JP2016132770A - Molding material for heat compression molding and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material for heat compression molding good in moldability as appropriate flow resistance are generated during molding, capable of providing a molded article having good appearance even with long term storage and excellent in storage stability.SOLUTION: A molding material for heat compression molding obtained by impregnating a resin composition (A) containing an unsaturated polyester resin (a1), a radical polymerizable diluent (a2), alcohol having 2 hydroxyl groups in a molecule (a3), alcohol having 3 or more hydroxyl groups in a molecule (a4), magnesium oxide and a polymerization initiator into a glass fiber (B), where the resin composition (A) contains 100 pts.mass of the unsaturated polyester resin (a1), 0.1 to 1.0 pts.mass of the alcohol (a3), 0.02 to 0.5 pts.mass of the alcohol (a4) and 0.1 to 5 pts.mass of the magnesium oxide, is used.SELECTED DRAWING: None

Description

  The present invention relates to a molding material for heat compression molding having excellent appearance quality of a molded product obtained by a heat compression molding method and good long-term storage stability, and the molded product thereof.

  In general, sheet molding compound (SMC), which is made of unsaturated polyester resin as matrix resin, and bulk molding compound called bulk molding compound (BMC) are used in bathtubs, bathrooms, waterproof pans and kitchen counters. -Widely used in housing equipment members such as wash counters, septic tank members, water tank panel members, automobile members, railway vehicle members, ship members, electrical members, construction / civil engineering materials members, etc.

SMC is a set of two resin compound layers in which a liquid resin compound consisting of a matrix resin, inorganic filler, curing agent, thickener, and other additives is applied to a carrier film with a constant thickness by a doctor knife coater method. The fiber reinforcement made of glass fiber, carbon fiber, etc. cut to a length of 0.5 to 3 inches is sandwiched between them, the fiber reinforcement is impregnated with resin compound, and then the resin compound is thickened to handle It is obtained as a sheet-shaped molding material excellent in the above. This resin compound is required to be in a liquid state when applied to a carrier film with a certain thickness and to thicken after being impregnated into a fiber reinforcement (B-stage formation). These sheet-shaped molding materials are sometimes referred to as prepregs.
On the other hand, BMC is mixed with a matrix resin, an inorganic filler, a curing agent, a thickener, other fillers, and a relatively short cut fiber reinforcing material called chopped strands to increase the viscosity. In this way, it is obtained as a massive molding material.

  Examples of the molding method of the SMC and BMC include a heat compression molding method and an injection molding method. The heat compression molding method is a method of using a press machine to insert SMC or BMC into a mold heated to a high temperature and closing the mold, and then curing the resin in the mold to obtain a molded product. It is. The injection molding method is a method of obtaining a molded product by injecting SMC or BMC having a normal temperature to a medium temperature into a high-temperature mold using an injection molding machine and then curing the resin in the mold.

  As the matrix resin of SMC and BMC, an unsaturated polyester resin having a carboxylic acid group is often used to increase the viscosity by reacting carboxylic acid and magnesium oxide from the viewpoint of mass productivity and cost of molding materials. . The thickening reaction between the carboxylic acid and magnesium oxide is affected by moisture and gradually proceeds with the passage of time, so that these molding materials have a drawback that the product life is short.

  When the SMC and BMC molding materials are subjected to heat compression molding or injection molding, air may be involved in the compound to cause appearance defects such as pinholes on the surface of the molded product. The stronger the thickening reaction, the higher the flow resistance of the compound during molding, making it difficult to entrain air. Therefore, the pinhole defect is less likely to occur, but if the thickening reaction is too strong, the production of SMC and BMC Sometimes the resin compound is not sufficiently impregnated into the glass fiber, and conversely, pinholes are often generated during molding, or the flow resistance during molding is too high and the compound and glass fiber do not flow to the mold end. There is a case where a defect called as occurs. On the other hand, if the thickening reaction is too weak, the flow resistance of the compound at the time of molding becomes low, which makes it easy to entrain air and the above-mentioned pinhole failure easily occurs. In addition, the compound and glass fiber are mixed together. In some cases, the glass content of the product terminal is low, and cracks and cracks may occur.

  The thickening reaction of carboxylic acid groups and magnesium oxide in the unsaturated polyester resin proceeds with time when stored at room temperature, so SMC and BMC are inferior in storage stability and have a short product life. Have That is, it has been difficult to obtain molding materials for SMC and BMC that have good heat compression moldability or injection moldability and excellent storage stability.

  For such a problem, for example, it contains an unsaturated polyester resin, a low shrinkage agent, a thickening agent, a thickening stabilizer, a filler and a fiber reinforcing material, and the thickening stabilizer has a hydroxyl group (meta) SMC, which is an acrylate and whose amount is 0.2 to 20 parts by weight with respect to a total of 100 parts by weight of an unsaturated polyester resin and a low shrinkage agent, has been proposed (Patent Document 1). However, if the thickening stabilizer is added within the above range, the thickening reaction is too early, and the impregnation property of the compound into the glass fiber deteriorates during SMC production, so that pinholes are generated due to air entrainment during heat compression molding. And a problem that the glass fibers are unevenly distributed on the surface of the molded product due to excessive flow resistance at the time of molding, and it is difficult to obtain a molded product with a good appearance.

  Further, 0.05 to 10 weight percent of an alcohol compound having a hydroxyl group which is a moisture adsorbent and a thickening initiator with respect to the total amount of unsaturated polyester resin, polymerizable monomer, low shrinkage agent, curing agent and filler. % SMC has been proposed (Patent Document 2). However, with this SMC, the handleability is good, but the heat compression moldability and storage stability are insufficient.

JP-A-8-104800 Japanese Patent Laid-Open No. 2003-213020

  The problem to be solved by the present invention is a heat compression molding that has good moldability because of proper flow resistance at the time of molding, and can obtain a molded product having a good appearance even when stored for a long period of time. Is to provide a molding material.

  The present inventors are for heat compression molding obtained by impregnating glass fibers with a resin composition containing an unsaturated polyester resin, a radical polymerizable diluent, a specific alcohol, magnesium oxide and a polymerization initiator in a specific ratio. The present inventors have found that the molding material is excellent in moldability and storage stability and completed the present invention.

  That is, unsaturated polyester resin (a1), radical polymerizable diluent (a2), alcohol having two hydroxyl groups in one molecule (a3), alcohol having three or more hydroxyl groups in one molecule (a4), oxidation A molding composition for heat compression molding obtained by impregnating glass fiber (B) with a resin composition (A) containing magnesium and a polymerization initiator, wherein the resin composition (A) is unsaturated. 0.1 to 1.0 part by mass of the alcohol (a3), 0.02 to 0.5 part by mass of the alcohol (a4), and 0.02 to 0.5 parts by mass of the magnesium oxide with respect to 100 parts by mass of the polyester resin (a1). It is related with the molding material for heat compression molding characterized by containing 1-5 mass parts.

  The molding material for heat compression molding of the present invention is excellent in storage stability and has high flow resistance at high temperature, so that appearance defects such as pinholes at the time of heat compression molding hardly occur and the surface appearance is good. Therefore, in addition to housing equipment members such as bathtubs and kitchen counters that are commonly used for SMC and BMC applications, applications that require the appearance quality of automobile members, ship members, aircraft members, etc., and applications that apply to the surface of molded products It can use suitably for.

  The molding material for heat compression molding of the present invention comprises an unsaturated polyester resin (a1), a radical polymerizable diluent (a2), an alcohol having two hydroxyl groups in one molecule (a3), and three or more in one molecule. A molding material for heat compression molding obtained by impregnating a glass fiber (B) with a resin composition (A) containing a hydroxyl group-containing alcohol (a4), magnesium oxide, and a polymerization initiator, wherein the resin composition The product (A) is 0.1 to 1.0 part by mass of the alcohol (a3) and 0.02 to 0.5 part of the alcohol (a4) with respect to 100 parts by mass of the unsaturated polyester resin (a1). It contains 0.1 to 5 parts by mass of the magnesium oxide.

  First, the resin composition (A) will be described. The resin composition (A) comprises an unsaturated polyester resin (a1), a radical polymerizable diluent (a2), an alcohol (a3) having two hydroxyl groups in one molecule, and three or more hydroxyl groups in one molecule. It contains alcohol (a4), magnesium oxide, and a polymerization initiator.

  The unsaturated polyester resin (a1) is an unsaturated polyester resin obtained by condensation polymerization of a polybasic acid component and a polyhydric alcohol component, and has an acid value in the range of 5 to 40 (mgKOH / g). However, it is preferable because the fluidity during high-temperature molding of the present invention is good and the storage stability is excellent, and the acid value is more preferably in the range of 10 to 30 (mgKOH / g).

  Examples of the polybasic acid component used as a raw material for the unsaturated polyester resin (a1) include maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these dibasic acids, adipic acid, sebacic acid, succinic acid, Examples include gluconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, and chlorendic anhydride. These polybasic acid components can be used alone or in combination of two or more.

  Examples of the polyhydric alcohol component that is a raw material of the unsaturated polyester resin (a1) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4- Butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, hydrogenated bisphenol A, dioxyethylene glycol, trioxyethylene glycol, dioxypropylene glycol, trioxy Examples include propylene glycol, octyl alcohol, oleyl alcohol, and trimethylolpropane. These polyhydric alcohol components can be used alone or in combination of two or more.

  Examples of the radical polymerizable diluent (a2) include vinyl monomers such as styrene and α-methylstyrene; (meth) acrylate monomers such as methyl (meth) acrylate and butyl (meth) acrylate, and the like. Is mentioned. These polymerizable unsaturated monomers can be used alone or in combination of two or more.

  In the present invention, the notation “(meth) acryl” represents one or both of “acryl” and “methacryl”.

  The addition amount of the radical polymerizable diluent (a2) may be appropriately adjusted for adjusting the viscosity of the resin composition (A), and is not particularly limited, but is a molding material for heat compression molding such as SMC. However, the range of 50 to 150 parts by mass is preferable with respect to 100 parts by mass of the unsaturated polyester resin (a1), and the range of 80 to 120 parts by mass is preferable. More preferred.

  Since the unsaturated polyester resin (a1) has a high viscosity, it is preferably diluted with the radical polymerizable diluent (a2) before mixing with the other components. Specifically, it is preferable to dilute with 50 to 100 parts by mass of the radical polymerizable diluent (a2) with respect to 100 parts by mass of the unsaturated polyester resin (a1).

  Although it does not specifically limit as alcohol (a3) which has two hydroxyl groups in the said molecule | numerator, For example, ethylene glycol, propylene glycol, butanediol, octanediol, hexanediol, bisphenol A etc. are mentioned. In particular, propylene glycol is preferred because the effects of the present invention are high and the resulting molded article has little discoloration.

  The alcohol (a4) having three or more hydroxyl groups in one molecule is not particularly limited, but trivalent alcohols such as glycerin and trimethylolpropane, tetrahydric alcohols such as pentaerythritol, saccharides such as dextrin, polyvinyl alcohol, and the like. And water-soluble polymers such as these, and derivatives thereof. Among these, trivalent alcohols such as trimethylolpropane and glycerin are preferable, and glycerin is particularly preferable because of good compatibility with the unsaturated polyester resin (a1) and the radical polymerizable diluent (a2). Further, since tetrahydric or higher alcohols and water-soluble polymers have high polarity and are often incompatible with the radical polymerizable diluent (a2), those obtained by alkoxylating a part of the hydroxyl groups are preferable. For example, what substituted some hydroxyl groups which polysaccharides, such as a cyclodextrin, have with a methoxy group is mentioned.

  The alcohol (a3) may be the same as the polyhydric alcohol component that is the raw material of the unsaturated polyester resin (a1), but generally the residual amount of polyhydric alcohol during the production of the unsaturated polyester is It is less than 0.1 parts by mass with respect to 100 parts by mass of the saturated polyester resin, and the alcohol (a3) and the alcohol (a4) of the present invention are not residues at the production of the unsaturated polyester resin (a1).

  Further, water or a monohydric alcohol such as methanol, ethanol or isopropyl alcohol can accelerate the thickening reaction between the carboxylic acid group and the magnesium oxide in the unsaturated polyester resin. Since the boiling point is lower than the molding temperature of the molding material, it is difficult to control the fluidity at high temperatures.

  The resin composition (A) contains 0.1 to 1.0 part by mass of the alcohol (a3) with respect to 100 parts by mass of the unsaturated polyester resin (a1). When the alcohol (a3) is less than the above range, the thickening reaction between the carboxylic acid and the magnesium oxide in the unsaturated polyester resin becomes insufficient, and the handling property (such as stickiness) as a molding material is deteriorated, or at high temperature The flow resistance of the resin becomes insufficient, and the heat compression moldability may deteriorate. On the other hand, if the amount exceeds the above range, the thickening reaction is too strong and the handling properties (cutting properties, etc.) as a molding material deteriorate, and conversely, a phenomenon called a thickening return occurs with the passage of time, resulting in handling properties. (Stickiness, etc.) may deteriorate.

  The resin composition (A) contains 0.02 to 0.5 parts by mass of the alcohol (a4) with respect to 100 parts by mass of the unsaturated polyester resin (a1). When the alcohol (a4) is less than the above range, the thickening reaction between the carboxylic acid and the magnesium oxide in the unsaturated polyester resin becomes insufficient, and handling properties (such as stickiness) as a molding material deteriorate, The flow resistance at the time becomes insufficient, and the heat compression moldability may deteriorate. On the other hand, if the amount is more than the above range, the thickening reaction is too strong and the handling properties (cutting properties, etc.) as a molding material are deteriorated, or the flow resistance at high temperature is too high, resulting in poor appearance or , Storage stability may deteriorate.

The alcohol (a4) is in the range of 10 to 70 parts by mass with respect to 100 parts by mass of the alcohol (a3), the handling property as a molding material and the appearance of the molded product are good, and It is preferable because of excellent storage stability.

Content of the said magnesium oxide in the said resin composition (A) is the range of 0.1-5 mass parts with respect to 100 mass parts of said unsaturated polyester resins (a1). If the amount is less than the above range, the thickening reaction may be insufficient in the previous period and handling properties (stickiness, etc.) as a molding material may be deteriorated, or the flow resistance at high temperatures may be insufficient and the heat compression moldability may be deteriorated. On the other hand, if the amount is more than the above range, the thickening reaction is too strong and the handling properties as a molding material (cutting properties, etc.) are deteriorated, or the flow resistance is too high at high temperatures to cause poor appearance, Storage stability may deteriorate. From the viewpoint of improving these performances, the magnesium oxide content is preferably in the range of 0.3 to 3 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a1).

  The polymerization initiator is not particularly limited, but is preferably an organic peroxide, such as a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl perester compound, a carbonate compound, and the like. And can be appropriately selected according to the molding conditions. These polymerization initiators can be used alone or in combination of two or more. These polymerization initiators are preferably contained in an amount of 0.4 to 4.0 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a1).

The resin composition (A) includes the unsaturated polyester resin (a1), the radical polymerizable diluent (a2), the alcohol (a3), the alcohol (a4), the magnesium oxide, and the polymerization initiator. Resin having radical polymerizable unsaturated bond and carboxylic acid group, low shrinkage agent, inorganic filler, polymerization inhibitor, mold release agent, pigment, viscosity reducer, anti-aging agent, plasticizer, flame retardant , Antibacterial agents, stabilizers, reinforcing materials, photocuring agents, and the like.

The resin having a radically polymerizable unsaturated bond and a carboxylic acid group in the resin composition (A) is a vinyl ester resin (epoxy acrylate resin), a phenol resin, a melamine resin, a furan resin, or the like, and has a carboxylic acid group. Things.

  Examples of the low shrinkage agent in the resin composition (A) include nylon resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, and copolymers thereof. And thermoplastic resins such as resins modified by the above. Among these, a polystyrene resin, a styrene-acrylic acid copolymer, a styrene-vinyl acetate copolymer, a styrene-butadiene copolymer, a styrene-olefin copolymer, and a poly (meth) acrylic acid ester are preferable. These low shrinkage agents can be used alone or in combination of two or more.

  When the low shrinkage agent is added, since these thermoplastic resins are solid, it may be diluted in advance with the radical polymerizable diluent (a2) within a range that does not impair the effects of the present invention. preferable. Specifically, it is preferable to dilute with 100 to 300 parts by mass of the radical polymerizable diluent (a2) with respect to 100 parts by mass of the thermoplastic resin.

  Since the content of the low shrinkage agent in the resin composition (A) of the present invention is good in heat compression moldability and the appearance of the resulting molded product, 100 parts by mass of the unsaturated polyester resin (a1). Is preferably 100 parts by mass or less, and more preferably 60 parts by mass or less.

  Examples of the inorganic filler in the resin composition (A) include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, and dolomite limestone. , Gypsum, aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide, cryolite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder, carbon black and the like. These inorganic fillers can be used alone or in combination of two or more.

  Further, the content of the inorganic filler in the resin composition (A) is not particularly limited, and may be appropriately adjusted from the heat compression moldability and the appearance of the obtained molded product. The range of 100-500 mass parts is preferable with respect to 100 mass parts of said unsaturated polyester resin (a1) from the balance of an external appearance.

  Examples of the polymerization inhibitor in the resin composition (A) include hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, and naphthene. Examples include acid copper and copper chloride. These polymerization inhibitors can be used alone or in combination of two or more. These polymerization inhibitors are preferably contained in an amount of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a1).

Examples of the release agent in the resin composition (A) include stearic acid, magnesium stearate, zinc stearate, calcium stearate, paraffin wax, polyethylene wax, and carnauba wax. These mold release agents can be used alone or in combination of two or more.

Examples of the glass fiber (B) include fibers obtained by cutting long fibers called roving, short fibers called chopped strands that have been cut short in advance. Further, glass fibers in a plain weave, satin weave, non-woven fabric, or mat shape can be used. These glass fibers can be used alone or in combination of two or more.

  As the kind of the glass fiber (B), for example, E glass, C glass, R glass, AR glass, low boron content glass, etc., with a fiber diameter of 10 to 25 μm and a linear density of 1000 to 5000 g / km (TEX) ) Or the like converged at (). Moreover, as a sizing agent (sizing agent), it is preferable to use together thermoplastic resins, such as an acrylic resin, a urethane resin, a vinyl resin, and a silane coupling agent, for example.

  The molding material for heat compression molding of the present invention is obtained by impregnating the glass fiber (B) with the resin composition (A), but the glass fiber (B in the molding material for heat compression molding is used. ) Content is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass, since the strength and surface smoothness of the resulting molded product are further improved.

  In addition, the molding material for heat molding of the present invention is preferably a sheet molding compound (SMC) or a bulk molding compound (BMC) from the viewpoint of handling as a molding material and moldability.

  As a method for producing the SMC, the unsaturated polyester resin (a1), the radical polymerizable diluent (a2), a mixer such as a normal roll, an intermixer, a planetary mixer, a kneader, and an extruder are used. Each component of the resin composition (A) such as the alcohol (a3), the alcohol (a4), the magnesium oxide, and the polymerization initiator is mixed and dispersed, and a uniform thickness is formed on the carrier film installed above and below. The glass fiber (B) that has been coated and cut to a predetermined length is sandwiched between the resin compounds of the carrier film placed above and below, and then the whole is passed between impregnating rolls to apply pressure. After impregnating the fiber reinforcing material with the resin compound, the SMC is obtained by winding it in a roll or folding it into a spell. This is followed by aging as necessary. When a thickener is blended, aging is preferably performed at a temperature of 25 to 60 ° C. As the carrier film, a polyethylene film, a polypropylene film, a nylon film, and a multilayer film thereof can be used. In the case of SMC, the length of the glass fiber (B) is preferably in the range of 10 to 60 mm from the viewpoint of the cutability of the glass fiber itself and the impregnation property with the resin composition (A). Moreover, you may mix the glass fiber of different length.

  As the method for producing the BMC, similarly to the method for producing the SMC, the unsaturated polyester resin component (a1), using a mixer such as a normal roll, an intermixer, a planetary mixer, a kneader, and an extruder, After the resin composition (A) containing the radical polymerizable diluent (a2), the alcohol (a3), the alcohol (a4), the magnesium oxide, the polymerization initiator, and the like is dispersed, A method of mixing and dispersing the glass fiber (B) is preferable. In the case of BMC, it is preferable to use a relatively short fiber as the glass fiber (B) from the viewpoint of dispersibility, for example, in the range of 5 to 13 mm in length.

  The molded product of the present invention can be obtained from the molding material for heat molding, but the molding method is not particularly limited, and examples thereof include a heat compression molding method and an injection molding method. Among these, the heat compression molding method of SMC or BMC is preferable from the viewpoint of handling as a molding material and moldability.

  As the heat compression molding method, for example, a predetermined amount of a molding material such as SMC and BMC is weighed, put into a mold heated in advance to 110 to 180 ° C., clamped by a press molding machine, and the molding material is A manufacturing method is used in which the molding material is cured by holding the molding pressure of 0.1 to 20 MPa and then the molding material is cured, and then the molded product is taken out. In this case, in a mold having a shear edge, at a mold temperature of 120 to 160 ° C., a prescribed time of 1 to 2 minutes per 1 mm of the thickness of the molded product is maintained, and a molding pressure of 1 to 15 MPa is maintained. The manufacturing method is preferred.

  The molding material for heat compression molding of the present invention can be molded by an injection molding method. As the injection molding method, for example, a molding material such as SMC and BMC is put into a hopper of an injection molding machine, and a cylinder temperature of 30 to 60 ° C. and a mold heated in advance to 110 to 180 ° C. are injected with an injection pressure of 1 A production method is used in which injection molding is performed at an injection pressure of ˜20 MPa and a holding pressure of 0.2 to 5 MPa, the molding material is cured by holding for 0.2 to 3 minutes, and then the molded product is taken out to obtain a molded product.

  The molding material for heat compression molding of the present invention is excellent in storage stability and has high flow resistance at high temperature, so that appearance defects such as pinholes at the time of heat compression molding hardly occur and the surface appearance is good. Therefore, in addition to housing equipment members such as bathtubs and kitchen counters that are commonly used for SMC and BMC applications, applications that require the appearance quality of automobile members, ship members, aircraft members, etc., and applications that apply to the surface of molded products It can use suitably for.

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

(Production Example 1: Production of Resin Composition (A-1))
A mixture of 100 parts by weight of unsaturated polyester resin (a1-1) and 69.5 parts by weight of styrene (“PS-520” manufactured by DH Material Co., Ltd.), 169.5 parts by weight, 8.2 parts by weight of polystyrene resin and styrene 15.2 parts by mass of a mixture (“PS-954N” manufactured by DH Material Co., Ltd.) 23.4 parts by mass, 254 parts by mass of calcium carbonate (average particle size 1.1 μm), propylene glycol 0.4 parts by mass, glycerin 0 2 parts by weight, 2 parts by weight of magnesium oxide, 2 parts by weight of a polymerization initiator (1) (“Kaya-Carbon BIC-75” manufactured by Kayaku Akzo Co., Ltd.) and 7 parts by weight of zinc stearate are mixed with a dissolver to obtain a resin composition (A-1) 458.5 parts by mass were obtained. The total amount of styrene in the resin composition (A-1) was 84.7 parts by mass.

(Production Example 2: Production of Resin Composition (A-2))
Resin composition (A-2) 458.5 by operating in the same manner as in Production Example 1 except that 0.2 parts by mass of glycerin used in Production Example 1 was changed to 0.2 parts by mass of trimethylolpropane. A mass part was obtained.

(Production Example 3: Production of Resin Composition (A-3))
By operating in the same manner as in Production Example 1 except that 0.2 parts by mass of glycerin used in Production Example 1 was changed to 0.2 parts by mass of methylated-β-cyclodextrin (manufactured by Junsei Chemical Co., Ltd.), 458.5 mass parts of resin compositions (A-3) were obtained.

(Production Example 4: Production of Comparative Resin Composition (RA-1))
Resin composition (RA-1) 457.9 masses by operating in the same manner as in Production Example 1 except that 0.4 parts by mass of propylene glycol and 0.2 parts by mass of glycerin used in Production Example 1 were not used. Got a part.

(Production Example 5: Production of comparative resin composition (RA-2))
458.3 mass parts of resin compositions (RA-2) were obtained by operating like the manufacture example 1 except not having used 0.2 mass part of glycerol used in the manufacture example 1. FIG.

(Production Example 6: Production of comparative resin composition (RA-3))
By operating in the same manner as in Production Example 1 except that 0.4 parts by mass of propylene glycol used in Production Example 1 was not used and 0.2 parts by mass of glycerin was changed to 0.4 parts by mass, the resin composition ( RA-3) 458.3 parts by mass were obtained.

(Production Example 7: Production of comparative resin composition (RA-4))
By using the same procedure as in Production Example 1 except that 0.4 parts by mass of propylene glycol used in Production Example 1 was not used and 0.2 parts by mass of glycerin was changed to 2 parts by mass, a comparative resin composition ( RA-4) 459.9 parts by mass were obtained.

  Table 1 shows the compositions of the resin compositions (A-1) to (A-3) and (RA-1) to (RA-4) obtained above.

(Example 1: Production and evaluation of molding material (1) for heat compression molding)
458.5 parts by mass of the resin composition (A-1) obtained in Production Example 1 was applied on two polypropylene carrier films installed one above the other so as to have a uniform thickness, to 25.4 mm. 153 parts by weight of the cut glass fiber (B-1) (“PG-571” manufactured by Nitto Boseki Co., Ltd.) is sandwiched between the resin compositions on the carrier film placed above and below, and the whole is sandwiched between impregnation rolls. The resin composition (A-1) is impregnated into the glass fiber (B-1) by applying pressure through it, then cured at 45 ° C. for 24 hours, and the glass fiber content is 25% by mass for compression molding. Material (1) was obtained. The unit weight of the molding material (1) for heat compression molding was 34.3 N / m ² .

  The molding material for heat compression molding (1) obtained above was stored at 25 ° C. after preparation, and the following evaluation was performed after 1 week (initial) and 1 month (after long-term storage).

[High-temperature fluidity evaluation]
Using a flow tester CFT-500D manufactured by Shimadzu Corporation, the high-temperature fluidity evaluation of the molding material for heat compression molding (1) obtained above was performed. Using a nozzle diameter of 2.095 mm (nozzle length of 8 mm), cut the molding material for heat compression molding (1) into about 5 mm square, and set the sample adjusted to a weight of 3.7 g in a cylinder heated to 60 ° C. Then, after holding at an applied load of 15 kgf for 2 minutes, the sample is heated at a heating rate of 6 ° C./min, the shear rate when the sample is discharged from the nozzle tip is measured, and the peak temperature at which the shear rate reaches the maximum value is measured. Recorded. One sample was measured three times, and the peak temperature was calculated from the average value of the three times.
The shear rate peak temperature of the initial molding material for heat compression molding (1) was compared with the shear rate peak temperature after long-term storage, and the storage stability was evaluated according to the following criteria.
〔Evaluation criteria〕
○: Change in the peak temperature of the shear rate is less than 5 ° C Δ: Change in the peak temperature of the shear rate is not less than 5 ° C and less than 10 ° C ×: Change in the peak temperature of the shear rate is not less than 10 ° C

[Production of molded plate]
The molding material (1) for heat compression molding obtained in Example 1 was cut into 250 × 250 mm, and the sample was adjusted so that a total of 650 g was obtained by stacking three sheets, and the sample was placed in the center of a 300 × 300 mm mold. The plate was placed and heat compression molded to obtain a 4 mm thick flat plate (1). The heat compression molding conditions were a mold temperature (lower) of 130 ° C./(upper) 145 ° C., a keeping time of 6 minutes, and a pressure of 10 MPa.

[Appearance (formability) evaluation]
The surface of the resulting molded plate (1) was lightly coated with a black aqueous magic, and then thoroughly wiped with a cloth soaked with isopropyl alcohol to confirm the occurrence of pinholes.
〔Evaluation criteria〕
○: No pinhole and surface gloss is good.
(Triangle | delta): It corresponds to either of these which has a little pinhole and surface gloss is a little inferior.
X: There is a pinhole, the surface gloss is inferior, the color tone is clearly yellowed, and any of these.

(Examples 2-3: Production and evaluation of molding materials (2) to (3) for heat compression molding)
Glass fiber-containing by operating in the same manner as in Example 1 except that the resin composition (A-1) used in Example 1 was changed to resin compositions (A-2) to (A-3). Molding materials (2) to (3) for heat compression molding having a rate of 25% by mass were obtained. The unit weight of these molding materials for heat compression molding (2) to (3) was 34.3 N / m ² .

  The same operation as in Example 1 is performed except that the molding material for heat compression molding (1) used in Example 1 is changed to the molding material for heat compression molding (2) to (3) obtained above. Thus, the high temperature fluidity and the appearance of the molded plate were evaluated.

(Comparative Examples 1-4: Production and Evaluation of Molding Materials for Heat Compression Molding (R-1) to (R-4))
By operating in the same manner as in Example 1 except that the resin composition (A-1) used in Example 1 was changed to resin compositions (RA-1) to (RA-4), the glass fiber content rate 25% by mass of molding materials (R-1) to (R-4) for heat compression molding were obtained. The unit weight of these heat compression molding materials (R-1) to (R-4) was 34.3 N / m ² .

  Except for changing the heat compression molding material (1) used in Example 1 to the heat compression molding materials (R-1) to (R-4) obtained above, the same as in Example 1. The high temperature fluidity and the appearance of the molded plate were evaluated.

  Table 2 shows the evaluation results of the molding materials for heat compression molding (1) to (3) and (R-1) to (R-4) obtained above.

  It turned out that the molding materials (1) to (3) for heat compression molding of Examples 1 to 3 have small changes in high-temperature fluidity with time, excellent storage stability, and good appearance of the molded products.

  On the other hand, Comparative Example 1 is an example in which the resin composition (A) does not contain an alcohol (a3) having two hydroxyl groups in one molecule and an alcohol (a4) having three or more hydroxyl groups in one molecule. However, the change in high-temperature fluidity with time was large and the storage stability was poor. In addition, some pinholes occur in the molded product obtained from the one-week storage product, and the appearance (moldability) is insufficient. The molded product obtained from the one-month storage product has a slightly inferior surface gloss, and the appearance (glossy). Was insufficient.

  Comparative Example 2 is an example in which the resin composition (A) does not contain an alcohol (a4) having three or more hydroxyl groups in one molecule, but the change in high-temperature fluidity with time is large and storage stability is poor. The appearance (gloss) of the molded product obtained from the one-month storage product was poor.

  Comparative Example 3 is an example in which the resin composition (A) does not contain an alcohol (a3) having two hydroxyl groups in one molecule, but a molded product obtained from a one-month storage product has a poor appearance (gloss). Met.

  Comparative Example 4 is an example in which the resin composition (A) does not contain an alcohol (a3) having two hydroxyl groups in one molecule and contains a large amount of an alcohol (a4) having three or more hydroxyl groups in one molecule. However, since the flow resistance is too high, the high temperature fluidity could not be evaluated. Further, the molded product obtained had a poor appearance (remarkably yellowing). Furthermore, the molded product obtained from the long-term storage product also had a poor appearance (glossy and marked yellowing).

Claims (4)

  Unsaturated polyester resin (a1), radical polymerizable diluent (a2), alcohol having two hydroxyl groups in one molecule (a3), alcohol having three or more hydroxyl groups in one molecule (a4), magnesium oxide, And a resin composition (A) containing a polymerization initiator, which is obtained by impregnating glass fibers (B) into a heat compression molding material, wherein the resin composition (A) is the unsaturated polyester resin. (A1) 0.1 to 1.0 parts by mass of the alcohol (a3), 0.02 to 0.5 parts by mass of the alcohol (a4), and 0.1 to 0.1 parts of the magnesium oxide with respect to 100 parts by mass. A molding material for heat compression molding comprising 5 parts by mass.   The molding material for heat compression molding according to claim 1, wherein the alcohol (a3) is propylene glycol.   A molded product obtained by molding the molding material for heat compression molding according to claim 1 or 2.   The molded article according to claim 3, which is obtained by a heat compression molding method of sheet molding compound (SMC) or bulk molding compound (BMC).