JPH0138127B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on fiber reinforced plastics (FRP).
Regarding a molding resin composition that is extremely useful as a molding material for the preform mated metal die method, prepreg method, bulk molding compound method, sheet molding compound method, etc., its purpose is to have low curing shrinkage. It is an object of the present invention to provide a molding resin composition which has excellent properties to prevent resin separation and which can be uniformly colored to any desired color tone. A resin composition obtained by adding a thickener to a mixture consisting of an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a curing catalyst, a mold release agent, a filler, a coloring agent, etc. can be used for glass fiber, etc. The molding resin composition obtained by coating and impregnating the reinforcing material, or kneading it with the reinforcing material using a kneader, etc., and increasing the viscosity is known as a so-called bulk molding compound or sheet molding compound. It is a new material. However, since the above-mentioned molding resin composition shrinks significantly during curing, the resulting molded product is likely to have distortions and sluggishness, and the reinforcing material may bulge out on the surface of the molded product, impairing its smoothness. It has its drawbacks. Conventionally, in order to eliminate such drawbacks, thermoplastic resins such as polymethyl methacrylate, polystyrene, saturated polyesters made of propylene glycol and adipic acid or sebacic acid are mixed with the above molding resin composition and cured. A method of significantly reducing shrinkage during curing is known. However, in molding resin compositions made by mixing these thermoplastic resins, the unsaturated polyester resin and the thermoplastic resin undergo phase separation, and the thermoplastic resin stands out on the surface of the composition. The thermoplastic resin remains sticky even after molding, the thermoplastic resin bulges out onto the surface of the molded product, creating a mottled pattern, making it impossible to obtain a uniformly colored molded product, and the paintability of the molded product being poor. There were flaws. The present inventors have conducted intensive studies to obtain a molding resin composition that has improved the above-mentioned drawbacks, and have found that titanate and/or
(1) When the unsaturated polyester resin and/or vinyl ester resin and the thermoplastic resin are added, a uniform resin composition for molding can be obtained without causing phase separation; (2) (3) This molding resin composition can be colored in any desired color, and even after molding, the thermoplastic resin does not remain on the surface of the molded product. (4) This molding resin composition has sufficient low shrinkage during molding, and the resulting molded product has excellent paintability. The inventors have discovered that the present invention has the following characteristics. That is, the present invention provides a molding material comprising an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a thermoplastic resin having compatibility with the monomer, and a titanate and/or a hydrate thereof. The present invention relates to a resin composition. The unsaturated polyester used in the present invention contains 50 to 100 mol% of α/β-unsaturated dibasic acid and 50 to 0 mol% of aliphatic saturated dihydrochloric acid, aromatic saturated dihydrochloric acid, or alicyclic dibasic acid. It is obtained by polycondensation reaction between an acid component consisting of the following and a polyhydric alcohol or an alkylene oxide. At this time, in order to exhibit sufficient low shrinkage during molding, it is preferable to use 60 mol% or more of α/β-unsaturated dibasic acid. α and β used in the production of unsaturated polyester
- Examples of unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid. Furthermore, examples of aliphatic saturated dibasic acids used in combination with α/β-unsaturated dibasic acids include adipic acid and sebacic acid, and examples of aromatic saturated dibasic acids include phthalic acid, Examples include phthalic anhydride, isophthalic acid, and terephthalic acid, and examples of alicyclic dibasic acids include tetraphthalic anhydride and endomethylenetetrahydrophthalic acid. In addition, polyhydric alcohols that are one of the components used in the production of unsaturated polyesters include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1.3
-Butanediol, 1,4-butanediol,
Examples include glycols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, and adducts of bisphenol A with propylene oxide, and triols such as glycerin and trimethylolpropane. Also, examples of the alkylene oxide include ethylene oxide and propylene oxide. Additionally, dicyclopentadiene, cyclopentadiene-maleic acid adducts are used as replacements for some of the raw materials mentioned above. The vinyl ester resin used in the present invention has a carboxyl group in an unsaturated basic acid per equivalent of epoxy group contained in the epoxy compound.
Within the range of 0.5 to 1.5 equivalents, in the presence of an esterification catalyst, heat at a temperature of 80 to 150 °C and react until the acid value becomes 20 to 0 (normal reaction time is 2 to 15 hours). It can be obtained by adding a polymerizable monomer to the resulting ester. This reaction may be carried out without a solvent, or in a non-reactive solvent such as toluene or benzene, or in a system using a polymerizable monomer such as styrene, vinyltoluene, or acrylic ester as a solvent. You can also do it with These non-reactive solvents and polymerizable monomers may be used alone or in combination of two or more. Examples of epoxy compounds used in the production of vinyl ester resins include 2-2'-bis(4-
diglycidyl ether obtained by the reaction of hydroxyphenyl)propane with epichlorohydrin or methylepiclorhydrin; diglycidyl ether obtained by the reaction of glycols with epichlorohydrin or methylepiclorhydrin diglycidyl ether obtained by the reaction of novolak obtained by the reaction of phenol and formaldehyde with epichlorohydrin or methylepiclorhydrin, polyepoxy compounds derived from polybutadiene, etc. These can be used alone or in combination of two or more. Examples of unsaturated basic acids include acrylic acid,
Examples include methacrylic acid and crotonic acid.
These unsaturated basic acids may be used in combination with saturated basic acids or polybasic acids, if desired. Examples of the esterification catalyst include secondary amines such as dimethylamine and diethylamine, N-
Examples include tertiary amines such as N'-dimethylaniline, pyridine, and triethylamine, quaternary ammonium salts such as tetramethylammonium chloride, and sulfonates such as paratoluenesulfonate. The polymerizable monomer to be mixed with the unsaturated polyester or vinyl ester resin is not particularly limited as long as it radically polymerizes with the unsaturated polyester or vinyl ester resin, and specifically, styrene, α
-Methylstyrene, chlorostyrene, vinyltoluene, divinyltoluene, diallyl phthalate,
Examples include diallylisophthalate, lower esters of acrylic acid or methacrylic acid, vinyl acetate, and trialcyanurate. The amount of the polymerizable monomer used is preferably 20 to 120 parts by weight per 100 parts by weight of the unsaturated polyester or vinyl ester resin. The thermoplastic resin used in the present invention is not particularly limited as long as it is compatible with the polymerizable monomer, and specifically includes styrene, ethylene, propylene, vinyl chloride, vinyl acetate, vinyl versatate, Homopolymers and copolymers of polymerizable monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, maleic acid monoester, acrylamide, styrene-acrylonitrile copolymers,
Examples include butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and saturated polyesters. The molecular weight of thermoplastic resin is 2000~
1,000,000, and the amount used is 1 to 40 parts by weight per 100 parts by weight of the total amount of unsaturated polyester and/or vinyl ester resin and polymerizable monomer.
Parts by weight are preferred. The titanate or hydrate thereof used in the present invention is a salt synthesized from titanium dioxide, such as potassium titanate, sodium titanate, barium titanate, lithium titanate, or a hydrate thereof, and is preferably a hydrate thereof. is potassium titanate or its hydrate. Examples of commercially available potassium titanate fibers and potassium titanate hydrate fibers include Fyhex (DuPont, USA), Daysmo-D or Daysmo-L (Otsuka Chemical Co., Ltd.). be. These may be used in combination. The amount of titanate and/or its hydrate added is
Use 0.01 to 20 parts by weight per 100 parts by weight of the resin composition, such as unsaturated polyester and/or vinyl ester resin, polymerizable monomer, thermoplastic resin, filler, curing catalyst, coloring agent, mold release agent, etc. It is preferable to do so. If the amount added is less than 0.01 part by weight, resin separation may occur or color unevenness may occur in the molded product, making it impossible to achieve the object of the present invention. Also, the amount added is 20
If the amount is more than 1 part by weight, it is no longer possible to expect an effect proportional to the amount added. Curing catalysts used in the present invention include benzoyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, cumene hydroperoxide, dicumyl peroxide, etc. Fillers include calcium carbonate, clay,
Barium sulfate, aluminum hydroxide, etc. Mold release agents include stearic acid metal salts, phosphoric acid esters, etc. Coloring agents include inorganic and organic types currently used for coloring unsaturated polyester resins and vinyl ester resins. pigments, reinforcing materials such as glass fibers, carbon fibers, organic fibers, thickeners such as alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, toughness imparting As the agent, all conventionally used agents can be used, such as unsaturated acrylic urethane prepolymers, and the amount used is determined by the intended resin composition for molding and the performance of the molded product. However, there are no particular restrictions. The molding resin composition of the present invention is a resin containing, for example, an unsaturated polyester and/or vinyl ester resin, a polymerizable monomer, a curing catalyst, a mold release agent, a filler, a coloring agent, a calcium titanate fiber, etc. A thickener is added to the composition and mixed with stirring, and before the thickening progresses, it is impregnated with a reinforcing material such as glass fiber, carbon fiber, or organic fiber, or the resin composition and the reinforcing material are kneaded. can be obtained. This molding resin composition can be produced by molding methods such as compression molding, injection molding, and transfer molding.
Preferably, the molding is carried out at a temperature of 100-170°C. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "parts" shown in the examples
means "parts by weight" unless otherwise specified. Production example of unsaturated polyester resin (1) 1161g of fumaric acid and 837g of propylene glycol
was reacted in a conventional manner at 200° C. for about 9 hours under a nitrogen stream to obtain an unsaturated polyester having an acid value of 30. After adding 0.02 parts of hydroquinone to 70 parts of this polyester, the mixture was dissolved in 30 parts of styrene monomer to obtain a liquid unsaturated polyester resin. This is called resin (A). (2) 444 g of phthalic anhydride, 686 g of maleic anhydride, and 837 g of propylene glycol under a nitrogen stream;
React at 200℃ for about 9 hours in a conventional manner, and the acid value
25 unsaturated polyesters were obtained. 0.02 part of hydroquinone was added to 65 parts of this polyester and then dissolved in 35 parts of styrene monomer to obtain a liquid unsaturated polyester resin. This is called resin (B). Production example of vinyl ester resin (3) Epicoat 827 manufactured by Ciel (Epoxy equivalent/
187) 561 g, 258 g of methacrylic acid, 0.25 g of hydroquinone as a polymerization inhibitor, 2.2 g of triethylamine as an esterification catalyst, and 384 g of styrene monomer as a polymerizable monomer were reacted at 120°C for 5 hours in a conventional manner to obtain an acid value of 8. A vinyl ester resin was obtained. This is called resin (C). Production example of thermoplastic resin (4) 1660g of isophthalic acid and propylene glycol
837 g was reacted in a conventional manner at 200°C under a nitrogen stream for about 17 hours to obtain a saturated polyester having an acid value of 35.6. After adding 0.02 parts of hydroquinone to 70 parts of this polyester, it was dissolved in 30 parts of styrene monomer to obtain a liquid saturated polyester. This is called resin (D). (5) Polystyrene (Dialex, HF-55,
(manufactured by Mitsubishi Monsanto) 40 parts as styrene monomer
Dissolved in 60 parts. This is called resin (E). Examples 1 to 5, Comparative Examples 1 to 3 Using the unsaturated polyester resins (A) and (B), vinyl ester resin (C), and thermoplastic resins (D) and (E) produced in the above examples, respectively A resin composition as shown in Table 1 was prepared. Resin composition obtained
After kneading 140 g with 60 g of glass chopped strands, a sheet with a thickness of about 2 mm was formed. Then,
After covering both sides of this sheet with polyethylene film, it was stored in a glass container at 40°C for 3 days. The obtained molding resin composition was examined for phase separation of the resin and for film peeling. Further, after appropriately cutting the molding resin composition, it was cured and molded using a disc-shaped mold at 50 kg/cm ² and 140°C for 5 minutes to create a disc-shaped molded product with a diameter of 40 mm and a thickness of 3 mm. However, the coloring property (presence or absence of color unevenness), shrinkage rate,
Paintability was investigated. These results are shown in Table-2.

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Claims (1)

[Claims] 1 Unsaturated polyester and/or vinyl ester resin, 20 to 120 parts by weight of polymerizable monomer per 100 parts by weight of the resin, 1 to 40 parts by weight per 100 parts by weight of the total amount of the resin and polymerizable monomer 100 parts by weight of a thermoplastic resin that is compatible with the monomer, and appropriate amounts of fillers, curing catalysts, colorants, mold release agents, thickeners, etc. added as necessary. 1. A molding resin composition having excellent phase separation prevention properties, comprising 0.01 to 20 parts by weight of a potassium titanate salt or a hydrate thereof.