JP2010202812A - Diallyl phthalate crosslinked low shrinkage unsaturated polyester resin composition for molding and molded article of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low shrinkage unsaturated polyester resin composition for molding without releasing odor from the molded article during production and heat molding/curing of the material for molding and when the molded article is used (at ambient temperature or at use temperature), and generating no VOCs (volatile organic compounds); and to provide a molded article using the same. <P>SOLUTION: Using an unsaturated polyester resin having a higher molar ratio of an unsaturated dibasic acid than that of a saturated dibasic acid, and using a diallyl phthalate as a polymerizable monomer and a styrene copolymer having a weight-average molecular weight of 50,000-500,000 as a shrinkage reducing agent, a low shrinkage unsaturated polyester resin composition for molding and a molded article thereof are obtained, which exhibit low shrinkage corresponding to that of the conventional styrenic BMC or SMC, and generate no VOCs (volatile organic compounds) nor specified substances having bad odor. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a low-shrinkable unsaturated polyester resin molding material composition and a molded article thereof. More specifically, the present invention relates to a low-shrinkable unsaturated polyester resin molding material that has no odor during the production of the molding material composition and during heating and pressure curing, and that does not generate VOC (volatile organic compounds) or specific malodorous substances. Low-shrinkable unsaturated polyester that is a composition and does not generate odors from molded articles that have been heat-pressed and cured at room temperature or at ambient temperatures higher than room temperature, and that does not generate VOC (volatile organic compounds) or specific malodorous substances. The present invention relates to a resin molding material composition and a molded product thereof.

  Conventionally, low-shrinkable unsaturated polyester resin molding materials are unsaturated polyester resin diluted in vinyl monomer, low-shrinkage agent as thermoplastic polymer, organic peroxide as curing agent, polymerization inhibitor, filling It is a resin composition in which glass fibers and the like are dispersed and mixed in a resin paste containing a material, a thickener, a release agent, a colorant and the like. A molding material obtained by semi-solidifying the resin composition into a lump is referred to as a bulk molding compound (hereinafter abbreviated as “BMC”) (lump molding material), and a molding material in the form of a sheet is referred to as a sheet molding compound (hereinafter “ (Abbreviated as “SMC”) (sheet-shaped molding material).

  These molding materials are compression molding (compression molding) method, transfer molding (transfer molding) method, injection molding (injection molding) method, so-called molding compound method such as injection compression molding (injection compression molding) method. It is molded into fiber reinforced plastic molded products (hereinafter abbreviated as FRP) by various molding methods, and is used for housing equipment (bathtubs, bathroom units, etc.), automobile / vehicle parts, industrial parts (electrical / electronic parts), etc. Widely used.

Many of these low-shrinkable unsaturated polyester resin molding materials use styrene as the vinyl-based monomer. It is known that styrene diffuses and evaporates and odor is generated in an environment where FRP which is a molded product thereof is used.
In recent years, environmental pollution and adverse effects on the human body have been a problem, and styrene has been subject to regulation as a VOC (volatile organic compound) and as a specific malodorous substance in the Odor Control Law. Regulations and regulations by local government regulations have begun.

  In order to comply with these voluntary regulations and regulations according to local regulations, 1) Use closed equipment and ventilate exhaust and air collection equipment in the manufacturing process and molding process of BMC and SMC molding materials. Method to mitigate environmental pollution and adverse effects on human body by methods 2) Post-curing FRP, which is the molded product, at a temperature higher than the temperature used in advance, forcibly stripping styrene and remaining in the cured FRP 3) As a curing agent for radical polymerization type thermosetting resin disclosed in JP 2007-146125 A, 0.1 to 5 parts by mass of a t-alkyl peroxyalkylate is disclosed. Although there is a method using a blended molding material, an effective method for not releasing styrene has not yet been found.

JP 2007-146125 A (pages 1 to 4)

  The present invention is a low-shrinkable unsaturated polyester having no odor from molded products at the time of production, heating and pressure curing, normal temperature or use atmosphere temperature, and no generation of VOC (volatile organic compound) or specific malodorous substances. It is providing the resin molding material composition and the molded article obtained by shape | molding using the molding material.

As a result of intensive studies to solve these problems, the present inventors used an unsaturated polyester resin in which the molar ratio of unsaturated dibasic acid was higher than the molar ratio of saturated dibasic acid, By using diallyl phthalate as the body and using a styrene copolymer having a weight average molecular weight of 50,000 to 500,000 as the low shrinkage agent, the low shrinkage is comparable to conventional styrene BMC and SMC. The present inventors have found that a low-shrinkable unsaturated polyester resin molding material composition and a molded article that exhibits shrinkage and does not generate VOC (volatile organic compounds) or specific malodorous substances can be obtained, thereby completing the present invention.
Furthermore, by using an organic peroxide having a low half-life temperature in combination with a conventionally used high-temperature decomposition organic peroxide as a curing agent, the molding conditions of conventional styrene-based BMC and SMC can be reduced. The present inventors have found that a low-shrinkable unsaturated polyester resin molding material composition and a molded product that can be molded under the same molding conditions without change are obtained, and have completed the present invention.

  That is, the low shrinkable unsaturated polyester resin molding material composition of the first invention in the present invention is an unsaturated polyester resin comprising an unsaturated polyester resin, a polymerizable monomer, a low shrinkage agent and a curing agent. In the molding material composition, the polymerizable monomer is diallyl phthalate, and the low shrinkage agent contains a styrene copolymer having a weight average molecular weight of 50,000 to 500,000. is there.

  The low-shrinkable unsaturated polyester resin molding material composition of the second invention is the composition of the first invention, wherein the molar ratio of unsaturated polyester resin polybasic acid is unsaturated polybasic acid: saturated polybasic acid = 100: 0. It is characterized by comprising a range of ˜50: 50.

The low-shrinkage unsaturated polyester resin molding material composition of the third invention is characterized in that, in the first invention, the low-shrinkage agent contains a copolymer of a styrene monomer and an acrylic acid monomer. It is what.

The low-shrinkage unsaturated polyester resin molding material composition of the fourth invention is the first to third inventions, wherein the low-shrinkage agent comprises 50-80% by weight of styrene monomer and 50-20% by weight of acrylic acid monomer. It is characterized by comprising a copolymer of

The low-shrinkage unsaturated polyester resin molding material composition of the fifth invention is characterized in that, in the first to fourth inventions, the low-shrinkage agent comprises a copolymer of styrene and butyl acrylate. is there.

  The low-shrinkable unsaturated polyester resin molding material composition of the sixth invention is the first to fifth inventions, wherein the curing agent is selected from organic peroxides having a 1-minute half-life temperature of 160 ° C. or higher. It contains two or more organic peroxides consisting of at least one or more and at least one selected from organic peroxides having a half-life temperature of 1 minute or more and less than 160 ° C. to less than 160 ° C. It is characterized by this.

  The low shrinkable unsaturated polyester resin molding material composition of the seventh invention is the composition of the first to sixth inventions, wherein (A) the unsaturated polyester resin is 40 to 60 parts by weight as a solid ester resin, It contains 40 to 60 parts by weight of a monomer and (C) 5 to 20 parts by weight of a low shrinkage agent as a resin component.

  The low-shrinkage unsaturated polyester resin molding material composition of the eighth invention is the first to seventh inventions, wherein (A) an unsaturated polyester resin, (B) a polymerizable monomer, (C) a low-shrinking agent. Resin component {(A) + (B) + (C)} consisting of 100 parts by weight of curing agent 0.5-5 parts by weight, thickener 0.1-1 part by weight, release agent 1-5 It contains 0.005 to 0.1 parts by weight of a polymerization inhibitor, 20 to 100 parts by weight of a reinforcing material, 0 to 300 parts by weight of a filler, and 0 to 20 parts by weight of other additives. Is.

  Furthermore, the molded article of the ninth invention is characterized by molding the low shrinkable unsaturated polyester resin molding material composition of any of the first to eighth inventions.

The diallyl phthalate crosslinked low-shrinkable unsaturated polyester resin molding material composition of the present invention and the molded product thereof can exhibit the following effects.
In the low shrinkable unsaturated polyester resin molding material composition of the present invention, the polymerizable monomer is diallyl phthalate, and the low shrinkage agent is a styrene copolymer having a weight average molecular weight of 50,000 to 500,000. Therefore, when diallyl phthalate is used compared to the conventional case where styrene is used as the polymerizable monomer, styrene has a strong odor, as VOC (volatile organic compound), and also prevents bad odor. While diallyl phthalate has no odor and is not a VOC (volatile organic compound) or a specific malodorous substance in the Odor Prevention Law, it is a VOC (volatile) Odorous organic compounds) and specific malodorous substances in the Odor Control Law can be cleared. Moreover, it can be set as the molding material and molded article which do not generate | occur | produce odor and have a bad influence on a human body in the manufacture environment of a molding material, a molding process environment, and use environment.

Further, as a low shrinkage agent used in conventional bulk molding materials (BMC) and sheet-like molding materials (SMC), polystyrene (PS), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), polyethylene (PE ), Polypropylene (PP), poly-ε-caprolactam, saturated polyester (PET, PBT), polyvinyl chloride (PVC), styrene-butadiene-styrene block copolymer (SBS) and other thermoplastic resins, polybutadiene (PB) Rubbers such as styrene butadiene rubber (SBR) and nitrile rubber (NBR), thermoplastic elastomers, and the like are used.
These low shrinkage agents are easily dissolved or swelled and softened in styrene, but are not easily dissolved in diallyl phthalate and swell and separate in a lump, or do not dissolve or swell at all. For this reason, diallyl phthalate cross-linked unsaturated polyester resin molding material compositions using these low shrinkage agents are not only able to obtain low shrinkage, but also partially have low shrinkage agents in the heating mold during molding. As a result, it sticks and soils the mold, and at the same time, the appearance of the molded product is impaired.

  However, the low shrinkage agent in the present invention is a styrene copolymer having a weight average molecular weight of 50,000 to 500,000, and is a copolymer of a styrene monomer and an acrylic acid monomer or a styrene monomer. Since it is a copolymer with vinyl acetate monomer, it not only easily dissolves in diallyl phthalate, but also has low shrinkage, does not stain the mold, and the appearance of the molded product is glossy and smooth. It is possible to obtain a good molded product having both of the above.

  In the low shrinkable unsaturated polyester resin molding material composition of a preferred embodiment, the molar ratio of the unsaturated polyester resin polybasic acid is in the range of unsaturated polybasic acid: saturated polybasic acid = 100: 0 to 50:50, Due to the high molar ratio of unsaturated polybasic acid and the increased number of crosslinking points with diallyl phthalate, compared to conventional styrene molding materials, heat molding of diallyl phthalate molding materials using diallyl phthalate as a polymerizable monomer The problem of slow curing in the mold can be solved.

  Furthermore, in the low-shrinkable unsaturated polyester resin molding material composition of a preferred embodiment, as a curing agent, an organic peroxide having a half-life temperature of 1 minute for 160 minutes or more and a half-life temperature of 1 minute for 130 minutes or more are used. By using an organic peroxide having a temperature lower than 160 ° C., the organic peroxide having a relatively low decomposition temperature is decomposed first, and then the decomposition of the high temperature decomposition organic peroxide is promoted to generate radicals. Compared to conventional styrenic molding materials, diallyl phthalate molding materials can solve the problem that the temperature of the thermoforming mold has to be increased, and if the curing time is not prolonged, the curing is slow. . In addition, since the curing in the molding die is accelerated, the curing shrinkage of the molded product is manifested in the early stage of the curing process, so that the disadvantage that the peelability of the burr from the molding die is poor can be solved.

  Moreover, the flash point of the diallyl phthalate crosslinked low-shrinkable unsaturated polyester resin molding material composition of the present invention is remarkably improved. Whereas the flash point of the conventional styrene-based molding material having a flash point of styrene derived from 32 ° C. is around 36 ° C., the flash point of diallyl phthalate is derived from 163 ° C. The flash point of the combustible unsaturated polyester resin molding material composition is 110 ° C or higher, the upper limit of the flash point measuring machine, and it is completely clear that less than 40 ° C of flammable solids in the second class flammable solids stipulated by the Fire Service Act. To do. As a result, the manufacturing process of molding materials such as BMC and SMC, and the use of explosion-proof equipment such as various types of equipment, buildings, and storage warehouses in the molding process are eliminated, and the amount of molding materials stored is not regulated. There is a great effect.

  Furthermore, the pot life (usable time) of the conventional styrenic molding material is short, and in the accelerated test by storage at 50 ° C., there is a disadvantage that the fluidity is lost in less than one week and the molding becomes impossible. The diallyl phthalate crosslinked low-shrinkable unsaturated polyester resin molding material composition has a long pot life (usable time), and in accelerated tests by storage at 50 ° C, there is little change over time in fluidity for more than 1 month, and it is long at room temperature. Even if it is stored for a period of time, fluidity of a certain level or more can be maintained and appropriate molding can be performed, so that not only refrigeration equipment is unnecessary, but also a stable molding process can be maintained for a long time.

  In addition, the diallyl phthalate crosslinked low-shrinkable unsaturated polyester resin molding material composition of the present invention has a viscosity of the molding material itself of about 3 times higher than that of conventional styrene molding materials (especially BMC and SMC). Therefore, it is possible not only to shorten or eliminate the heating and aging period for improving the handling property that is usually performed, but also to prevent filling of the molding mold with air, so that the mold mold can be filled. As a result, it is possible to eliminate filling defects (spores, voids, etc.), which are peculiar defects occurring in styrenic molding materials, reduce the defective rate, and obtain good molded products.

Next, a preferred embodiment of the present invention will be described in detail.
In the present invention, the unsaturated polyester resin preferably has a polybasic acid molar ratio in the range of unsaturated polybasic acid: saturated polybasic acid = 100: 0 to 50:50, More preferably, the molar ratio of the polybasic acid of the unsaturated polyester resin is in the range of unsaturated polybasic acid: saturated polybasic acid = 100: 0 to 60:40, particularly 100: 0 to 80:20. By selecting an unsaturated polyester resin having this molar ratio, the reactivity of the unsaturated polyester resin solid ester resin and diallyl phthalate as the polymerizable monomer is improved, and the gel time and curing time in the high-temperature curing test are further improved. The maximum exothermic temperature generated during polymerization can be shortened to the same maximum exothermic temperature as when styrene is used as the polymerizable monomer.

The unsaturated polyester resin in the present invention is obtained by synthesis by a known method, for example, by an addition reaction between a polybasic acid containing an unsaturated polybasic acid and a polyhydric alcohol, or a dehydration condensation reaction.
For example, the trade name “8524” manufactured by Nippon Iupika Co., Ltd. is a medium-reactive resin having a unsaturated polybasic acid: saturated polybasic acid molar ratio of ≧ 50: ≦ 50, and is a solid terephthalic acid-based unsaturated polyester resin. It is an ester resin and has a number average molecular weight of about 3890. In addition, the product name “7365” manufactured by Nippon Iupika Co., Ltd. is a highly reactive resin having an unsaturated polybasic acid: saturated polybasic acid molar ratio of 80-100: 20-0, and is a solid ester resin / diallyl phthalate. An unsaturated polyester resin dissolved in 55/45% by weight diallyl phthalate, the number average molecular weight of the solid ester portion is about 2890. “7360” manufactured by the same company is a highly reactive resin having an unsaturated polybasic acid: saturated polybasic acid molar ratio of 80 to 100: 20 to 0 and a solid ester / styrene ratio of 55/45. Unsaturated polyester resin dissolved in weight percent styrene, the number average molecular weight of the solid ester portion is also about 2890.

The unsaturated polybasic acid used in the unsaturated polyester resin of the present invention is a compound (preferably having 2 to 20 carbon atoms) having at least one carbon-carbon double bond and at least two carboxylic acid groups. preferable. Examples of the unsaturated polybasic acid include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, chloromaleic acid, or dialkyl thereof (preferably alkyl having 1 to 20 carbon atoms). ) Esters can be mentioned. These unsaturated polybasic acids can be used alone or in combination of two or more. Moreover, it is preferable that a saturated polybasic acid is a compound (preferably C2-C10) which does not have a carbon-carbon double bond and has at least two carboxylic acid groups. Examples of saturated polybasic acids include, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, het acid, hexahydrophthalic anhydride, adipic acid, sebacic acid, azelaic acid, etc. Can do. These saturated polybasic acids can be used alone or in combination of two or more.
As the polybasic acids, unsaturated polybasic acids may be used alone or in combination with saturated polybasic acids.

  Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 , 2-pentanediol, 1,6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerol monoallyl ether, hydrogenated bisphenol A, 2,2-bis Diols such as (4-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane, triols such as trimethylolpropane, tetraols such as pentaerythritol, etc. It can gel. These polyhydric alcohols can be used alone or in combination of two or more.

  The polymerizable monomer used in the present invention is a monomer having two or more radically polymerizable unsaturated groups in one molecule, and contains a so-called crosslinking agent as an essential component. Diallyl phthalate as the polymerizable monomer is a monomer that is liquid at room temperature, and any of diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate can be used. The said polymerizable monomer may be used independently and may be used in combination of 2 or more types.

Generally, the low shrinkage agent is a component for suppressing the curing shrinkage of the thermosetting resin, increasing the dimensional accuracy of the cured product (FRP), and improving the surface smoothness and gloss of the molded product. is there.
The low shrinkage agent used in the present invention is a styrene copolymer having a weight average molecular weight of 50,000 to 500,000. The styrene copolymer is preferably a copolymer of a styrene monomer and an acrylic acid monomer or vinyl acetate monomer. The styrene copolymer is preferably a non-crosslinked styrene copolymer.

Examples of the styrenic monomer include styrene derivatives such as α-methylstyrene, vinyltoluene, and pt-butylstyrene in addition to styrene.
On the other hand, examples of the acrylic monomer include acrylic acid and derivatives of acrylic acid, particularly acrylic esters. The acrylic ester may be an ester of acrylic acid and an alcohol having 1 to 20 carbon atoms (particularly 1 to 10) (for example, a monohydric alcohol or a polyhydric (for example, 2 to 4) alcohol). Examples of acrylic acid derivatives are, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, acrylic Undecyl acid, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, acrylic Acid methoxydipropylene glycol, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraacrylate Lenglycol, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, N-vinyl-2-pyrrolidone acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate , Hydroxybutyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, acrylonitrile, acrylamide, N-methylol acrylamide, diacetonacrylamide and the like.
Among these, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable from the viewpoint of adjusting the glass transition temperature of the polymer as a low shrinkage agent. The above-mentioned low shrinkage agent of a copolymer of styrene monomer and acrylic acid monomer (particularly non-crosslinked styrene copolymer) may be used alone or in combination of two or more.
A vinyl acetate monomer may be used in place of or in addition to the acrylic acid monomer.

  The low shrinkage agent used in the present invention is preferably a copolymer of 50 to 80% by weight of styrene monomer and 50 to 20% by weight of acrylic acid monomer or vinyl acetate monomer. When the styrene monomer is 50 to 80% by weight, the solubility in diallyl phthalate is high, and the mechanical strength given to the cured molded article by the low shrinkage agent is high. A more preferable use ratio of the styrene monomer is 65 to 75% by weight.

Moreover, the weight average molecular weight of the low shrinkage agent used in the present invention is preferably 50,000 to 500,000, more preferably 80,000 to 300,000.
When the weight average molecular weight of the low shrinkage agent is smaller than 50,000, the solubility of the low shrinkage agent in diallyl phthalate is very easy and good, but diallyl phthalate crosslinked low shrinkage unsaturated polyester resin molding When the BMC is kneaded, the viscosity of the material composition is low, and the adhesion to the equipment is severe. When the SMC sheet is prepared, the resin component is easily separated, the sheet is very soft and the handling property is poor. In addition, it is easy to stick to sticking in the measurement at the time of molding, and the workability is extremely poor.
On the other hand, when the weight-average molecular weight of the low shrinkage agent is larger than 500,000, the solubility of the polymerizable monomer in diallyl phthalate is slow and the viscosity of the melt becomes very high, and as a result, the resin molding composition As a result of the extremely high viscosity, the kneaded material does not mix well when kneading BMC, and the viscosity of the resin matrix becomes high when creating SMC sheets, so the resin matrix can be evenly applied on the film. Or the fall from the container is very slow, resulting in reduced production efficiency. Furthermore, the handling workability is extremely poor in weighing or the like during molding.
Moreover, it is preferable that the glass transition temperature of the low shrinkage agent used for this invention has 30-100 degreeC. When the glass transition temperature is 30 to 100 ° C., heat resistance and solubility are good. A more preferable glass transition temperature is 55 to 75 ° C.

The production method of the low shrinkage agent used in the present invention is not particularly limited and can be produced by a known method such as bulk polymerization or suspension polymerization.
For example, trade names “CS-40” and “CS-20” manufactured by Sekisui Plastics Co., Ltd. have a styrene: butyl acrylate weight percentage ratio of 75:25, and their respective weight average molecular weights are 56,000 and 1 , 000,000. The invention further includes a styrene random copolymer made by the same company and having a weight percent ratio of styrene: butyl acrylate of 75:25 and having a weight average molecular weight of 110,000, 190,000 and 260,000. Was used. The trade name “Modiper S501” manufactured by NOF Corporation is a styrene block copolymer having a styrene: vinyl acetate monomer weight% ratio of 50:50 and a weight average molecular weight of 213,000.

As the curing agent used in the present invention, an organic peroxide is used, and a high-temperature decomposition type organic peroxide having a half-life temperature of 1 minute or more of 160 ° C. and a half-life temperature of 1 minute of 130 ° C. to 160 ° C. Molding process under molding conditions equivalent to styrene-based BMC and SMC, even if it is a diallyl phthalate cross-linked low-shrinkable unsaturated polyester resin molding material composition by using it in combination with a mesothermal decomposition type organic peroxide below can do.
As an organic peroxide having a half-life temperature of 160 ° C. or more for 1 minute, dicumyl peroxide, for example, “Park Mill D” manufactured by NOF Corporation, t-butyl peroxybenzoate, for example, manufactured by NOF Corporation More preferably, t-butyl peroxybenzoate effectively acts on the curing reaction of the diallyl phthalate crosslinked low-shrinkable unsaturated polyester resin molding material composition.

  The organic peroxide having a 1 minute half-life temperature of 130 ° C. to less than 160 ° C. combined with an organic peroxide having a 1 minute half-life temperature of 160 ° C. or higher is preferably 1,1 bis (t-hexylper Oxy) 3,3,5 trimethylcyclohexane, for example “Perhexa TMH” manufactured by NOF Corporation, 1,1 di (t-hexylperoxy) cyclohexane, for example “Perhexa HC” manufactured by NOF Corporation, t-butylperoxy Organic peroxides based on isopropyl monocarbonate, such as “Percure HI” manufactured by NOF Corporation, 1,6-bis (t-butylperoxycarbonyloxy) hexane, such as “Kayalen 6” manufactured by Kayaku Akzo Corporation 70 ", benzoyl peroxide, such as" NIPER BW "manufactured by NOF Corporation, and more preferably 1,1 bis (t-hex Peroxy) 3,3,5 trimethylcyclohexane, for example, “Perhexa TMH” manufactured by NOF Corporation or 1,6 bis (t-butylperoxycarbonyloxy) hexane, for example, “Kayalen 6-70” manufactured by Kayaku Akzo More effectively acts on the curing reaction of the diallyl phthalate crosslinked low shrinkable unsaturated polyester resin molding material composition.

The ratio of use of the organic peroxide having a half-life temperature of 160 ° C. or higher for one minute and the organic peroxide having a half-life temperature of 130 ° C. to less than 160 ° C. for 1 minute to be combined is preferably 65 to 85/35. -15% by weight, more preferably 70-80 / 30-20% by weight.
When the use ratio of the organic peroxide having a half-life temperature of 1 minute or more is from 65% by weight to 85% by weight, the curing rate is appropriate, and the diallyl phthalate crosslinked low-shrinkable unsaturated polyester resin molding material The pot life of the composition is appropriate, the molding processability is stable, the molding curing time is suitable, and the molding efficiency is good. Furthermore, burr peeling is good and workability is high.

The resin component used for the low shrinkable unsaturated polyester resin molding material composition of the present invention is (A) 40 to 60 parts by weight as a solid ester portion of the unsaturated polyester resin, and (B) a polymerizable monomer 40 to 60. It is preferably composed of 5 parts by weight of (C) a low shrinkage agent.
The ratio of (A), (B), and (C) can be changed depending on the desired application and is not particularly limited. However, when the solid ester portion of the unsaturated polyester resin is 40 to 60 parts by weight, the molded product The strength properties are high and low shrinkage is obtained.
When the polymerizable monomer is 40 to 60 parts by weight, the viscosity of the resin component is low and the molding material is sufficiently kneaded and mixed, so that the workability is good and a uniform molded product is obtained. Further, when the amount of the low shrinkage agent is 5 to 20 parts by weight, a low shrinkage rate is obtained, and the physical properties of the molded product are good.

  The low shrinkable unsaturated polyester resin molding material composition of the present invention comprises a resin component (A) comprising (A) a solid ester portion of an unsaturated polyester resin, (B) a polymerizable monomer, and (C) a low shrinkage agent. ) + (B) + (C), 100 parts by weight of curing agent 0.5-5 parts by weight, thickener 0.05-1 part by weight, release agent 1-5 parts by weight, polymerization inhibitor 0 0.005 to 0.1 parts by weight, reinforcing material 20 to 100 parts by weight, filler 0 to 300 parts by weight, and other additives 0 to 20 parts by weight, for example 0.1 to 10 parts by weight. It is a thing.

An organic peroxide is used as the curing agent, and the blending amount thereof is an organic peroxide having a half-life temperature of 160 ° C. or higher for 1 minute and an organic material having a half-life temperature of 1 minute of 130 ° C. to less than 160 ° C. Resin component (A) + (B) consisting of (A) solid ester portion of unsaturated polyester resin, (B) polymerizable monomer, (C) low shrinkage agent 0.5-5 weight part is preferable with respect to 100 weight part of + (C), More preferably, it is 1-3 weight part.
When the total amount of the curing agent is 0.5 to 5 parts by weight, the curing rate of the low-shrinkable unsaturated polyester resin molding material composition of the present invention is appropriate, and an instantaneous curing reaction does not occur. The demolding of the molded product is good and the peelability of the burrs attached to the mold is also good.

The thickening agent is for increasing the viscosity of the molding material composition and facilitating handling, and for example, an oxide of a divalent metal or a hydroxide thereof is used. It is apparently added to the end group of the resin to increase the molecular weight of the resin.
Examples of the thickener include alkaline earth metal oxides or hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, potassium oxide, potassium hydroxide, and zinc oxide. From the viewpoint of thickening, for example, “Kyowa Mag 150” manufactured by Kyowa Chemical Industry Co., Ltd. is preferably used. In some cases, an isocyanate-based thickener or a swellable thermoplastic resin powder can be used.
The blending amount of the thickener is (A) a resin component (A) + (B) + (A) comprising a solid ester portion of an unsaturated polyester resin, (B) a polymerizable monomer, and (C) a low shrinkage agent. 0.05 to 1 part by weight is preferable with respect to 100 parts by weight of C), more preferably 0.1 to 0.5 part by weight. When the blending amount of the thickener is 0.05 to 1 part by weight, a sufficient thickening effect of the low shrinkable unsaturated polyester resin molding material composition of the present invention can be obtained, and the handling property of the molding material composition is improved. It is good and an appropriate material viscosity can be obtained.

The mold release agent is a component for facilitating release of the molded product from the mold, and melts at a heated mold temperature and oozes out at the interface between the resin molded product and the mold, and the molded product and the mold. It separates the mold.
The mold release agent is, for example, kneaded into the BMC kneaded material or previously mixed and dispersed in the SMC resin liquid when the low shrinkable unsaturated polyester resin molding material composition of the present invention is prepared. Examples include aliphatic organic acids such as stearic acid, zinc stearate, calcium stearate, metal salts of aliphatic organic acids such as aluminum stearate and magnesium stearate, waxes, silicones, and the like. You may use, and may use it in combination of 2 or more types.

These mold release agents are appropriately selected depending on molding conditions, particularly the mold temperature. When the mold temperature is 120 to 160 ° C., zinc stearate such as “SZ2000” manufactured by Adeka Corporation is preferably used.
The blending amount is (A) a solid ester portion of an unsaturated polyester resin, (B) a polymerizable monomer, and (C) a resin component (A) + (B) + (C) composed of a low shrinkage agent. It is preferable to set it as 1-5 weight part with respect to 100 weight part. If the blending amount is within this range, the releasability is good, the appearance of the molded product is not impaired, and the strength properties are not affected.

  The polymerization inhibitor is used when the solid ester portion of the unsaturated polyester resin is heated and dissolved in the polymerizable monomer to suppress crosslinking between the solid ester portion of the unsaturated polyester resin and the polymerizable monomer. In order to allow the molding material to flow in the mold without gelation as much as possible at the molding temperature of the heating mold.

Examples of such a polymerization inhibitor include hydroquinones such as hydroquinone, methylhydroquinone, pt-butylcatechol, or mono-t-butylhydroquinone, hydroquinone monomethyl ether, or di-t-butyl-p-cresol. Quinones such as benzoquinone, p-benzoquinone, naphthoquinone, or p-toluquinone, di-t-butylhydroxytoluene, 2,6-di-t-butyl-4-methylphenol, copper naphthenate Examples thereof include copper salts and phenothiazine.
These are usually 100 weights of resin component (A) + (B) + (C) comprising (A) solid ester portion of unsaturated polyester resin, (B) polymerizable monomer, and (C) low shrinkage agent. 0.005 to 0.1 parts by weight (50 to 1,000 ppm) is blended with respect to parts.

The reinforcing material is a component for improving the mechanical properties of the molded product, suppressing the occurrence of cracks and the like in the molded product, and improving the thermal characteristics.
The reinforcing material is not particularly limited as long as it does not impair various properties such as strength performance and appearance. For example, inorganic fiber such as glass fiber, ceramic fiber and whisker, amide, and aramid And organic fibers such as vinylon, polyester and phenol, carbon fibers, metal fibers, and natural fibers such as pulp and cotton.

  These reinforcing materials may be used singly or in combination of two or more. However, in consideration of performance of the obtained molded product, economy, etc., glass fiber, organic fiber are preferable. Carbon fiber, natural fiber, etc. are selected.

  In particular, in the case of glass fiber, specifically, milled glass fiber, chopped strand glass fiber and the like can be mentioned. These glass fiber lengths are appropriately selected from a short one of about 10 μm to a long one of about 2 inches, and 2 alone. It can be used even if more than one species is used in combination. Moreover, it can also be used while cutting the glass roving.

  For the low shrinkable unsaturated polyester resin molding material composition of the present invention, chopped strands cut to 3 to 25 mm (1/8 to 1 inch) in glass fiber length or rovings wound with glass fiber can be used. The surface of the monofilament is 6 to 13 μm, surface-treated with a silane coupling agent, and 200 to 800 monofilaments are focused with a binder resin such as a polyester resin, an epoxy resin, a urethane resin, or a vinyl acetate resin. Can be used effectively.

For example, “CS03MB498A” manufactured by Asahi Fiber Glass Co., Ltd. and “ECS03B-157” manufactured by Nippon Electric Glass Co., Ltd. are suitable.
When the fiber reinforcement is used, the blending amount is (A) a resin component (A) + (B ) +100 parts by weight of (C), which is 20 to 100 parts by weight, and an appropriate blending amount is determined by strength properties and fluidity required for the molding material composition.

The filler is a component for improving the flowability of the molding material, an extender, improving the rigidity of the cured product, reducing shrinkage, and improving surface smoothness and gloss.
The filler is not particularly limited as long as the properties such as strength performance and appearance are not impaired. For example, calcium carbonate, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate. , Calcium sulfate, aluminum oxide, kaolin, clay, talc, alumina powder, quartz sand, quartzite powder, silica powder, glass powder, shirasu balloon, glass balloon, glass beads, mica, mica powder, cryogenic stone, marble powder, crushed stone, etc. Examples thereof include organic fillers obtained by pulverizing inorganic fillers, synthetic fibers, natural fibers and the like.
The inorganic filler can be used from a surface treated with a surface treating agent such as a silane coupling agent to an untreated product. The average particle size of these fillers is preferably 0.1 to 100 μm, more preferably 1 to 50 μm in average particle size, which gives the appearance smoothness of the molded product and good handleability. These fillers may be used alone or in combination of two or more.

Among them, calcium carbonate and aluminum hydroxide are preferably used. Calcium carbonate, for example, “Whiteon B” manufactured by Shiraishi Calcium Co., “Super S” manufactured by Maruo Calcium Co., Ltd. is advantageous in terms of economy. For example, “Heidilite H-32” manufactured by Showa Denko Co., Ltd. and “Light Fine Aluminum Hydroxide B-153” manufactured by Nippon Light Metal Co., Ltd. are used to impart flame retardancy or to give a translucent feeling to molded products.
When the filler is used, the compounding amount is (A) a resin component (A) + (B) comprising a solid ester portion of an unsaturated polyester resin, (B) a polymerizable monomer, and (C) a low shrinkage agent. It is 0-300 weight part with respect to 100 weight part of + (C), Preferably, it is 150-200 weight part.

In addition, various additives other than the above can be used in the low-shrinkable unsaturated polyester resin molding material composition of the present invention as long as the performance is not impaired.
Such additives include inorganic pigments such as titanium oxide, carbon black and petals, various organic pigments, coloring agents such as dyes, anti-separation agents or compatibilizers for low shrinkage agents, thinning agents, viscosity reducing agents, etc. As the addition amount, (A) a solid ester portion of an unsaturated polyester resin, (B) a polymerizable monomer, and (C) a resin component (A) + (B) + ( It is 0-20 weight part with respect to 100 weight part of C), for example, 0.1-10 weight part.
These additives can be used alone or in combination of two or more as required.

  The bulky molding material BMC (hereinafter referred to as “diallyl phthalate-based BMC”), which is one type of the low-shrinkable unsaturated polyester resin molding material composition of the present invention, is the resin component, filler, and reinforcing material. It is a block molding material obtained by blending and the like. The diallyl phthalate-based BMC can be obtained using a mixing apparatus similar to the conventional method for producing a styrene-based BMC, and the order of mixing and the mixing method are not particularly limited. A diallyl phthalate-based BMC can be obtained according to the intended use by appropriately changing the order of charging various raw materials and the shape and speed of the stirring / kneading blade. As an apparatus for uniformly mixing and kneading, apparatuses such as a stirrer, a kneader, a mixer, a roll mill, and a screw extruder can be used.

As a method for preparing a resin component, for example, Nippon Iupika Co., Ltd., commercially available as an unsaturated polyester resin, which is a terephthalic acid solid ester resin having an unsaturated polybasic acid: saturated polybasic acid molar ratio of ≧ 50: ≦ 50, is first used. Using “8524” manufactured by Daiso, dissolved in diallyl phthalate (registered trademark of “Daiso Dup Monomer” manufactured by Daiso) or styrene (manufactured by Kishida Chemical Co., Ltd.) so that the solid ester resin / polymerizable monomer is 55/45 wt%. did.
A specified amount of polymerizable monomer is poured into a dissolution tank equipped with a reflux condenser, and when the polymerizable monomer is diallyl phthalate, 80 to 90 ° C. warm water is circulated through the jacket of the dissolution tank, and the polymerizable monomer If the body is styrene, circulate 50-60 ° C warm water through the jacket of the dissolution tank, rotate the high-speed stirring blade at 150-250 rpm, and disperse and dissolve the polymerization inhibitor while stirring the polymerizable monomer. Then, the specified amount of solid ester resin “8524” was gradually added and dissolved.

Furthermore, the unsaturated polyester resin used for the low shrinkable unsaturated polyester resin molding material composition of the present invention is, for example, “7365” manufactured by Nippon Iupika Co., Ltd., wherein the molar ratio of unsaturated polybasic acid: saturated polybasic acid is 100. Is an unsaturated polyester resin having a solid ester / diallyl phthalate of 55/45% by weight within the range of 0-80: 20. This is an unsaturated polyester resin in which the molar ratio of unsaturated polybasic acid: saturated polybasic acid is in the range of 100: 0 to 80:20 and the solid ester / styrene is 55/45% by weight.
Since these unsaturated polyester resins “7365” and “7360” were already dissolved in the polymerizable monomer, they were used as they were without being dissolved in diallyl phthalate or styrene as the polymerizable monomer.

Next, as a method for dissolving the low shrinkage agent as the other resin component, for example, the low shrinkage agent is a random copolymer of styrene and butyl acrylate (non-crosslinked styrene copolymer) or styrene. A block copolymer with vinyl acetate was added to each of diallyl phthalate (registered trademark “Daisodap Monomer” manufactured by Daiso) and styrene (manufactured by Kishida Chemical Co., Ltd.). Dissolved to 8% by weight.
A specified amount of a polymerizable monomer is poured into a dissolution tank provided with a reflux condenser, and when the polymerizable monomer is diallyl phthalate, 80 to 90 ° C. warm water is circulated through the jacket of the dissolution tank, and the polymerizable monomer When the body is styrene, circulate hot water at 50-60 ° C through the jacket of the dissolution tank, rotate the high-speed stirring blade at 150-250 rpm, and stir the polymerizable monomer while adding the prescribed amount of the low shrinkage agent. Slowly charged and dissolved.

In addition, as a low shrinkage agent used for the low shrinkable unsaturated polyester resin molding material composition of the present invention, for example, a copolymer of styrene and butyl acrylate, and a weight% ratio of styrene: butyl acrylate is 75. A copolymer having a weight average molecular weight of 56,000 (“CS-40” manufactured by Sekisui Plastics Co., Ltd.), a weight average molecular weight of 110,000 (developed by the company 1), and a weight average molecular weight of 190,000 ( Company-developed product 2) and weight average molecular weight 260,000 (company-developed product 3).
Further, a block copolymer of styrene-vinyl acetate monomer (“Modiper S501” styrene / vinyl acetate = 50/50 wt% ratio manufactured by NOF Corporation) was also used as a low shrinkage agent.

Further, as a comparative example of the low shrinkage agent, for example, a copolymer of styrene and butyl acrylate, a copolymer having a weight percent ratio of styrene: butyl acrylate of 75:25, and a weight average molecular weight of 1, 000,000 (“CS-20” manufactured by Sekisui Plastics Co., Ltd.), polystyrene (“MS-200” manufactured by Sekisui Plastics Co., Ltd., weight average molecular weight 340,000 and “S-90” weight average molecular weight 57,000) And polyethylene powder (“Flowsen UF20S” manufactured by Sumitomo Seika Co., Ltd.) were selected.
In the same way, these shrinkage reductions are caused by 41.2 / 58 of the low shrinkage agent / polymerizable monomer in each of diallyl phthalate (registered trademark of “Daisodap Monomer” manufactured by Daiso) and styrene (manufactured by Kishida Chemical) It was dissolved to 8 wt%.
A specified amount of polymerizable monomer is poured into a dissolution tank equipped with a reflux condenser, and when the polymerizable monomer is diallyl phthalate, 80 to 90 ° C. warm water is circulated through the jacket of the dissolution tank, and the polymerizable monomer If the body is styrene, circulate 50-60 ° C warm water through the jacket of the dissolution tank, rotate the high-speed stirring blade at 150-250 rpm, and stir the polymerizable monomer, and adjust the prescribed amount of the low shrinkage agent. It was gradually added to dissolve, swell and disperse.

The diallyl phthalate-based BMC, which is one form of the low-shrinkable unsaturated polyester resin molding material composition of the present invention, can be produced by the following method in the same manner as the conventional styrene-based bulk molding material (BMC). .
Examples of the method of kneading the block molding material include, for example, a pressure kneader having a water-cooled tank and a double-armed Banbury blade, powders such as a thickener, a release agent, a filler, and other additives. Feed the raw materials, close the pressure lid and mix for 1-2 minutes. Next, the pressure lid is opened and a liquid component such as a resin component is added. Further, a curing agent is added, and the blade is kneaded for 5 to 10 minutes until it turns into a putty while rotating inward in different directions. Gradually throw in over 1 to 2 minutes, and after the prescribed amount is filled in, close the pressure lid and knead for 5 to 10 minutes until the glass fibers converge and disperse uniformly.
After the kneading is completed, the pressure lid is opened, the pressure kneader is turned over, the blade is rotated outwardly, and the mass molding material kneaded while rotating inwardly is taken out. Packaging.
If necessary, the block-shaped molding material taken out may be extruded into a rod shape having a circular or square cross section with a cone type twin screw extruder, cut at a desired weight, and packaged with the film.

The diallyl phthalate-based sheet-shaped molding material (SMC), which is one form of the low-shrinkable unsaturated polyester resin molding material composition of the present invention, is manufactured by the following method in the same manner as conventional styrene-based sheet-shaped molding materials can do.
As a method for producing a sheet-shaped molding material, for example, first, a resin liquid component such as an unsaturated polyester resin or a low shrinkage agent dissolved in a polymerizable monomer, a curing agent excluding a reinforcing material such as glass fiber, A resin matrix is prepared by uniformly mixing a viscosity agent, a release agent, a filler and other additives with a high viscosity stirrer. Next, this resin matrix is applied to the carrier film with a uniform thickness, a fiber reinforcement such as glass fiber is spread on the resin matrix, and the resin matrix is similarly applied to the other carrier film with a uniform thickness. Apply to the end and sandwich the fiber reinforcing material at the end, press impregnation and defoaming with the roll of the impregnation device, impregnate the fiber reinforcing material with the resin matrix and wind it up in a roll, or dedicated container Folded into packs and aged at room temperature to 50 ° C. for 1-7 days as needed.
Examples of the film used in the method for producing a sheet-shaped molding material include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyamide film, and a laminated film using these. These films may be used alone or in combination of two or more.

Furthermore, the low shrinkable unsaturated polyester resin molding material composition of the present invention can be heat-cured by a technique such as compression molding, transfer molding, injection molding, injection compression molding, and the like to obtain a molded product.
As molding conditions such as compression molding, transfer molding, injection molding and injection compression molding, the mold temperature is preferably 130 to 170 ° C., more preferably 140 to 160, considering the appearance and physical properties of the obtained molded product. It is preferably heated to a temperature of 0 ° C., the molding pressure is preferably 2 to 50 MPa, more preferably 5 to 30 MPa, and the heating and pressing time is molded with a thickness of the molded product of 2 mm / min to 3 mm / min. These molding conditions may be almost the same molding conditions as styrene-based molding materials.

The use of the molded product of the present invention is not particularly limited. For example, wall materials such as a system kitchen, a wash unit, and a system bath, a ceiling, a waterproof pan, a wash basin, an apron, a bathtub, a wash basin, a counter And various housing equipment such as septic tanks and building materials, construction parts such as pipes, tanks, manholes and bridges, aero parts, sunroofs, headlamp reflectors, hood bulges, bonnets, fenders and other vehicle parts.
Further, the molding material comprising the low-shrinkable unsaturated polyester resin molding material composition of the present invention, particularly a bulk molding material (BMC), is a white goods appliance such as a refrigerator, a washing machine, an air conditioner, a vacuum cleaner, a microwave oven, etc. It is useful as a BMC for sealing motors of hybrid cars, electric cars, and industrial products. Furthermore, it can also be used as an electric insulation part for various electric and electronic products.

  Hereinafter, although the embodiment will be described more specifically with reference to examples and comparative examples, the present invention is not limited to these examples. Further, the blending units in the table represent parts by weight unless otherwise specified.

[Preparation of unsaturated polyester resin]
10.5 parts of an unsaturated polybasic acid: saturated polybasic acid molar ratio ≧ 50: ≦ 50 terephthalic acid solid ester resin (“8524” manufactured by Nippon Iupika Co., Ltd.) and diallyl phthalate (“Daisodap monomer manufactured by Daiso”) "Registered trademark" or 8.59 parts of styrene (manufactured by Kishida Chemical Co., Ltd.) was dissolved so that the solid ester resin / polymerizable monomer was 55/45 wt%.
Hereinafter, this unsaturated polyester resin dissolved in diallyl phthalate is abbreviated as “8524-D”, and this unsaturated polyester resin dissolved in styrene used as a comparative example is abbreviated as “8524-S”.
The dissolution condition of the solid ester resin is such that a specified amount of polymerizable monomer is poured into a dissolution tank provided with a high-speed stirrer and a reflux condenser, and when the polymerizable monomer is diallyl phthalate, 85 ° C. is applied to the jacket of the dissolution tank. When the polymerizable monomer is styrene, 55 ° C. warm water is circulated through the jacket of the dissolution tank, and the stirring blade is rotated at 200 rpm, while stirring each polymerizable monomer, After dispersing and dissolving 0.003 part of a polymerization inhibitor (“Hydroquinone” reagent special grade manufactured by Katayama Chemical Co., Ltd.), a prescribed amount of solid ester resin “8524” was gradually added and dissolved.
On the other hand, 19.09 parts of an unsaturated polyester resin (Nippon Iupika "7365") is an unsaturated polyester resin having a solid ester / diallyl phthalate of 55/45% by weight. 7360 ") 19.09 parts are also unsaturated polyester resins of 55/45 wt% solid ester / styrene, so these unsaturated polyester resins are soluble in diallyl phthalate or styrene polymerizable monomers. Without using it.

[Production example of styrene copolymer]
In 2000 g of water in an autoclave having an internal volume of 5 L, 7.2 g of magnesium pyrophosphate and 0.47 g of alkylbenzene sulfonate (Neogen SL-200 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added and dispersed as a suspension stabilizer. Into this was added a mixed solution in which 1200 g of styrene prepared in advance, 400 g of butyl acrylate, and 12.9 g of benzoyl peroxide (Nippo BW, NOF Corporation 74.2%) as a polymerization initiator were dissolved. It was. Next, the mixture was heated to 85 ° C. and polymerized at 85 ° C. for 5 hours while stirring at 170 rpm, and subsequently reacted at 110 ° C. for 3 hours to reduce unreacted monomers. The particles obtained here were treated with hydrochloric acid, washed and filtered, and then dried to obtain resin particles (low shrinkage agent). The weight average molecular weight of the obtained resin particles was 110,000, and the glass transition temperature was 61 ° C.

Resin particles (low shrinkage agent) were obtained in the same manner as above except that 6.9 g of benzoyl peroxide was used and the reaction time at 85 ° C. was 9 hours. The obtained resin particles had a weight average molecular weight of 190,000 and a glass transition temperature of 61 ° C.
Furthermore, resin particles (low shrinkage agent) were obtained in the same manner as described above except that 4.7 g of benzoyl peroxide was used and the reaction time at 85 ° C. was 12 hours. The weight average molecular weight of the obtained resin particles was 260,000, and the glass transition temperature was 60 ° C.

[Solution of low shrinkage agent to polymerizable monomer]
A styrene-butyl acrylate copolymer having a styrene: butyl acrylate weight percent ratio of 75:25, a weight average molecular weight of 56,000 (“CS-40” manufactured by Sekisui Plastics Co., Ltd.), and a weight average molecular weight of 110 , 1,000 (developed product 1), heavy average molecular weight 190,000 (developed product 2), heavy average molecular weight 260,000 (developed product 3) and heavy average molecular weight 1,000,000 (manufactured by “ CS-20 ") is dissolved in 6.41 parts of diallyl phthalate (registered trademark of" Daiso Dup Monomer "manufactured by Daiso) or 6.41 parts of styrene (manufactured by Kishida Chemical Co., Ltd.). The polymerizable monomer was dissolved so as to be 41.2 / 58.8% by weight.

  In addition, as another low shrinkage agent, polystyrene (manufactured by Sekisui Plastics Co., Ltd., “MS-200” weight average molecular weight 340,000 and “S-90” weight average molecular weight 57,000), styrene-vinyl acetate block 4.5 parts of each of the copolymer (“MODIPER S501” styrene / vinyl acetate = 50/50 manufactured by NOF Corporation) and polyethylene powder (“FLOWSEN UF20S” manufactured by Sumitomo Seika Co., Ltd.) are similarly treated with diallyl phthalate (Daiso). "Dyso Dup Monomer" registered trademark) 6.41 parts or styrene (Kishida Chemical Co., Ltd.) 6.41 parts so that the low shrinkage agent / polymerizable monomer is 41.2 / 58.8 wt% Dissolved in.

  The dissolution condition of the low shrinkage agent is such that a specified amount of polymerizable monomer is poured into a dissolution tank provided with a high-speed stirrer and a reflux condenser, and when the polymerizable monomer is diallyl phthalate, 85 is added to the jacket of the dissolution tank. When the polymerizable monomer is styrene, circulate 55 ° C hot water through the jacket of the dissolution tank, rotate the stirring blade at 200 rpm, and stir the polymerizable monomer to reduce the shrinkage. The specified amount of the agent was gradually added and dissolved.

[Measurement of high temperature curing characteristics of resin liquid]
The test was conducted according to the 130 ° C. high temperature curing characteristics described in 5.8 of JIS K 6901: 1999 (confirmed in 2003). However, the organic peroxide as a hardening | curing agent melt | dissolved the kind and the usage-amount of the organic peroxide used for each Example and the comparative example in the resin component.
The test results are as follows: t ₁ : gel time (time until the sample temperature reaches 80 ° C. to 140 ° C.), t ₂ : curing time (time until the sample temperature reaches 80 ° C. to the maximum temperature), T: maximum exothermic temperature (Maximum temperature) and ° C./second: indicated by reaction rate (tangent tan δ at the inflection point of the temperature curve).

[Measure flash point]
Set 5 g of diallyl phthalate molding material or styrene molding material in the center of the sample tank of the setter hermetic flash point measuring instrument and close the lid. The temperature of the tank was raised to a temperature slightly lower than the expected temperature of the flash point, held for 1 minute, and the lid was opened and ignited immediately after 1 minute to confirm the presence or absence of ignition.
In each sample, change the temperature of the tank near the flash point, repeat measurement at each measurement temperature three times, and the temperature that showed the lowest temperature among the temperatures ignited twice or more is the flash point (flash temperature). It was.

[Measurement of viscosity]
It measured using the BMC viscosity measuring machine (Nippon Iupika Co., Ltd. "form: BMC-100T (touch panel type)"). 50 g of diallyl phthalate block molding material or styrene block molding material (BMC) is put into a sample pot at 40 ° C., the piston is lowered and held for 3 minutes. Thereafter, the piston is lowered at a constant speed (10 mm / sec), and the bulk molding material (BMC) is caused to flow out from a monohole having a diameter of 4 mm × L 10 mm provided at the center of the bottom of the sample pot. The load applied to the extrusion piston at this time was calculated.

[Measurement of fluidity]
Molding machine: 37-ton transfer molding machine ("Transfer ATA37 type" manufactured by North Cross)
Measurement mold: EMMI spiral flow (manufactured by Daiso)
Measurement temperature: 150 ° C. (mold temperature)
Injection pressure: 490 MPa (50 kg / cm ² )
Sample amount: 15cc x specific gravity (about 30g)
Pressurization time: 180 sec
The longest length of a part in which the molding material was cured and formed into a spiral shape such as a thin spiral mosquito coil was measured, the length was made fluid, and the change in the length was measured in time series.
The storage stability was measured under the above conditions by storing the molding material at a specified temperature (50 ° C.) and allowing it to cool to room temperature when the specified number of days was reached.
[Measurement of curing characteristics]
Molding machine: 37-ton compression molding machine (“37-ton compression press” manufactured by Shindo Metal Co., Ltd.)
Measuring mold: □ 300mm stainless steel mirror plate x 2 (Daiso's own production)
Measurement temperature: 150 ° C. (mold heating temperature)
Compression pressure: 196 MPa (gauge pressure: 20 kg / cm ² )
Sample amount: 25 g x 2 pieces Thermocouple: T-type thermocouple (0 to 400 ° C, wired to recorder)
Pressurization time: Shows the maximum exothermic temperature, and until the temperature shows a decrease Using the above equipment and conditions, connect the temperature recorder to the central part between 25g x 2 pieces of diallyl phthalate molding material or styrene molding material The T-type thermocouple is sandwiched and placed in the central portion between the stainless steel mirror plates of a 37-ton compression press heated to 150 ° C., and the gauge pressure is increased to 20 kg / cm ² . Resin plates with a thickness of 4 mm are set at the four corners of the stainless steel mirror plate, and stoppers are provided so that the molding material is not further pressurized.
From the chart of the recorder, from 50 ° C to the tangential intersection (the temperature rising slope of the temperature time curve and the linear tangent intersection of the maximum slope after the start of the curing reaction) gel time (seconds), 50 ° C to the point showing the maximum exothermic temperature Curing time (seconds), maximum exothermic temperature was the maximum exothermic temperature (° C.), and tangent tan δ at the inflection point of the temperature curve was the reaction rate (° C./second).

[Press molding]
(Compression molding)
Molding machine:
50 and 70 ton compression molding machines (manufactured by Shimazu Machinery),
60-ton compression molding machine (Marunansha "MS-0")
Mold: JIS K 6911 Various test specimen molds (manufactured by Daiso)
Molding temperature: 150 ° C (mold temperature)
Molding pressure: 490 MPa (50 kg / cm ² )
Sample amount: (the volume of each test piece × the specific gravity of each molding material × 1.05) g × the number of cavities (the number of cavities).
Pressurization time: 20 sec / mm (15 mmt) to 50 sec / mm (3 mmt)
Molding:
Charpy impact (□ 15mm × 90mml) × 4 pieces tensile strength (dumbbell shape) × 1 piece heat deformation temperature (□ 13mm × 127mml) × 2 pieces: heat deformation temperature, arc resistant circle for measuring compression strength cutting Plate (diameter 100mm x 3.2mmt) x 1 piece: For measuring arc resistance, tracking resistance, volume resistivity

(Transfer molding)
Molding machine: 37-ton transfer molding machine ("Transfer ATA37 type" manufactured by North Cross)
Mold: JIS K 6911 Test piece set mold (manufactured by Daiso)
Molding temperature: 150 ° C (mold temperature)
Injection pressure: 686 MPa (70 kg / cm ² )
Sample amount: 35 cc x specific gravity of each molding material (about 60 to 65 g)
Pressurization time: 180 sec
Molding:
Bending strength (10 mmw x 80 mm x 4 mmt) x 2 water absorption discs (diameter 50 mm x 3 mmt) x 1 sheet: boiling water absorption, appearance after heating, dielectric constant, dielectric breakdown voltage for dielectric loss tangent measurement (diameter 90 mm x 2 mmt) × 1

[Measurement of residual styrene content of molded product (FRP)]
The amount of residual styrene in the molded product was quantified by headspace-gas chromatography-mass spectrometry.
Analyzer: “HS-GC-MS system” manufactured by Shimadzu Corporation
Headspace: PerkinElmer “HS-40XL”
Gas chromatograph: “GC-17A” manufactured by Shimadzu Corporation
Mass spectrometer: “GCMS-QP5050A” manufactured by Shimadzu Corporation
A molded and hardened test piece (bending strength test piece for transfer molding) was shaved with a cutter knife and sealed in a vial at 100 ° C. for 60 min. The heated sample was used as a measurement sample.

[Mold shrinkage]
Using an arc-resistant disk (diameter 100 mm × 3.2 mmt) obtained by compression molding under the above pressing conditions, the inner diameter of a mold for forming the disk 100 mm × 3.2 mmt in diameter is 45 at room temperature. The shrinkage was determined by the following equation from the difference between the average value measured at 4 points shifted by 4 ° and the average value of the dimensions at 4 points shifted by 45 ° from the outer diameter of the actually compressed disk.
Shrinkage rate (%) = {(inner diameter dimension of mold−outer diameter dimension of disk) / inner diameter dimension of mold} × 100

[Surface characteristics of cured molded products]
(Glossiness)
Measuring machine: Gloss meter ("MYCRO-TRI-gloss" manufactured by BYK Gardner)
Incident light angle: 60 °
The value of 60 ° reflection gloss was read.

(Surface roughness)
Measuring machine: Surface roughness meter ("Surfcom 570A" manufactured by Tokyo Seimitsu Co., Ltd.)
Stylus: Tip diamond 1μmR 55 ° cone Measuring force: about 0.2mN
Measurement range: ± 40μm max
Measurement values: center line average roughness Ra, maximum height Rmax

[Physical properties of molded products]
Measurement was performed according to JISK6911.

(1) Solubility of low shrinkage agent in polymerizable monomer Diallyl phthalate ("Dai Sodap Monomer" manufactured by Daiso Co., Ltd.) was placed in a dissolution tank in which a high-speed stirrer and a reflux condenser were placed and 85 ° C hot water was circulated through the jacket. "Registered trademark" 6.41 parts or 6.41 parts of styrene (manufactured by Kishida Chemical Co., Ltd.) was poured into a dissolving tank in which 55 ° C hot water was circulated in the jacket, and the stirring blade was rotated at 200 rpm while stirring. Styrene-butyl acrylate copolymer, weight average molecular weight 56,000, glass transition temperature 60 ° C. (manufactured by Sekisui Plastics Co., Ltd., “CS-40”), weight average molecular weight 110,000, glass transition temperature 61 ° C. (Sekisui Product 1) developed by Kasei Kogyo Co., Ltd., weight average molecular weight 190,000, glass transition temperature 61 ° C. (product developed by Sekisui Plastics Kogyo Co., Ltd. 2), weight average molecular weight 260,000, glass transition temperature Gradually, 4.5 parts each at a temperature of 60 ° C. (development product 3 manufactured by Sekisui Plastics Industry Co., Ltd.) and a weight average molecular weight of 1,000,000 and a glass transition temperature of 61 ° C. (“CS-20” manufactured by Sekisui Plastics Industry Co., Ltd.) And dissolved in 2.5 hours.

  Similarly, polystyrene (manufactured by Sekisui Plastics Co., Ltd., “MS-200” weight average molecular weight 340,000, glass transition temperature 105 ° C. and “S-90” weight average molecular weight 57,000, glass transition temperature 100 ° C.), styrene -Each 4.5 parts of vinyl acetate block copolymer ("MODIPER S501" styrene / vinyl acetate = 50/50 manufactured by NOF Corporation) and polyethylene powder ("FLOWEN UF20S" manufactured by Sumitomo Seika Co., Ltd.) are diallyl phthalate. (Daiso "Daisodap Monomer" registered trademark) 6.41 parts or styrene (Kishida Chemical Co., Ltd.) 6.41 parts was gradually added and stirred for 2.5 hours by rotating the stirring blade at 200 rpm.

The solubility of these low shrinkage agents in the polymerizable monomer was determined as follows.
(Double-circle): It is easy to dissolve quickly and completely dissolves.
◯: Completely dissolved, and the solution is in a transparent or white dissolved state.
Δ: Partially dissolved, swollen or undissolved, and there is a lump.
X: It is the state which is not melt | dissolving or swelling at all.
Table 1 shows the results of evaluating the solubility of the low shrinkage agent in the polymerizable monomer.

The following was found from the evaluation results in Table 1 above.
The styrene-butyl acrylate copolymer (No. 1 to 10) is not affected by the molecular weight, and “Modiper S501” (No. 15 and 16) is not limited to diallyl phthalate or styrene. Although it dissolves well, polystyrene “MS-200” (No. 11, 12) and “S-90” (No. 13, 14) are soluble in styrene, but diallyl phthalate is swelled or undissolved. The cocoon-like lump was separated into a bowl shape. Of course, the polyethylene powder “Flocene UF20S” (No. 17, 18) does not dissolve or swell in diallyl phthalate or styrene, but is only dispersed and left alone in a state of being separated from the monomer component. there were.
As a result, the styrene-butyl acrylate copolymer (weight ratio 75:25) dissolves well in diallyl phthalate regardless of the molecular weight within the glass transition temperature range (40-80 ° C.). I found out that

(2) High-temperature curing characteristics of resin liquid Using the same dissolution tank as the above-described dissolution conditions of the low shrinkage agent, each low shrinkage agent solution, partially undissolved liquid or dispersion (No in Table 1) .1-18) 19.09 parts of unsaturated polyester resin ("7365" manufactured by Nippon Iupika Co., Ltd.) and 9.09 parts of each low shrinkage agent dissolved or mixed in diallyl phthalate (No. 1 in Table 1). ), And stirred at 200 rpm for 1 hour at 85 ° C. to dissolve, and 19.09 parts of unsaturated polyester resin (“7360” manufactured by Nippon Yupica Co., Ltd.), each low shrinkage agent dissolved in styrene Or it added to what was mixed (No. of Table 1 is an even number), and it stirred at 200 rpm for 1 hour with 55 degreeC, and was dissolved.
Next, in each resin solution, 0.45 parts of organic peroxide t-butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF Corporation) and 1,1 bis (t-hexylperoxy) 3 as two kinds of curing agents. , 3,5 trimethylcyclohexane (“Perhexa TMH” manufactured by NOF Corporation) was stirred and dissolved for 15 minutes at the same temperature and the same number of revolutions as described above. 101-118 were obtained.
In addition, resin liquid No. 119 is an unsaturated polyester resin (Nippon Iupika "7365") 19.09 parts only, organic peroxide t-butyl peroxybenzoate (Nippon "Perbutyl Z") 0.45 parts and 1, A resin solution prepared by mixing and dissolving 0.15 part of 1 bis (t-hexylperoxy) 3,3,5 trimethylcyclohexane (“Perhexa TMH” manufactured by NOF Corporation). No. 120 prepared the resin liquid which mixed and dissolved the same said organic peroxide only in 19.09 parts of unsaturated polyester resin ("7360" by Nippon Iupika Co., Ltd.) on the said conditions.
Tap water was poured into the jacket of the dissolution tank after dissolution, and these resin liquids were cooled.
The high temperature curing characteristics of these (partially omitted) resin liquids were tested in accordance with the 130 ° C. high temperature curing characteristics described in 5.8 of JIS K 6901: 1999 (2003 confirmation), and the following characteristics were obtained. .
t ₁ : Gel time (time until the sample temperature reaches 80 ° C. to 140 ° C.)
t ₂ : Curing time (time until the sample temperature reaches 80 ° C. to the maximum temperature)
T: Maximum exothermic temperature (temperature indicating the highest point)
° C / sec: reaction rate (tangent tan δ at the inflection point of the temperature curve)
Table 2 shows the measurement results of the high-temperature curing characteristics of the resin liquid.

The following was found from the measurement results in Table 2 above.
The diallyl phthalate resin solution (resin solution No. is an odd number) has longer gel time and curing time than the styrene resin solution (resin solution No. is an even number), but there is not much difference in the maximum exothermic temperature. The reaction rate of the diallyl phthalate resin solution was faster or almost equal to that of the styrene resin solution.

  However, resin liquid No. using a low shrinkage agent solution of polystyrene “MS-200”. 111 and resin liquid no. 112 and a resin solution No. 112 using a low shrinkage agent solution of “Modiper S501”. 115 and resin liquid no. When 116 was compared, the reaction rate of the diallyl phthalate resin solution was slower than that of the styrene resin solution. This is because in the case of polystyrene “MS-200” as a low shrinkage agent, the solubility in diallyl phthalate was poor and there was a lump in the state of an unsaturated polyester resin (“7365” manufactured by Nippon Iupika Co., Ltd.). Furthermore, it is considered that the lump in an untreated state was separated from the dissolved resin solution, and the reactivity of the non-uniform resin solution was measured.

As a result, by using a curing agent in which a highly reactive unsaturated polyester resin and an organic peroxide having a low half-life temperature are used, for example, a co-polymer of styrene-butyl acrylate in which a low shrinkage agent is easily dissolved in diallyl phthalate. When a polymer (weight% ratio is 75:25) is used, even if diallyl phthalate is used as a crosslinking agent for an unsaturated polyester resin, it reacts with an exothermic temperature equal to or higher than that of an unsaturated polyester resin using styrene as a crosslinking agent. It turns out that speed is obtained.
In addition, resin liquid No. which does not contain a low shrinkage agent solution. 119 and No. No. 120 is a diallyl phthalate-based resin liquid No. 120 similar to the resin liquid containing the low shrinkage agent solution. 119 is a styrene resin liquid No. Compared to 120, both the gel time and the curing time were longer, but both had higher maximum exothermic temperatures than the resin solution containing the low shrinkage agent solution, and the reaction rate was very fast. This is probably because the ratio of the curing agent to the resin was increased because the low shrinkage agent solution was not included.

Example 1
To a 3 L pressure kneader (Moriyama Seisakusho Co., Ltd.) with water-cooled jacket and double-arm Banbury blade, 1750 g of filler aluminum hydroxide (“Hijilite H-32” made by Showa Denko KK), magnesium cross-linking agent magnesium oxide ( Kyowa Chemical Industry Co., Ltd. “Kyowa Mag 150”) 1.05 g and mold release agent zinc stearate (Adeka “SZ2000”) 35 g are put in, the pressure lid is closed, and the Banbury blade is turned in the opposite direction at 25 rpm. Mixed for minutes.
Next, the pressure lid was opened, and the resin liquid No. shown in Table 2 as a resin component was mixed into the powder component while mixing. 101 was heated to 85 ° C., and 1071 g thereof was gradually added and kneaded for 4 minutes until it was uniformly putty.

Further, while continuing kneading, 700 g of reinforcing glass fiber (“CS03MB498A” manufactured by Asahi Fiber Glass Co., Ltd.) was added to the putty-like material over a period of 2 minutes. The mixture was kneaded for 5 minutes until it was dispersed and dispersed uniformly.
After completion of the kneading, the lid of the pressure kneader was opened, the kneader tank was turned over, the kneaded product was taken out while the Banbury blade was rotated forward and reverse, and was wrapped and stored with a PET film.

  This resin component includes 668.15 g “7365” manufactured by Nippon Iupika Co., Ltd. as an unsaturated polyester resin, a styrene-butyl acrylate copolymer as a low shrinkage agent, a weight average molecular weight of 56,000, a glass transition temperature of 60 ° C. ( No. 1 in Table 1 in which 157.5 g of Sekisui Plastics Co., Ltd., “CS-40”) was dissolved in 224.35 g of diallyl phthalate (registered trademark of “Daiso Dup Monomer” manufactured by Daiso). 1 is 381.85 g, organic peroxide t-butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF Corporation) as curing agent, 15.75 g and 1,1 bis (t-hexylperoxy) 3, 3, 5 5.25 g of trimethylcyclohexane (NOF Corporation "Perhexa TMH") is included.

Example 2
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 103 was used as the resin component. The resin component low shrinkage agent is a styrene-butyl acrylate copolymer having a weight average molecular weight of 110,000 and a glass transition temperature of 61 ° C. (developed by Sekisui Plastics Co., Ltd. 1) dissolved in diallyl phthalate. No. The same components as in Example 1 except for 3.

Example 3
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 105 was used as the resin component. The resin component low shrinkage agent is a styrene-butyl acrylate copolymer having a weight average molecular weight of 190,000 and a glass transition temperature of 61 ° C. (developed by Sekisui Plastics Co., Ltd. 2) dissolved in diallyl phthalate. No. Except for 5, it contains the same components as in Example 1.

Example 4
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 107 was used as the resin component. The resin component low shrinkage agent is a styrene-butyl acrylate copolymer having a weight average molecular weight of 260,000 and a glass transition temperature of 60 ° C. (developed by Sekisui Plastics Co., Ltd. 3) dissolved in diallyl phthalate. No. Except for 7, it contains the same components as in Example 1.

Example 5
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 115 was used as the resin component. This resin component low shrinkage agent is a styrene-vinyl acetate copolymer having a weight average molecular weight of 213,000 and glass transition temperatures of 30 ° C. and 100 ° C. (“MODIPER S501” manufactured by NOF Corporation) diallyl. No. 1 of Table 1 dissolved with phthalate. Except for 15, it contains the same components as in Example 1.

Example 6
In the resin liquid 1071 g, an unsaturated polyester resin is abbreviated as “8524-D” 668., which is obtained by dissolving 367.5 g of “8524” manufactured by Iupika Japan Co., Ltd. No. of Table 1 which melt | dissolved 15g and the low shrinkage | contraction agent with diallyl phthalate with the weight average molecular weight 110,000 and glass transition temperature 61 degreeC (development 1 by Sekisui Plastics Co., Ltd.) with a styrene-butyl acrylate copolymer. . A kneaded product was obtained in the same manner as in Example 1 except that it contained the same components as in Example 1.

Comparative Example 1
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 102 was heated to 55 ° C. and used as a resin component. The unsaturated polyester resin of this resin component is “7360” manufactured by Nippon Iupika Co., Ltd., No. 1 in Table 1 using styrene (manufactured by Kishida Chemical Co., Ltd.) instead of diallyl phthalate as the solvent for the low shrinkage agent. Except for 2, it contains the same components as in Example 1.

Comparative Example 2
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 109 was used as the resin component. Implemented except that the resin component low shrinkage agent is a styrene-butyl acrylate copolymer with a weight average molecular weight of 1,000,000 and a glass transition temperature of 61 ° C. (“CS-20” manufactured by Sekisui Plastics Co., Ltd.). Contains the same ingredients as in Example 1.

Comparative Example 3
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 111 was used as the resin component. This resin component contains the same components as in Example 1 except that the resin component has a polystyrene ("MS-200" manufactured by Sekisui Plastics Co., Ltd., a weight average molecular weight of 340,000, and a glass transition temperature of 105 ° C).

Comparative Example 4
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 11 3 was used as a resin component. This resin component contains the same components as in Example 1 except that the low shrinkage agent is polystyrene (“S-90” manufactured by Sekisui Plastics Co., Ltd., weight average molecular weight 57,000, glass transition temperature 100 ° C.). .

Comparative Example 5
Resin liquid No. shown in Table 2 A kneaded material was obtained in the same manner as in Example 1 except that 117 was used as the resin component. This resin component has the same components as in Example 1 except that the low shrinkage agent is polyethylene powder ("Flocene UF20S" manufactured by Sumitomo Seika Co., Ltd.).

Comparative Example 6
To a 3L pressure kneader (Moriyama Seisakusho Co., Ltd.) with water-cooled jacket and double-arm Banbury blade, 1750g of filler aluminum hydroxide ("Hijilite H-32" manufactured by Showa Denko KK), magnesium cross-linker magnesium oxide ( Kyowa Chemical Co., Ltd. “Kyowa Mag 150”) 1.05 g and mold release agent zinc stearate (Adeka “SZ2000”) 35 g were put in, the pressure lid was closed, and the Banbury blade was turned in the opposite direction at 25 rpm for 1 minute. Mixed.
Next, the pressure lid was opened, and while mixing, 1071 g of the following resin liquid as a resin component was heated to 85 ° C. while being mixed, and gradually added and kneaded for 4 minutes until evenly putty-like. .

Further, while continuing the kneading, 700 g of reinforcing agent glass fiber (“CS03MB498A” manufactured by Asahi Fiber Glass Co., Ltd.) was added to the putty-like material over 2 minutes, and then the pressure lid was closed to converge the glass fiber. The mixture was kneaded for 5 minutes until it was separated and uniformly dispersed.
After completion of the kneading, the lid of the pressure kneader was opened, the kneader tank was turned over, the kneaded product was taken out while the Banbury blade was rotated forward and reverse, and was wrapped and stored with a PET film.

  In the above-mentioned resin liquid 1071 g, an unsaturated polyester resin is an abbreviation “8524-D” 668 in which 367.5 g of “8524” manufactured by Iupika Japan Co., Ltd. is dissolved in 300.65 g of diallyl phthalate (registered trademark of “Daiso Dup Monomer” manufactured by Daiso). 157.5 g of polystyrene as a low shrinkage agent (“MS-200” manufactured by Sekisui Plastics Co., Ltd., weight average molecular weight 340,000, glass transition temperature 105 ° C.) 157.5 g diallyl phthalate (“Dai Sodap Monomer manufactured by Daiso”) "Registered trademark" No. 1 in Table 1 which was partially dissolved in 224.35 g and separated into a cocoon-like lump while partially swollen. 11 was 381.85 g, organic peroxide t-butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF Corporation) as a curing agent, and 1,1 bis (t-hexylperoxy) 3, 3, 5 And 5.25 g of trimethylcyclohexane (“Perhexa TMH” manufactured by NOF Corporation).

Comparative Example 7
As a resin liquid, an unsaturated polyester resin is 668.15 g of abbreviation “8524-S” obtained by dissolving 367.5 g of “8524” manufactured by Nippon Iupika Co., Ltd. in 300.65 g of styrene (manufactured by Kishida Chemical Co., Ltd.), and a low shrinkage agent. No. 1 in Table 1 in which 157.5 g of polystyrene (manufactured by Sekisui Chemical Co., Ltd., “MS-200”, weight average molecular weight 340,000, glass transition temperature 105 ° C.) was dissolved in 224.35 g of styrene (manufactured by Kishida Chemical Co., Ltd.). 38.85 g of No. 12 and 15.75 g of organic peroxide t-butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF Corporation) and 1,1 bis (t-hexylperoxy) 3, 3, 5 as a curing agent 3.25 g of trimethylcyclohexane (“Perhexa TMH” manufactured by NOF Corporation). A kneaded material was obtained in the same manner as in Comparative Example 6 except that the resin liquid was heated to 55 ° C.

Comparative Example 8
A kneaded material was obtained in the same manner as in Comparative Example 6 except that the curing agent contained only 21 g of an organic peroxide t-butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF Corporation) as the resin component.

(3) The resin liquid components used in Examples 1 to 6 and Comparative Examples 1 to 8 are described in detail in the list 3 of the resin liquid components and curing agents in Examples and Comparative Examples.
The details of the polymerizable monomer, the low shrinkage agent, the unsaturated polyester resin, and the curing agent are shown in the table with the following abbreviations.
Type of polymerizable monomer (DAP: diallyl phthalate, St: styrene).
Low shrinkage agent (St-BA: styrene-butyl acrylate copolymer,
PS: polystyrene,
PS-PVAc: styrene-vinyl acetate copolymer, PE: polyethylene),
Heavy average molecular weight (MW), glass transition temperature (Tg), part number (part number) of each low shrinkage agent.
Types of unsaturated polyester resins (molar ratio: unsaturated polybasic acid / saturated polybasic acid) and product number.
Type and presence / absence of curing agent (TBP: “Perbutyl Z”, TMH: “Perhexa TMH”).
Yes: Yes, No: ×

  The properties and various properties of the molding material will be described in detail below with respect to examples and comparative examples of the composition of the resin liquid component and the curing agent in Table 3.

(4) Kneadability, flash point, viscosity, fluidity, and curing characteristics of molding material The kneadability of the molding material was evaluated as follows.
◎: Kneaded in a very good state and no adhesion to the pressure kneader ◯: Kneaded in a good state and almost no adhesion to the pressure kneader △: The kneaded product has a high viscosity and has a dryness is there. There is no adhesion to the pressure kneader. X: The viscosity of the kneaded material is low, sticky, and much adhesion to the pressure kneader Table 4 shows the evaluation results of the kneadability, flash point, viscosity, fluidity, and curing characteristics of the molding material. Indicates.

Regarding the examples and comparative examples in Table 4, the kneadability, flash point, viscosity, fluidity, and curing characteristics will be described in detail below.
The pressure kneader kneadability in the examples and comparative examples in Table 4 was determined by hand feeling and visual judgment.
The diallyl phthalate-based molding materials of Examples 1 to 4 and 6, which are one form of the low-shrinkable unsaturated polyester resin molding material composition of the present invention, have a styrene-butyl acrylate copolymer as a low-shrinkage agent. An excellent kneadability was exhibited by using “CS-40” and others (manufactured by Sekisui Plastics Co., Ltd.) having a weight average molecular weight of 56,000 to 260,000 and a glass transition temperature of 60 to 61 ° C.

Further, the diallyl phthalate molding material of Example 5 in which the low shrinkage agent is a styrene-vinyl acetate block copolymer and “Modiper S501” (manufactured by NOF Corporation) with styrene / vinyl acetate = 50/50 is also used. Excellent kneadability was exhibited.
On the other hand, in the styrene molding materials of Comparative Examples 1 and 7, “CS-40” (Sekisui Chemical Co., Ltd.) having a low-shrinkage agent and a weight average molecular weight of 56,000 styrene-butyl acrylate copolymer and a glass transition temperature of 60 ° C. (Manufactured by Kogyo Co., Ltd.) and “MS200” (manufactured by the same company) having a polystyrene weight average molecular weight of 340,000 and a glass transition temperature of 105 ° C. were used. There was much adhesion.
Similarly, in Comparative Example 5 using the polyethylene powder “Flusen UF20S” (manufactured by Sumitomo Seika Co., Ltd.), the kneadability of the molding material was very poor, sticky, and often adhered to the pressure kneader. It was.
In Comparative Example 2, “CS-20” (manufactured by Sekisui Plastics Co., Ltd.) having a weight average molecular weight of 1,000,000 and a glass transition temperature of 61 ° C. of a styrene-butyl acrylate copolymer as a low shrinkage agent. Comparative Examples 3, 6, and 8 are diallyl phthalate-based molding materials using “MS200” (manufactured by the same company) having a polystyrene weight average molecular weight of 340,000 and a glass transition temperature of 105 ° C., and are attached to a pressure kneader. Although there was no padding, it was in a poorly organized state as a bulk molding material (BMC).
Comparative Example 4 having good kneadability among Comparative Examples is “S-90” (manufactured by Sekisui Plastics Co., Ltd.) having a polystyrene weight average molecular weight of 57,000 and a glass transition temperature of 100 ° C. as a low shrinkage agent. Is a diallyl phthalate-based molding material using a low-shrinkage agent, and its molecular weight is smaller than that of “MS200” (manufactured by the same company) having a weight average molecular weight of 340,000. It is considered that a kneaded state with a good ratio was obtained.

  The flash point of the molding material which is one type of the low-shrinkable unsaturated polyester resin molding material composition of the present invention is as shown in Table 4, Examples 1 to 6 of the diallyl phthalate molding material and Comparative Examples 2 to 2 6 and 8 showed a measurement limit of 110 ° C. or more of the setter closed flash point measuring instrument, whereas Comparative Examples 1 and 7 of the styrenic molding material were 36 ° C. and 35 ° C., respectively. This flammable solid (with a flash point of less than 40 ° C.) requires various types of equipment in the molding material manufacturing process and molding process, and explosion-proof equipment in buildings and storage warehouses, and the amount of molding material stored is restricted. Therefore, the low-shrinkable unsaturated polyester resin molding material composition of the present invention eliminates the need for various equipment in the production process and molding process, and the explosion-proof equipment of buildings and storage warehouses, and its economic effect is very large.

The viscosity of the molding material was very low for the styrenic molding materials of Comparative Examples 1 and 7 and showed low values of 1.7 kPa · s and 2.5 kPa · s, respectively. Examples 1 to 6 of the diallyl phthalate-based molding material, which is one form of the resin molding material composition, are 4.2 to 10.0 kPa · s, which is about 2.5 to 4 times that of the styrene-based molding material. High value was shown.
This improves the fillability and moldability inside the mold during the heat and pressure molding process by the mold, and occurs inside the molded product and on the surface, which is a characteristic defect of styrenic molding materials. This eliminates molding defects such as "s" and "voids".

The storage stability of the flowability of the molding material is determined by storing the molding material hermetically packaged in a PET film in a hot air dryer at 50 ° C., measuring the spiral flow after a specified number of treatment days, and changing the fluidity over time. It is what investigated.
In Comparative Example 1 of the styrenic molding material, which had a flow length of 130 cm after 1 day of storage, the flowability became 0 cm after 7 days of storage, and it did not flow at all and was hardened. Another comparative example 7 of the styrene-based molding material is that “8524-S” (Nippon Iupika Co., Ltd.) is less reactive than unsaturated polyester resin “7360” (Nippon Iupika Co., Ltd.) with styrene. Although a longer stability than Comparative Example 1 was exhibited, the fluidity on storage day was 96 cm, the storage day was 33 cm, the storage day was 15 cm, and the storage day was 15 cm. Fillability into the mold became insufficient.
On the other hand, Examples 1 and 3 of diallyl phthalate-based molding materials, which are one form of the low-shrinkable unsaturated polyester resin molding material composition of the present invention, are highly reactive unsaturated polyester resins “7365” (Nippon Iupika). In spite of using the product manufactured by the company, the fluidity was 20 cm or more even after 30 days of storage, and it was found that the fluidity was highly stable.
However, Example 5 of the diallyl phthalate molding material similarly uses a copolymer “S501” (manufactured by NOF Corporation) of styrene and vinyl acetate as a low shrinkage agent, but the flowability is small. , It was 58 cm in 1 day of storage, 47 cm in 7 days of storage, and became 0 cm in 30 days of storage.
Even in the case of diallyl phthalate molding material using highly reactive unsaturated polyester resin “7365”, in Comparative Examples 4 and 5, the low shrinkage agent is the conventional low molecular weight polystyrene “S-90” (Sekisui Plastics Co., Ltd.). ), Polyethylene powder “UF20S” (manufactured by Sumitomo Seika Co., Ltd.), but the fluidity after 30 days is 9 cm and 0 cm, respectively, and they are gelled or cured, and cannot be molded. became.

The measurement results of the curing characteristics are different from the measurement results of the high temperature curing characteristics of the resin liquid in Table 2 described above, and the measurement conditions may be different, but the maximum exothermic temperature is 158 to 167 ° C. in both the examples and the comparative examples. The reaction rate was very low, 0.4 to 1.9 ° C./sec.
Among them, the curing time of Comparative Example 8 using an unsaturated polyester resin “8524-D” having low reactivity and using only perbutyl Z (TBP) as a curing agent was 195 seconds and the reaction rate was 0.4 ° C./second. In Comparative Example 6 where the curing agent Perhexa TMH (TMH) having a low decomposition temperature was combined with the curing agent in the same system, the curing time was 161 seconds and the reaction rate was 0.4 ° C./second. And the curing was slow.
On the other hand, in the styrene-based molding material, the curing time is 56 seconds and 71 seconds, respectively, as compared with Comparative Example 1 and Comparative Example 7 using the unsaturated polyester resin “8524-D” having low reactivity. The speeds were also relatively fast, 1.9 ° C./sec and 1.3 ° C./sec, respectively, and it was said that curing was fast among these.
Examples 1 and 3 of diallyl phthalate-based molding materials, which are one form of the low-shrinkable unsaturated polyester resin molding material composition of the present invention, have a curing time as short as 105 seconds and 86 seconds, respectively, and the reaction rate is also low. These were positioned between 0.8 ° C./second and 1.0 ° C./second respectively.
In any case, the reason why the maximum exothermic temperature of these molding materials is low is that a large amount of inorganic filler aluminum hydroxide and inorganic fiber glass fiber are included, so unsaturated polyester resin and reactive monomer are cured. It can be presumed that the exothermic reaction heat generated during crosslinking by the agent is absorbed by these inorganic fillers and inorganic fibers.

(5) Residual styrene content, shrinkage, surface characteristics (glossiness, surface roughness) of molded products
The appearance of the molded product was evaluated as follows by touch and visual observation of the surface of the molded product.
A: Very good luster and surface smoothness, and clear when a lit fluorescent lamp is photographed.
◯: Good gloss and surface smoothness, and slightly clear when a lit fluorescent lamp is photographed.
Δ: Slightly inferior in gloss and surface smoothness and blurred when a lit fluorescent lamp is photographed.
X: There is roughness or undulation, there is no gloss and surface smoothness, and the appearance is not revealed even if a lit fluorescent lamp is copied.
Table 5 shows the evaluation and measurement results of the amount of residual styrene, appearance, shrinkage, and surface characteristics (glossiness and surface roughness) of the molded product.

Regarding the examples and comparative examples in Table 5, the amount of residual styrene, appearance, shrinkage, and surface characteristics of the molded product will be described in detail below.
As a matter of course, the amount of residual styrene of the molded product is found that Comparative Example 1 and Comparative Example 7 of the styrenic molding material dissipate very much styrene at 206 mg / kg and 498 mg / kg, respectively. For this reason, the odor of styrene is generated and becomes a problem as a VOC (volatile organic compound) and as a specific malodorous substance.
On the other hand, the residual styrene content of the diallyl phthalate molding material is 1.0 mg / kg in Examples 1 to 6 and Comparative Examples 2 to 6 and 8 which are the low shrinkable unsaturated polyester resin molding material compositions of the present invention. The amount of trace was less than 4.0 mg / kg from the trace level of less than kg.
Although the regulation value of the amount of VOC (volatile organic compound) generated is not yet legally established, the target value is about 10-15 mg / kg (ppm) as the self-regulatory value of each local government, each organization and each company. The low-shrinkable unsaturated polyester resin molding material composition of the present invention was also adapted to this self-regulated value.
In these diallyl phthalate molding materials, a small amount of residual styrene was detected because the residual styrene was 0.2 to 0.7 wt% in the styrene-butyl acrylate copolymer or polystyrene used as the low shrinkage agent. This is because the styrene-vinyl acetate copolymer is the same.

As for the appearance of the molded product, the surface of an arc-resistant disk with a diameter of 100 mm and a thickness of 3.2 mm formed by press molding conditions using a mold with mirror grinding and hard chrome plating is touched by hand. It was performed based on the above evaluation criteria by touch and visual observation.
Examples 1 to 4 using a styrene-butyl acrylate copolymer “CS-40” having a weight average molecular weight of 56,000 to 260,000 as a low shrinkage agent and a styrene-vinyl acetate copolymer “Modiper S501” The appearance of the diallyl phthalate molding material of Example 5 using "" had very good gloss and surface smoothness, and the outer shape was clearly visible when a lit fluorescent lamp was photographed.

However, the appearance of Comparative Example 2 of a diallyl phthalate molding material using a styrene-butyl acrylate copolymer having a weight average molecular weight of 1,000,000 as a low shrinkage agent is slightly more than that of Examples 1-5. It was inferior in gloss and surface smoothness, and when the lit fluorescent lamp was photographed, the outer shape was slightly clearly visible.
On the other hand, the appearance of Comparative Example 1, which is a styrene-based molding material using a styrene-butyl acrylate copolymer having a weight average molecular weight of 56,000 as a low shrinkage agent, is very bad and rough due to the hand feeling. In addition, there was no gloss or surface smoothness, and the external shape was not found at all even when a lit fluorescent lamp was photographed.

Similarly, in Comparative Example 7, which is a styrenic molding material, polystyrene “MS200” having a weight average molecular weight of 340,000, which has been conventionally used as a low shrinkage agent, was used. Since “8524-S” in which a saturated polyester resin is dissolved in styrene is used, the gloss and surface smoothness are slightly inferior to those of Examples 1 to 5, and when the lit fluorescent lamp is copied, the outer shape is slightly clearly reflected. Met.
Further, Comparative Example 6 using “8524-D” in which a solid unsaturated polyester resin having a slightly low reactivity was dissolved in diallyl phthalate also used the same “8524-D”, and perbutyl Z (TBP) as a curing agent. The diallyl phthalate-based molding material of Comparative Example 8 using only polystyrene also used polystyrene “MS200” having a weight average molecular weight of 340,000 as the low shrinkage agent, but the solubility in diallyl phthalate was poor and remained in this state. As a result, the appearance was very poor, the surface was undulated, there was no gloss or surface smoothness, and the external shape was not revealed even when a lit fluorescent lamp was copied.
In addition, Comparative Example 3 using “MS200” having a weight average molecular weight of 340,000 as a low shrinkage agent, Comparative Example 4 using “S-90” of 57,000, and polyethylene powder “Flocene UF20S” In Comparative Example 5 using No. 1, the appearance was inferior to that of Examples 1-5.

The shrinkage rate of the molded product was measured by the method described in [Molding shrinkage rate] using an arc-resistant disc having a diameter of 100 mm and a thickness of 3.2 mm used for appearance determination of the molded product.
The shrinkage ratio of Examples 1 to 4, which is a diallyl phthalate molding material using a styrene-butyl acrylate copolymer having a weight average molecular weight of 56,000 to 260,000 as a low shrinkage agent, is 0.17 to 0. As small as 19%, it was possible to obtain a small shrinkage ratio that could not be achieved with diallyl phthalate molding materials.
Further, although the shrinkage of Example 5 using “Modiper S501” of a styrene-vinyl acetate block copolymer was 0.15%, a very small value was obtained, but a slightly unsaturated solid unsaturated polyester. Example 6 using “8524-D” in which the resin was dissolved in diallyl phthalate had a shrinkage ratio despite using a styrene-butyl acrylate copolymer having a weight average molecular weight of 110,000 as the low shrinkage agent. Increased slightly to 0.25%. This is considered to be due to the appearance of undulations on the surface resulting from the use of “8524-D”.

  In addition, the shrinkage rate of Comparative Example 2 of the diallyl phthalate-based molding material using a styrene-butyl acrylate copolymer having a weight average molecular weight of 1,000,000 as a low shrinkage agent is also small and good at 0.17%. Although it was a value, in the said external appearance, it was inferior to an Example.

On the other hand, the shrinkage ratio of Comparative Example 1 which is a styrene-based molding material using a styrene-butyl acrylate copolymer having a weight average molecular weight of 56,000 as a low shrinkage agent is 0.15% numerically. Although small and good, the appearance was very inferior and the surface was rough.
Similarly, Comparative Example 7, which is a styrenic molding material, uses polystyrene “MS200” having a weight average molecular weight of 340,000, which has been conventionally used as a low shrinkage agent. Since “8524-S” in which an unsaturated polyester resin was dissolved in styrene was used, the shrinkage ratio was as large as 0.3%.

Further, Comparative Example 6 using “8524-D” in which a solid unsaturated polyester resin having a slightly low reactivity was dissolved in diallyl phthalate also used “8524-D”, and perbutyl Z (TBP) as a curing agent. The diallyl phthalate-based molding material of Comparative Example 8 using only polystyrene also used polystyrene “MS200” having a weight average molecular weight of 340,000 as the low shrinkage agent, but the solubility in diallyl phthalate was poor and remained in this state. Because of this, the shrinkage ratio was as large as 0.35% and 0.55%, which could not be said to be a low-shrinkable molding material.
In the diallyl phthalate-based molding material, Comparative Example 3 using “MS200” having a polystyrene weight average molecular weight of 340,000 as a low shrinkage agent, and Comparative Example 4 using “S-90” having 57,000. And Comparative Example 5 using polyethylene powder “Flocene UF20S”, the shrinkage ratios are large, 0.22%, 0.25%, and 0.30%, respectively, which are inferior to Examples 1-4. Met.

The surface characteristics of the molded product were evaluated by measuring glossiness (a numerical value of reflection gloss at an incident light angle of 60 ° C.) and surface roughness (centerline average roughness Ra, maximum height Rmax).
In the diallyl phthalate-based molding material, the glossiness of Examples 1 to 4 using a styrene-butyl acrylate copolymer having a weight average molecular weight of 56,000 to 260,000 as the low shrinkage agent is 69 to 73. There is a comparison using “MS200” having a glossiness of 70 in Comparative Example 2 having the same low shrinkage agent and a weight average molecular weight of 1,000,000 and polystyrene having a weight average molecular weight of 340,000 as the low shrinkage agent. The glossiness of Comparative Example 4 using “S-90” of Example 3 and 57,000 showed good glossiness almost equal to 69 and 72, respectively.
On the other hand, the glossiness of Comparative Examples 1, 6 and 8, which had a poor appearance, was 48, 54 and 50, which were low values, respectively.
In Example 5, the diallyl phthalate-based molding material using a styrene-vinyl acetate block copolymer “Modiper S501” had a glossiness as good as 72, but the polyethylene powder “Flocene UF20S” was used. Comparative Example 5 was 60, polystyrene “MS200” having a weight average molecular weight of 340,000 was used as a low shrinkage agent in a styrene-based molding material, and a solid unsaturated polyester resin having a slightly low reactivity was dissolved in styrene “8524-S. Comparative Example 7 using "" was slightly inferior to 64.

As for the surface roughness of the molded product, the center line average roughness Ra and the maximum height Rmax were determined by a surface roughness measuring machine.
Regarding the center line average roughness Ra, except for the large value of 0.7 μm of Comparative Example 1 which is a styrenic molding material, most of the other are very small values of 0.1 to 0.2 μm, which are good. It was. In Comparative Example 1, it was considered that Ra had a large value since there was a roughness in the appearance determination and the result was x and there was no gloss.
On the other hand, the maximum height Rmax of Examples 1-4 was good at a small value of 5.9-6.5 μm, but the Rmax of Comparative Example 1, Comparative Example 3, Comparative Examples 6, 7, and 8 was good. The value of 11.4 μm to 22.4 μm was a large value. The Rmax of Comparative Example 1 was increased, as was the case with Ra, which was due to the fact that there was a roughness in the appearance judgment, and that there was no gloss. The poor solubility in phthalate seems to have an effect.
Further, the reason why the Rmax of Example 6 and Comparative Examples 6, 7, and 8 was increased was that unsaturated polyester resins “8524-D” and “8524-S” having slightly low reactivity were used. This is thought to be due to the increase in the surface of the molded product.
In Comparative Example 1 and Comparative Example 7 using styrene as the polymerizable monomer, the maximum height Rmax was particularly large, 19.9 and 22.4, respectively.

(6) Physical properties of molded products (physical properties, thermal properties)
Table 6 shows the measurement results of physical properties (physical properties, thermal properties) of molded products.

With respect to the examples and comparative examples in Table 6, the physical properties and thermal properties of the molded products will be described in detail below.
Among the physical properties, in boiling water absorption, Examples 1 and 3 of diallyl phthalate molding materials were 0.28% and 0.29%, respectively, and the values were small and good.
On the other hand, the boiling water absorption of the styrenic molding material was as small as 0.22% and 0.26% in Comparative Examples 1 and 7, respectively, but the difference from the Examples was small.
However, Example 5 using a diallyl phthalate-based molding material using a styrene-vinyl acetate block copolymer “Modiper S501” was 0.79%, and Comparative Example 5 using a polyethylene powder “Flocene UF20S” was 0.00. It was very large at 89%, and then the largest value was obtained by using “8524-D” in which a solid unsaturated polyester resin having slightly low reactivity was dissolved in diallyl phthalate, and perbutyl Z (TBP) as a curing agent. It was 0.54% of the comparative example 8 which used only.
The boiling water absorption rates of the other Comparative Examples 3, 4 and 6 were 0.34%, 0.31% and 0.27%, respectively, which were almost good values.

Further, Rockwell hardness of a surface hardness of the molded article (H R _M scale) is an unsaturated polyester resin which is highly reactive, as in Example 1, 3 and 5 using the "7365" of diallyl phthalate Comparison While the values of Examples 3 to 5 were 94 to 100, the value of Comparative Example 1 using a styrenic “7360” was also slightly inferior to 81, similarly with a highly reactive unsaturated polyester resin. .
On the other hand, the value of Rockwell hardness of Example 6 and Comparative Examples 6 to 8 using “8524-D” and “8524-S” of medium to low reactivity unsaturated polyester resins was 61 to 73 and the polymerization was small. The crosslink density with the monomer is inferior.

Next, among the thermal properties, the appearance after heating was measured by placing a water-absorbing disk having a diameter of 50 mm × 3 mmt in a hot air circulating dryer at 190 ° C. and 210 ° C. and taking it out after 2 hours of heat treatment, until it reached room temperature in a desiccator. After allowing to cool, the weight reduction rate was determined from the weight before and after the heat treatment.
According to this, the weight reduction rate in the treatment at 190 ° C. for 2 hours was small and good in Examples 1 and 3 as 0.50% and 0.46%, but Comparative Examples 3, 4, 5 and 6-8. Shows a slightly large value of 0.50% to 0.69%.
However, in the case of diallyl phthalate-based molding material, Example 5 using the styrene-vinyl acetate block copolymer “Modiper S501” has a large weight loss rate of 0.89%, which is as bad as the above-mentioned boiling water absorption rate. It was a result.
On the other hand, the weight reduction rate in the treatment at 210 ° C. for 2 hours showed a value larger than the value for the treatment at 190 ° C. for 2 hours, but showed the same tendency as the weight reduction rate for the treatment at 190 ° C. for 2 hours. Are 1.38% and 1.35% in Examples 1 and 3, while Comparative Examples 3, 4 and 5 are slightly larger from 1.38% to 1.80%. Example 5 using the vinyl block copolymer “Modiper S501” showed a maximum value of 2.03%.

The thermal deformation temperature of the other thermal property is 260 for Examples 1, 3 and 5 and Comparative Examples 1 and 3-5 using highly reactive unsaturated polyester resins “7365” and “7360”. Example 6 and Comparative Examples 6 to 8 using unsaturated polyester resins “8524-D” and [8524-S] with slightly low reactivity were 195 ° C. The value was as low as ˜232 ° C.
Thus, it has been found that the heat distortion temperature is affected by the high reactivity of the unsaturated polyester resin.

(7) Molded product properties (strength properties)
Table 7 shows the measurement results of the physical properties of the molded product (strength physical properties).

Regarding the examples and comparative examples in Table 7, the strength properties of the molded products will be described in detail below.
The strength properties depend on the type, length, amount used and degree of dispersion of the glass fibers used.
In all the formulations of Examples 1 to 6 and Comparative Examples 1 to 8, the type, length, and amount of glass fiber used are the same, the kneader kneading procedure and the kneading time are the same, but depending on the viscosity of the resin liquid Since the viscosity of the kneaded product is changed, the degree of dispersion of the glass fibers is different, and it is considered that a difference in the value of the strength physical properties has occurred.

(8) Physical properties of molded products (electrical properties)
Table 8 shows the measurement results of the physical properties (electrical properties) of the molded products.

Regarding the examples and comparative examples in Table 8, the electrical characteristics of the molded products will be described in detail below.
Among the electrical characteristics, the strength of dielectric breakdown was as follows: Examples 1 and 3 for both the short time method and the step method, 16.9 MV / m, 16.6 MV / m for the short time method, and 13.7 MV / m for the step method. A good value as high as 13.5 MV / m was exhibited.
On the other hand, Example 6 and Comparative Examples 1 and 3 to 8 show low values of 11.4 MV / m to 14.8 MV / m by the short time method and 10.9 MV / m to 12.3 MV / m by the step method. It was.
However, the dialylic phthalate molding material, which has the worst results in boiling water absorption and heating weight reduction rate (appearance after heating), is a styrene-vinyl acetate block copolymer “Modiper S501”. In Example 5, the short time method was 16.5 MV / m, and the step method was 13.2 MV / m, which was almost the same as in Examples 1 and 3.

As for the volume resistivity of other electrical characteristics, the measured values in the normal state are from 5.7 to 8.4E + ¹³ Ω-cm (5.7 to 8.4 × 10 ¹³ Ω-cm) to 1.4 to both in Examples and Comparative Examples. 2.7E + 14 Ω-cm (1.4 to 2.7 × 10 ¹⁴ Ω-cm), which was good, but the measured values after boiling were Examples 1, 3, 5 and Comparative Examples 3, 4, 7 In Example 6 and Comparative Examples 1, 6, and 8, while the value of was favorable as 1.2 to 4.5E + ¹¹ Ω-cm (1.2 to 4.5 × 10 ¹¹ Ω-cm), It decreased by 1.2 orders of magnitude from 1.2 to 2.6E + 10 Ω-cm (1.2 to 2.6 × 10 ¹⁰ Ω-cm).
However, Comparative Example 5 in which the volume resistivity after boiling was further greatly reduced was a diallyl phthalate molding material using polyethylene powder “Flocene UF20S” as a low shrinkage agent, and the value was <2. It was 5E + 7 Ω-cm (<2.5 × 10 ⁷ Ω-cm), which was below the lower limit of measurement of a superinsulation measuring instrument that cannot be said to be an insulator.

  On the other hand, the arc resistance and tracking resistance all showed very good values in all Examples and Comparative Examples. All arc resistance was 180 seconds or more, and tracking resistance was 600 V or more.

  Also, all the examples and comparative examples showed good values in terms of dielectric constant and dielectric loss tangent, and the dielectric constant was in the range of 4.7 to 5.1 and the dielectric loss tangent was in the range of 0.014 to 0.026. It was.

As described above, Example 1 in which diallyl phthalate was used as a polymerizable monomer and a styrene copolymer having a weight average molecular weight of 50,000 to 500,000 was used as a low shrinkage agent as described above. -6 is excellent in kneadability, flash point, viscosity, fluid storage stability, and curing characteristics as characteristics of the molding material itself, and the amount of residual styrene, appearance, shrinkage, surface as characteristics of the molded product after molding In terms of properties and various physical properties, it was an excellent diallyl phthalate-based molding material that had never been obtained.
In particular, since diallyl phthalate is used as the polymerizable monomer, there is no emission or evaporation of styrene, and it effectively acts as a measure against VOC (volatile organic compounds) and as a measure against bad odor.
In addition, these techniques can be widely applied not only to unsaturated polyester resin molding materials that do not emit styrene and molded articles thereof, but also to unsaturated polyester resins that do not emit styrene.
Further, since the flash point is surely greatly improved, the explosion-proof equipment in the production factory is unnecessary, and a great economic efficiency can be realized.

Claims (9)

In the unsaturated polyester resin molding composition comprising an unsaturated polyester resin, a polymerizable monomer, a low shrinkage agent and a curing agent, the polymerizable monomer is diallyl phthalate, and the low shrinkage agent is a weight average. A low shrinkable unsaturated polyester resin molding material composition comprising a styrene copolymer having a molecular weight of 50,000 to 500,000. 2. The low shrinkable unsaturated polyester resin molding composition according to claim 1, wherein the molar ratio of the polybasic acid of the unsaturated polyester resin is in the range of unsaturated polybasic acid: saturated polybasic acid = 100: 0 to 50:50. object. The low shrinkable unsaturated polyester resin molding material composition according to claim 1 or 2, wherein the low shrinkage agent comprises a copolymer of a styrene monomer and an acrylic acid monomer. The low shrinkage unsaturated polyester resin molding material according to any one of claims 1 to 3, wherein the low shrinkage agent comprises a copolymer of 50 to 80% by weight of a styrene monomer and 50 to 20% by weight of an acrylic acid monomer. Composition. The low-shrinkage unsaturated polyester resin molding material composition according to any one of claims 1 to 4, wherein the low-shrinkage agent comprises a copolymer of styrene and butyl acrylate. The curing agent is composed of at least one organic peroxide selected from organic peroxides having a half-life temperature of 160 ° C. or higher for 1 minute and organic peroxides having a half-life temperature of 1 minute to 130 ° C. to less than 160 ° C. The low shrinkable unsaturated polyester resin molding material composition according to any one of claims 1 to 5, comprising two or more organic peroxides comprising at least one selected from the inside. (A) The unsaturated polyester resin contains 40 to 60 parts by weight as a solid ester part, (B) 40 to 60 parts by weight of a polymerizable monomer, and (C) 5 to 20 parts by weight of a low shrinkage agent as a resin component. The low-shrinkable unsaturated polyester resin molding material composition according to any one of claims 1 to 6. (A) Solid ester portion of unsaturated polyester resin, (B) polymerizable monomer, (C) resin component consisting of low shrinkage agent {(A) + (B) + (C)} 100 parts by weight 0.5 to 5 parts by weight of a curing agent, 0.05 to 1 part by weight of a thickener, 1 to 5 parts by weight of a release agent, 0.005 to 0.1 parts by weight of a polymerization inhibitor, and 20 to 100 of a reinforcing material. The low shrinkable unsaturated polyester resin molding material composition according to any one of claims 1 to 7, comprising 0 part by weight, 0 to 300 parts by weight of a filler, and 0 to 20 parts by weight of other additives. A molded article formed by molding the low shrinkable unsaturated polyester resin molding material composition according to claim 1.