.

  Epoxy (meth) acrylate is obtained by reacting an epoxy resin having at least two epoxy groups in one molecule with an unsaturated monobasic acid, and adding an acid group of an unsaturated monobasic acid to the epoxy group. Preferably, it relates to di (meth) acrylate and / or tri (meth) acrylate. This epoxy (meth) acrylate is obtained by reacting an epoxy resin having an average epoxy equivalent preferably in the range of 100 to 500 with an unsaturated monobasic acid in the presence of an esterification catalyst. As the epoxy resin, the following compounds are exemplified as typical ones.

  Examples of the epoxy resin having a terminal epoxy group include a reaction product of bisphenol A and epichlorohydrin, a reaction product of bisphenol F and epichlorohydrin, a reaction product of hydrogenated bisphenol A and epichlorohydrin, a reaction product of cyclohexanedimethanol and epichlorohydrin, norbornane. Reaction product of dialcohol and epichlorohydrin, reaction product of tetrabromobisphenol and epichlorohydrin, reaction product of tricyclodecane dimethanol and epichlorohydrin, reaction product of phenol novolac and epichlorohydrin, reaction product of cresol novolac and epichlorohydrin, 1 , 6 Reaction product of naphthalenediol and epichlorohydrin, epoxy resin having dicyclopentadiene skeleton, dicyclopentadiene alicyclic Diepoxy adipate, alicyclic diepoxy carbonate, alicyclic diepoxy acetal, include alicyclic diepoxy carboxylate.

  Further, as a glycidyl ether type compound in which ethylene oxide and / or propylene oxide is added to a terminal hydroxyl group of a compound having two or more hydroxyl groups, for example, the oxide is added to a compound having two or more hydroxyl groups, and epichlorohydrin is reacted. Is obtained. For example, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, cyclohexanedimethanol ethylene oxide adduct, cyclohexanedimethanol propylene oxide adduct, hydrogenated bisphenol A Examples thereof include glycidyl ether type compounds such as ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, diphenylethylene oxide adduct, diphenylpropylene oxide adduct and the like.

  In addition, a compound having two or more hydroxyl groups may be used for adjustment of epoxy elongation, and specific compounds include bisphenol A, hydrogenated bisphenol A, cyclohexanedimethanol, norbornane dialcohol, tetrabromobisphenol. A, tricyclodecane dimethanol, 1,6-naphthalenediol and the like. The said epoxy resin may be used independently or may be used in combination of 2 or more type in the range which does not impair performance.

  Typical examples of unsaturated monobasic acids used in preparing epoxy (meth) acrylates include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethyl malate, and monopropyl maleic acid. Rate, monobutyl malate and the like, and acrylic acid and methacrylic acid are particularly preferable.

  In addition, these unsaturated monobasic acids may be used individually by 1 type, and may use 2 or more types together. The reaction between the epoxy resin and the unsaturated monobasic acid can be synthesized by a known method, preferably at a temperature in the range of 60 to 140 ° C., particularly preferably 80 to 120 ° C. , Using an esterification catalyst. The use amount of the epoxy resin and the unsaturated monobasic acid is preferably 0.7 to 1.3 / 1, more preferably 0.8 to 1.2 / 1 in terms of an equivalent ratio of acid group / epoxy group.

  As the esterification catalyst, known and commonly used compounds can be used as they are, and among them, triethylamine, N, N-dimethylbenzylamine, 2-methylimidazole, N, N-dimethylaniline, And amines such as diazabicyclooctane, diethylamine hydrochloride, tin, zinc, iron, chromium, vanadium, and phosphorus-containing compounds.

  In addition, the epoxy (meth) acrylate may introduce a carboxyl group by reacting a compound capable of imparting a carboxyl group to at least a part of the hydroxyl group. The method for introducing a carboxyl group is not particularly limited, but an acid anhydride is reacted with a hydroxyl group generated by a reaction between an epoxy resin and an unsaturated monobasic acid, that is, a hydroxyl group generated by a ring-opening reaction of an epoxy group. It is preferable to obtain it. In this reaction, after the epoxy (meth) acrylate is produced, an acid anhydride is added to the epoxy (meth) acrylate, or an acid anhydride is added to the mixture of the epoxy (meth) acrylate and the polymerizable unsaturated monomer. It is obtained by adding.

  Examples of preferred acid anhydrides that can impart a carboxyl group include maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydroanhydride. Examples thereof include phthalic acid, halogenated phthalic anhydride, trimellitic anhydride, and 2,3-naphthalenedicarboxylic anhydride. In addition, as said compound which can provide a carboxyl group, although the said acid anhydride is preferable, for example, the compound which has an isocyanate group and a carboxyl group, the compound which has a silyl group and a carboxyl group, etc. can also be used.

  The number average molecular weight of the epoxy (meth) acrylate is preferably in the range of 500 to 3,000. In addition, the number average molecular weight here is a number average molecular weight in terms of polystyrene by gel permeation chromatography.

  Each of the above-described unsaturated polyester and epoxy (meth) acrylate used in combination in the present invention is usually dissolved using a polymerizable unsaturated monomer and used as a thermosetting resin composition. The use ratio is preferably 5 to 60% by mass of the polymerizable unsaturated monomer with respect to the total of 40 to 95% by mass of the above-described unsaturated polyester and epoxy (meth) acrylate used together as necessary. .

  If desired, a polymerization inhibitor can be added to the unsaturated polyester resin composition of the present invention. Examples of the polymerization inhibitor include those conventionally used for unsaturated polyester resins, such as hydroquinone, trihydrobenzene, benzoquinone, P-benzoquinone, methylhydroquinone, trimethylhydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, catechol, Examples thereof include t-butylcatechol, 2,6-di-t-butyl-4-methylphenol. This polymerization inhibitor can be added in the range of 10 to 1000 ppm with respect to the unsaturated polyester resin composition.

  The unsaturated polyester resin composition of the present invention is easily cured by room temperature curing or heat curing by adding a radical curing agent and a curing accelerator commonly used in ordinary unsaturated polyester resins, or by a photo radical initiator. Can be made. Examples of radical curing agents include organic peroxides, specifically, diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, and hydroperoxides such as cumene hydroperoxide. And known ones such as dialkyl peroxides such as dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters, and carbonates. These radical curing agents can be added in the range of 0.1 to 6 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.

  Examples of the curing accelerator include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate and the like. Metal chelates, 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- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl- -N, N-substituted anilines such as toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p -Amines such as toluidine and 4- (N, N-substituted amino) benzaldehyde. These curing accelerators can be added in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.

  The photo radical initiator is a photo sensitizer, specifically, a benzoin ether type such as benzoin alkyl ether, a benzophenone type such as benzophenone, benzyl, methyl orthobenzoyl benzoate, benzyl dimethyl ketal, and 2,2-diethoxy. Acetophenones such as acetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2 -Thioxanthone series such as isopropylthioxanthone and the like can be mentioned. These photo radical initiators can be added in the range of 0.1 to 6 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.

In the unsaturated polyester resin composition of the present invention, various additives such as thixotropic agent, thixotropic agent, coloring agent, ultraviolet absorber, thickener, antifoaming agent, wax, plasticizer and the like are appropriately blended. May be.
In particular, when used as an FRP matrix, FRP molded product gel coat or top coat, a thixotropic agent and thixotropic agent may be added to impart thixotropic properties. preferable. Specific examples of the thixotropic agent include anhydrous fine powder silica, asbestos, clay and the like. Specific examples of the thixotropic agent include polyethylene glycol, glycerin, polyhydroxycarboxylic acid amide, organic quaternary ammonium salt, BYK-R-605 (trade name; manufactured by Big Chemie Japan Co., Ltd.) and the like. Is mentioned. By adding these thixotropic agents, it is possible to impart thixotropic properties (thixotropic properties) to the resin, making it difficult for the resin to sag, and evenly applying the resin not only to the horizontal surface but also to the standing surface. A resin cured coating film can be formed. These thixotropic agents can be added in the range of 0.2 to 10 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.

  In addition, when the unsaturated polyester resin composition of the present invention is used for an FRP matrix or a top coat of an FRP molded product, a wax may be added. Specific examples of the wax include at least one selected from the group consisting of petroleum wax, olefin wax, polar wax, and special wax. Examples of petroleum waxes include paraffin wax and microcrystalline wax. Examples of the olefin wax include polyethylene and polypropylene. Further, examples of polar waxes include waxes obtained by introducing polar groups (such as hydroxyl groups and ester groups) into these petroleum waxes and olefin waxes, and unsaturated fatty acid esters such as oleic acid, linoleic acid, and linolenic acid. Examples of the special wax include Byk LPS-6665 manufactured by Big Chemie. These waxes can be added in the range of 0.01 to 2 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition. By using these waxes, when the unsaturated polyester resin composition is cured, it precipitates on the surface of the coating film and the lining layer and works effectively as an oxygen blocking agent, and the surface drying property of the coating film and lining layer is good. (Inhibition of curing or the like by air or oxygen on the surface can be prevented). Without these waxes, it may be difficult to obtain good surface drying properties.

Specific examples of the colorant include organic pigments, inorganic pigments, dyes and the like.
Specific examples of the plasticizer include chlorinated paraffin, phosphate ester, phthalate ester and the like.
Specific examples of the thickener include metal oxides such as magnesium oxide, calcium oxide, and zinc oxide.
As specific examples of the antifoaming agent, known ones such as silicon-based and polymer-based ones can be used.
Specific examples of the ultraviolet absorber include known ones such as benzotriazoles such as 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, benzophenones such as 2,4-dihydroxybenzophenone, and benzoates. Can be used. Furthermore, a hindered amine system etc. can also be used. These ultraviolet absorbers can be added in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.

  The unsaturated polyester resin composition of the present invention can be combined with at least one of a fiber reinforcing material, a filler and an aggregate to produce a resin composite composition. Examples of the fiber reinforcement used include organic fibers such as glass fibers, amides, aramids, vinylons, polyesters, and phenols, and inorganic fibers such as carbon fibers, metal fibers, and ceramic fibers. You may use independently and may use it in combination of 2 or more types. In consideration of workability and economy, glass fibers and organic fibers are preferable, and glass fibers are particularly preferable. Further, the fiber forms include plain weave, satin weave, non-woven fabric, mat, roving, chop, knitted fabric, braided fabric, and composite structures of these, but the mat shape is preferable due to construction method, thickness maintenance and the like. Moreover, it is also possible to cut glass roving into 20-100 mm and use it as a chopped strand. As a compounding quantity of a fiber reinforcement material, Preferably it is 1-300 mass parts with respect to 100 mass parts of unsaturated polyester resin compositions of this invention, More preferably, it is 5-200 mass parts. If the blending amount of the fiber reinforcing material is less than 1 part by mass, sufficient strength as FRP cannot be obtained, and if it exceeds 300 parts by mass, sufficient alcohol resistance cannot be obtained.

  Examples of the filler include calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, and glass powder. Examples of the aggregate include quartz sand, gravel, and crushed stone. When used for mortar applications, those having a particle size of about 5 mm or less are preferred. The blending amount of the filler or aggregate is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition of the present invention.

  The method for molding the unsaturated polyester resin composition of the present invention is not particularly limited, and examples thereof include a hand lay-up molding method, a spray-up molding method, a filament winding molding method, a resin injection molding method, and a resin transfer molding method.・ Pull molding, vacuum molding, pressure molding, compression molding, injection molding, casting, spraying, etc. can be applied.

  Moreover, when apply | coating a gel coat layer to a FRP molded product, the method performed normally, such as a hand layup and a spray-up method, is employable. For example, FRP molding in which a gel coat layer is applied after steps of applying and curing an unsaturated polyester resin composition for gel coat, laminating and curing an FRP layer, and demolding by mold release treatment, spray method or brush coating method, etc. Goods are obtained. Moreover, the FRP molded article or lining coating structure which apply | coated the topcoat layer is obtained by apply | coating and hardening the unsaturated polyester resin composition for topcoats in the finishing of a molded article.

  The unsaturated polyester resin composition of the present invention can also be used for molding materials such as BMC (Bulk Molding Compound) and SMC (Sheet Molding Compound).

  The unsaturated polyester resin composition of the present invention has an alcohol resistance performance equivalent to or higher than that of a novolak-type epoxy (meth) acrylate resin and is excellent in economic efficiency. And extremely useful.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In addition, the ratio of fumaric acid in the unsaturated dibasic acid component of the obtained unsaturated polyester was determined using fumaric acid and others using a nuclear magnetic resonance analyzer (JNM-LA300 FT NMR SYSTEM: manufactured by JEOL Ltd.). It calculated from the integral ratio with unsaturated dibasic acid.

[Preparation of unsaturated polyester]
<Production Example 1>
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 3.1 mol of maleic anhydride, 2.2 mol of ethylene glycol and 0.9 mol of 1,5-pentanediol, While heating and stirring under a nitrogen stream, the temperature was raised to 200 ° C., and an esterification reaction was carried out by a conventional procedure. When the acid value reached 30.8 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 78 mol%. Next, 0.50 part by mass of hydroquinone was added to this unsaturated polyester and dissolved in styrene to prepare an unsaturated polyester resin composition (PE-1) having a styrene content of 45% by mass.

<Production Example 2>
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, fumaric acid 3.3 mol, 1,2-propanediol 2.3 mol and 1,5-pentanediol 1.0 mol The mixture was heated to 200 ° C. with heating and stirring under a nitrogen stream, and an esterification reaction was carried out by a conventional procedure. When the acid value reached 28.6 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester, and then 0.50 part by mass of hydroquinone was added to the unsaturated polyester to obtain an unsaturated polyester. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-2) having a styrene content of 45% by mass.

<Production Example 3>
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, maleic anhydride 3.2 mol, 2-methyl-1,3-propanediol 2.2 mol and 1,5-pentane 1.0 mol of diol was charged, the temperature was raised to 200 ° C. with heating and stirring under a nitrogen stream, and an esterification reaction was carried out according to a conventional procedure. When the acid value reached 23.3 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. Next, 0.50 part by mass of hydroquinone was added to the unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 85 mol%. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-3) having a styrene content of 45% by mass.

<Production Example 4>
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 3.4 moles of maleic anhydride, 2.4 moles of ethylene glycol and 1.0 moles of dipropylene glycol under a nitrogen stream. The temperature was raised to 200 ° C. while stirring with heating, and an esterification reaction was carried out by a conventional procedure. When the acid value reached 27.2 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester, and then 0.50 part by mass of hydroquinone was added to the unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 81 mol%. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-4) having a styrene content of 45% by mass.

<Production Example 5>
A four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser is charged with 3.2 mol of maleic anhydride, 2.2 mol of 1,2-propanediol and 1.0 mol of dipropylene glycol. Then, the temperature was raised to 200 ° C. while stirring under heating in a nitrogen stream, and an esterification reaction was carried out according to a conventional procedure. When the acid value reached 24.5 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester, and then 0.50 part by mass of hydroquinone was added to the unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 93 mol%. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-5) having a styrene content of 45% by mass.

<Production Example 6>
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, 0.9 mol of isophthalic acid, 2.2 mol of 1,2-propylene glycol and 0.9 mol of 1,5-pentanediol The mixture was heated to 190 ° C. with heating and stirring under a nitrogen stream, and then gradually heated to 215 ° C. for esterification, and cooled when the acid value reached 9.5 mgKOH / g. At 220 ° C., 2.2 mol of fumaric acid was charged, and an esterification reaction was conducted at 150 to 210 ° C. by a conventional method. When the acid value reached 9.8 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. Next, 0.50 part by mass of hydroquinone was added to the unsaturated polyester. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-6) having a styrene content of 45% by mass.

<Production Example 7>
A four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser was charged with 3 mol of fumaric acid and 3 mol of 1,5-pentanediol, and the temperature was raised to 200 ° C. while heating and stirring under a nitrogen stream. The mixture was warmed and the esterification reaction was carried out according to a conventional procedure. When the acid value reached 9.8 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. Next, 0.50 part by mass of hydroquinone was added to the unsaturated polyester. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-7) having a styrene content of 45% by mass.

<Production Example 8>
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, 0.7 mol of maleic anhydride, 0.7 mol of fumaric acid, and dihydric phenol of bisphenol A and propylene oxide The adduct was charged in an amount of 1.4 mol, heated to 200 ° C. with stirring under a nitrogen stream, and an esterification reaction was carried out according to a conventional procedure. When the acid value reached 9.8 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. Next, 0.50 part by mass of hydroquinone was added to the unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 93 mol%. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-8) having a styrene content of 45% by mass.

<Production Example 9>
A four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser was charged with 0.8 mol of isophthalic acid, 1.0 mol of 1,2-propanediol and 1.8 mol of neopentyl glycol, While heating and stirring under a nitrogen stream, the temperature was raised to 190 ° C., then gradually raised to 215 ° C. for esterification reaction, and cooled when the acid value reached 9.5 mgKOH / g, and anhydrous at 120 ° C. 2.0 mol of maleic acid was charged and an esterification reaction was carried out at 150 to 210 ° C. according to a conventional procedure. When the acid value reached 9.8 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. Next, 0.50 part by mass of hydroquinone was added to the unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 90 mol%. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-9) having a styrene content of 45% by mass.

<Production Example 10>
In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, maleic anhydride 1.2 mol, phthalic anhydride 1.8 mol, ethylene glycol 0.9 mol and 1,2-propane 2.1 mol of diol was charged, the temperature was raised to 200 ° C. with heating and stirring under a nitrogen stream, and an esterification reaction was carried out by a conventional procedure. When the acid value reached 9.8 mgKOH / g, the mixture was cooled to obtain an unsaturated polyester. Next, 0.50 part by mass of hydroquinone was added to the unsaturated polyester. In addition, the ratio of the fumaric acid in an unsaturated dibasic acid component was 85 mol%. This was dissolved in styrene to prepare an unsaturated polyester resin composition (PE-10) having a styrene content of 45% by mass.

<Production Example 11>
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 476 parts by mass of a novolac-based epoxy resin (Epicron N-740: manufactured by Dainippon Ink Co., Ltd., epoxy equivalent 180), The temperature was raised to 100 ° C. with stirring, and then 0.7 parts by weight of methylhydroquinone, 228 parts by weight of methacrylic acid, and 3.5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol (sequol TDMP) (catalyst ), The temperature was raised with stirring, and the esterification reaction was carried out at a temperature of 120 ° C. to 130 ° C. by a conventional procedure. When the acid value reached 9.5 mgKOH / g, the mixture was cooled to obtain a novolak-type epoxy methacrylate, which was dissolved in styrene to obtain a novolak-type epoxy methacrylate resin composition (VE-1) having a styrene content of 30% by mass. Prepared.

<Adjustment of cast products of Examples 1 to 6 and Comparative Examples 1 to 5>
Unsaturated polyester resin composition obtained in Production Examples 1 to 10 or novolak-type epoxy methacrylate resin composition obtained in Production Example 11: 1 part by mass of Parmek N (manufactured by NOF Corporation) as a polymerization initiator with respect to 100 parts by mass Pour between 0.5 parts by weight and 0.5 parts by weight of 8% cobalt octylate, pour between glass plates set to a thickness of 3 mm, let stand for 1 day, cure at room temperature, and after cure at 120 ° C. for 2 hours. A casting plate was produced.
The obtained casting plate was cut into a 5 cm × 5 cm square to obtain a test piece for evaluating ethanol resistance.

<Evaluation of ethanol resistance>
About ethanol resistance, the test piece produced above was immersed in the ethanol liquid of temperature 40 +/- 1 degreeC, and evaluation was performed by the mass change rate of the test piece one month later, and the Barcol hardness retention. The Barcol hardness was measured by a method based on “JIS-K-6911 Barcol hardness”. That is, 10 points or more were performed on the test piece using the Barcol hardness meter 934-1, and the average value of each measurement result was defined as Barcol hardness.

  As can be seen from the results in Tables 1 and 2, the unsaturated polyester resin compositions of Examples 1 to 6 are equivalent to the novolak epoxy methacrylate resin of Comparative Example 5 in both mass change rate and Barcol hardness retention rate. More ethanol resistance was obtained. On the other hand, the unsaturated polyester resin compositions of Comparative Examples 1 to 4 did not have sufficient ethanol resistance performance.

Claims (5)

In an unsaturated polyester resin composition comprising an unsaturated polyester obtained from a dibasic acid component and a polyhydric alcohol component, and a polymerizable unsaturated monomer,
The dibasic acid component is composed of 70 to 100 mol% unsaturated dibasic acid and 0 to 30 mol% saturated dibasic acid, and the polyhydric alcohol component has 1 to 3 carbon atoms in the main chain. And the unsaturated polyester resin composition characterized by containing 50-100 mol% of glycols whose number of side chains is 0 or 1.   The unsaturated polyester resin composition according to claim 1, wherein the polyhydric alcohol component contains only glycol having no side chain.   The unsaturated polyester resin composition according to claim 1 or 2, wherein the polyhydric alcohol component contains only glycol that does not contain an ether bond.   The unsaturated polyester resin composition according to claim 1, wherein the dibasic acid component contains only an unsaturated dibasic acid.   The resin composite obtained by mix | blending at least 1 sort (s) selected from the group which consists of a fiber reinforcement, a filler, and an aggregate with respect to the unsaturated polyester resin composition as described in any one of Claims 1-4. Composition.