JP2022067272A - Molding material, molded article, and artificial marble - Google Patents

Abstract

To provide a molding material from which a molded article excellent in whiteness, transparency, glossiness, and image clarity is obtained, the molded article, and artificial marble.SOLUTION: Essential raw materials of a molding material are a polymer component (A) containing an unsaturated polyester (a1), an unsaturated monomer (B), a hardener (C), a thickener (D), an inorganic filler (E) containing a hollow filler (e1) and glass powder (e2), and glass fiber (F) of a fiber length of 1.5-6 mm. The inorganic filler (E) is 150-400 pts.mass to 100 pts.mass of the total amount of the polymer component (A) and the unsaturated monomer (B). The hollow filler (e1) is 0.3-10 mass% in the inorganic filler (E).SELECTED DRAWING: None

Description

The present invention relates to molding materials, molded products, and artificial marble.

Conventionally, a resin composition based on a thermosetting resin such as an unsaturated polyester resin or a vinyl ester resin is molded and cured to manufacture artificial marble products such as counters, washbasins, and bathtubs.

Under these circumstances, as a composition suitable for artificial marble having excellent transparency, an unsaturated polyester resin composition in which an unsaturated polyester, a copolymerizable monomer, a crosslinkable polymer particle, and an inorganic filler are mixed has been proposed. (See, for example, Patent Document 1).

However, in applications where higher designability is required, there is a problem that the molded product obtained from this composition has insufficient whiteness, transparency, mapability and the like.

Japanese Unexamined Patent Publication No. 9-302009

An object to be solved by the present invention is to provide a molding material, a molded product thereof, and artificial marble, which can obtain a molded product having excellent whiteness, transparency, gloss, and imageability.

As a result of diligent research to solve the above problems, the present inventors have made a molding material containing a specific polymer component, an unsaturated monomer, a curing agent, a thickener, an inorganic filler, and glass fiber as essential raw materials. From this, it was found that a molded product and artificial marble having excellent whiteness, transparency, luster, and imageability could be obtained, and the present invention was completed.

That is, in the present invention, the polymer component (A) containing the unsaturated polyester (a1), the unsaturated monomer (B), the curing agent (C), the thickener (D), the hollow filler (e1) and the glass powder. A molding material containing the inorganic filler (E) containing (e2) and the glass fiber (F) having a fiber length of 1.5 to 6 mm as essential raw materials, the polymer component (A) and the unsaturated single amount. The inorganic filler (E) is 150 to 400 parts by mass with respect to 100 parts by mass of the total amount of the body (B), and the hollow filler (e1) in the inorganic filler (E) is 0.3 to 10 parts. It relates to a molding material characterized by mass%.

Since the molding material of the present invention can obtain a molded product having excellent transparency, gloss, and imageability, bathroom members (bathroom, waterproof pan, counter, wall), washbasin counter, kitchen counter, kitchen sink, etc. It can be suitably used for housing equipment members and the like.

The molding material of the present invention includes a polymer component (A) containing an unsaturated polyester (a1), an unsaturated monomer (B), a curing agent (C), a thickener (D), a hollow filler (e1) and glass. A molding material containing an inorganic filler (E) containing a powder (e2) and a glass fiber (F) having a fiber length of 1.5 to 6 mm as essential raw materials, the polymer component (A) and the unsaturated single. The inorganic filler (E) is 150 to 400 parts by mass with respect to 100 parts by mass of the total amount of the polymer (B), and the hollow filler (e1) in the inorganic filler (E) is 0.3 to 0.3 to It is 10% by mass.

The unsaturated polyester (a1) is obtained by reacting a polybasic acid containing an unsaturated polybasic acid with a polyhydric alcohol.

Examples of the unsaturated polybasic acid include unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and maleic anhydride. Among these, the strength and heat resistance of the molded product are water resistant. Maleic acid, maleic anhydride, and fumaric acid are preferable because they are excellent in toughness, high gloss, high image quality, and transparency. These unsaturated polybasic acids can be used alone or in combination of two or more.

As the polybasic acid, examples of the saturated polybasic acid that can be used in combination with the unsaturated polybasic acid include phthalic acid, phthalic acid anhydride, phthalic acid halide, isophthalic acid, terephthalic acid, and hexahydrophthalic acid. , Hexahydrohydric acid, hexahydroterephthalic acid, hexahydroisophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic acid, tetrahydroterephthalic acid, tetrahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1, 12-Dodecanedioic acid, cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyl Saturated dibasic acids such as dicarboxylic acids can be mentioned, but among these, isophthalic acid, terephthalic acid, and phthalic acid are excellent in terms of strength, heat resistance, toughness, high gloss, high image quality, and transparency of the molded product. , Dicarboxylic acid anhydride, is preferable. These saturated polybasic acids can be used alone or in combination of two or more.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, and 1, , 6-Hexanediol, neopentyl glycol, hydride bisphenol A, 1,4-butanediol, propylene oxide or ethylene oxide adduct of bisphenol A, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane , 1,3-Propanediol, 1,2-Cyclohexaneglycol, 1,3-Cyclohexaneglycol, 1,4-Cyclohexaneglycol, 1,4-Cyclohexanedimethanol, Paraxylene glycol, Bicyclohexyl-4,4'-diol , 2,6-decalin glycol, 2,7-decalin glycol, etc. Among these, propylene glycol is excellent in strength, water resistance, heat resistance, toughness, high gloss, and high image quality of the molded product. , Neopentyl glycol and hydride bisphenol A are preferred. These polyhydric alcohols may be used alone or in combination of two or more.

The weight average molecular weight of the unsaturated polyester (a1) is 5,000 to 40,000, but the glass fiber impregnation property and kneadability after the addition of the thickener are further improved, and the moldability is more suitable. It is preferably 7,000 to 35,000, more preferably 8,000 to 30,000, because the viscosity is obtained and the appearance of the molded product is further improved. The weight average molecular weight in the present invention is a value converted into polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.

As for the solid acid value of the unsaturated polyester (a1), the initial thickening behavior is gradual, the glass fiber impregnation property and kneading property after the addition of the thickener are further improved, and a viscosity suitable for molding can be obtained. 20 to 40 mgKOH / g is preferable because the appearance of the molded product is further improved. The acid value in the present invention is a value obtained by a measuring method based on JIS K6901 (2018) 5.3.2.

The present invention contains the unsaturated polyester (a1) as the polymer component, but other polymer components such as vinyl ester (a2) can be used in combination.

The vinyl ester (a2) is obtained by reacting an epoxy resin with (meth) acrylic acid.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like. Novolak type epoxy resin, oxazolidone modified epoxy resin, glycidyl ether of phenol such as brominated epoxy resin of these resins, dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol A , Glycidyl ether of polyhydric alcohol such as diglycidyl ether of hydride bisphenol A, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4 -Alicyclic epoxy resin such as epoxycyclohexane, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ester such as dimer acid glycidyl ester, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-m -Xylenediamine, triglycidyl-p monoaminophenol, glycidylamine such as N, N-diglycidylaniline, 1,3-diglycidyl-5,5-dimethylhydantin, heterocyclic epoxy resin such as triglycidylisocyanurate, etc. Can be mentioned. Among these, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable because the balance between the fluidity of the molding material at the time of molding and the strength, transparency and gloss of the molded product is further improved. These epoxy resins may be used alone or in combination of two or more.

The epoxy equivalent of the epoxy resin is preferably 220 to 470 because the toughness of the molded product is further improved.

The unsaturated polyester (a1) in the polymer component (A) is preferably in the range of 50 to 100% by mass, preferably 60 to 100% by mass, from the viewpoint of the balance between low shrinkage, transparency, gloss, and mapping property. Is more preferred.

The vinyl ester (a2) in the polymer component (A) is preferably in the range of 0 to 50% by mass, preferably 0 to 40% by mass, from the viewpoint of the balance between low shrinkage and transparency, gloss, and mapping property. The range is more preferred.

The polymer component (A) in the molding material of the present invention is preferably 10 to 30% by mass from the viewpoint of the balance between low shrinkage and transparency, gloss and image quality.

Examples of the unsaturated monomer (B) include styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth). Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate alkyl ether, polypropylene glycol (meth) acrylate alkyl ether, 2-ethylhexyl Methacrylate, Isodecyl (meth) acrylate, Lauryl (meth) acrylate, Isotridecyl (meth) acrylate, n-stearyl (meth) acrylate, Tetrahydrofurfuryl methacrylate, Isobornyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, Di Monofunctional (meth) acrylate compounds such as cyclopentanyl methacrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butane. Didioldi (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenoldi (meth) acrylate, 1,4 -Di (meth) acrylate compounds such as cyclohexanedimethanol di (meth) acrylate; vinyl toluene, α-methylstyrene, diallyl phthalate, divinylbenzene, etc., among these, heat resistance, water resistance, and resistance of molded products. Acrylate is preferable because it has better chemical properties and transparency. These unsaturated monomers may be used alone or in combination of two or more.

The unsaturated monomer (B) in the molding material of the present invention is preferably 4 to 10% by mass from the viewpoint of the balance between low shrinkage and transparency, gloss and image quality.

The mass ratio (A / B) of the polymer component (A) to the unsaturated monomer (B) is 80/20 to 20 from the viewpoint of the balance between low shrinkage and transparency, gloss, and image quality. The range of 60/40 is preferable, and the range of 75/25 to 65/35 is more preferable.

The refractive index of the cured product of the resin composition composed of the polymer component (A) and the unsaturated monomer (B) is 1.54 to 1.59 because the transparency of the molded product is further improved. Is preferable.

The curing agent (C) is not particularly limited, but an organic peroxide is preferable, and for example, a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl per ester compound, and a per carbonate are used. Examples thereof include compounds and peroxyketal, which can be appropriately selected depending on the molding conditions. These curing agents (C) may be used alone or in combination of two or more.

The curing agent (C) is preferably 0.3 to 5 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the polymer component (A) and the unsaturated monomer (B). It is more preferably 3 parts by mass.

Examples of the thickener (D) include metal oxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, metal hydroxides, isocyanate compounds, and the like, and the film peeling property and touch. Magnesium oxide is preferable because the balance between the handleability of the molding material such as properties and the moldability is further improved. These thickeners (D) may be used alone or in combination of two or more.

Since the thickener (D) further improves the fluidity in the mold of the molding material, the thickener (D) is 0. It is preferably 3 to 5 parts by mass, and more preferably 0.5 to 2.5 parts by mass.

By using the hollow filler (e1) and the glass powder (e2) as the inorganic filler (E), a molded product having both excellent whiteness and transparency can be obtained.

Examples of the hollow filler (e1) include glass balloons, silica balloons, alumina balloons, and the like, but glass balloons are preferable because the transparency of the molded product is further improved.

The average particle size (median particle size) of the hollow filler (e1) is preferably 50 μm or less, more preferably 40 μm or less, because the gloss and image quality of the molded product are further improved.

The hollow filler (e1) in the inorganic filler (E) is 0.3% by mass or more, preferably 0.5% by mass or more, and is preferably 0. 7% by mass or more is more preferable.

The hollow filler (e1) in the inorganic filler (E) is 10% by mass or less, but 8% by mass or less from the viewpoint of productivity due to an increase in viscosity of the molding material, gloss and image quality of the molded product. It is preferable, and 5% by mass or less is more preferable.

Examples of the glass powder (e2) include glass frit, milled fiber, and glass powder, but glass frit is preferable because the transparency, gloss, and image quality of the molded product are further improved.

The average particle size of the glass powder (e2) is preferably 50 μm or less, more preferably 20 μm or less, still more preferably 13 μm or less, because the imageability and gloss of the molded product are further improved.

As the inorganic filler (E), other fillers (e3) other than the hollow filler (e1) and the glass powder (e2) may be used in combination, and for example, aluminum hydroxide, calcium carbonate, and magnesium carbonate may be used in combination. , Barium sulfate, mica, talc, kaolin, clay, silica, silica sand, gypsum, alumina, cold water stone, silica sand, talc removal, titanium oxide and the like. In addition, these inorganic fillers (E) can be used alone or in combination of two or more.

The refractive index of the inorganic filler (E) is preferably 1.54 to 1.59 because the transparency of the molded product is further improved.

Since the inorganic filler (E) further improves the appearance and smoothness of the molded product, it is 150 to 400 with respect to 100 parts by mass of the total amount of the polymer component (A) and the unsaturated monomer (B). It is preferably parts by mass, more preferably 200 to 350 parts by mass, and even more preferably 250 to 350 parts by mass.

As the glass fiber (F), those having a fiber length of 1.5 to 6 mm or less are used, but those having a fiber length of 1.5 to 3 mm or less are more preferable because the gloss and image quality of the molded product are further improved.

The filament diameter of the glass fiber (F) is preferably 5 to 15 μm because the gloss and image quality of the molded product are further improved.

The glass fiber (F) in the molding material is preferably 1 to 17% by mass, more preferably 1 to 12% by mass, because the gloss and image quality of the molded product are further improved.

The molding material has components other than the above-mentioned essential components such as a hyposhrinking agent, a polymerization inhibitor, a colorant, an ultraviolet absorber, a thickener, an antioxidant, a flame retardant, a surfactant, a water repellent, and a repellent. It can contain various additives such as oils.

The content of the low shrinkage agent such as crosslinked polystyrene in the molding material is preferably 15% by mass or less, preferably 10% by mass, based on the total amount of the resin and the low shrinkage agent component, because the transparency of the molded product is further improved. % Or less is more preferable.

The molding material of the present invention is preferably a bulk molding compound (BMC) because the handleability and moldability as a molding material are further improved.

As a method for producing the BMC, the polymer component (A), the unsaturated monomer (B), and the curing using a mixer such as a normal roll, an intermixer, a planetary mixer, a kneader, and an extruder are used. Examples thereof include a method of mixing the agent (C), the thickener (D), the inorganic filler (E), the glass fiber (F), a low shrinkage agent, an internal mold release agent, and the like, if necessary. ..

Although the artificial marble of the present invention can be obtained from the molding material, the heat compression molding method of BMC is preferable as the molding method because the handleability and moldability as the molding material are further improved.

As the heat compression molding method, for example, a predetermined amount of a molding material such as BMC is weighed, put into a mold preheated to 100 to 180 ° C., molded by a compression molding machine, and the molding material is molded. A manufacturing method is used in which the molding material is cured by holding a molding pressure of 1 to 20 MPa, and then the molded product is taken out to obtain an artificial marble. In this case, heat compression molding is performed in a mold having a share edge at a mold temperature of 110 to 160 ° C. for a specified time of 1 to 2 minutes per 1 mm of the thickness of the artificial marble while maintaining a molding pressure of 5 to 15 MPa. The manufacturing method is preferable.

Since the artificial marble of the present invention has excellent transparency, luster, and imageability, it can be used as a bathroom member (bathtub, waterproof pan, counter, wall), a washbasin counter, a kitchen counter, a kitchen sink, and other housing equipment members. , Can be suitably used for building members such as walls and floors.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The acid value of the resin was measured in accordance with JIS K6901 (2018) 5.3.2., And the weight average molecular weight was measured under the following GPC measurement conditions.

[GPC measurement conditions]
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (sample concentration 4 mg / mL tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.

(Polystyrene monodisperse)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation 1
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

(Synthesis Example 1: Synthesis of unsaturated polyester resin (1))
A 2 L glass flask equipped with a nitrogen gas introduction tube, a thermometer, a recirculation condenser, and a stirrer is charged with 208 parts by mass of neopentyl glycol, 53 parts by mass of propylene glycol, 264 parts by mass of hydrogenated bisphenol A, and 290 parts by mass of isophthalic acid. Heating was started under a nitrogen stream. A dehydration condensation reaction was carried out at an internal temperature of 215 ° C. by a conventional method, and when the solid acid value reached 5 (mgKOH / g), the mixture was cooled to 190 ° C. Then, 196 parts by mass of maleic acid was added to continue the dehydration condensation reaction, and when the solid acid value reached 29 (mgKOH / g), 0.4 parts by mass of toluhydroquinone was added. The unsaturated polyester (a1-1) was dissolved in a styrene monomer so as to have a concentration of 70% by mass to obtain an unsaturated polyester resin (1). The weight average molecular weight of the unsaturated polyester (a1-1) was 10,000. The refractive index of the unsaturated polyester resin (1) was 1.55.

(Synthesis Example 2: Synthesis of Vinyl Ester Resin (1))
In a 2L flask equipped with a nitrogen introduction tube, a thermometer, and a stirrer, 246 parts by mass of epoxy resin ("Epiclon 860-C" manufactured by DIC Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 240), epoxy resin (DIC Co., Ltd.) "Epiclon 1050", bisphenol A type epoxy resin, epoxy equivalent 470) 750 parts by mass, 214 parts by mass of methacrylic acid, and 0.42 parts by mass of dibutyl hydroxytoluene were added, and nitrogen and air were mixed 1: 1. Under circulation, the temperature was raised to 100 ° C. To this, 0.97 parts by mass of 2-methylimidazole was added, the temperature was raised to 110 ° C., and the reaction was carried out. When the solid acid value became 6 (mgKOH / g) or less, 0.48 parts by mass of toluhydroquinone was added and dissolved in styrene monomer so that the vinyl ester (a2-1) concentration was 70% by mass, and vinyl was added. The ester resin (1) was obtained. The epoxy equivalent of the epoxy resin of this vinyl ester (a2-1) was 380. The refractive index of the vinyl ester resin (1) was 1.58.

(Manufacturing example 1: Manufacture of handle material)
100 parts by mass of styrene solution of unsaturated polystyrene resin (styrene content 40% by mass), 250 parts by mass of aluminum hydroxide, 5 parts by mass of white colorant, 1 part by mass of curing agent, and 2 parts by mass of curing accelerator are kneaded. I got the compound. The compound obtained above was poured into a metal vat having a thickness of 15 mm, cured at room temperature for 24 hours, and then heat-cured in a dryer at 80 ° C. for another 3 hours to obtain a cured product made of the compound. The cured product is coarsely pulverized with a shear crusher, further pulverized with a pin mill pulverizer, and then subjected to a 165 mesh and 28 mesh metal mesh sieve (JIS Z8801-1) to be white with a particle size of 100 to 600 μm. A grain pattern material was obtained.

(Example 1: Production and evaluation of molding material (1))
Unsaturated polyester resin (1) 100 parts by mass, colorant (“PT6885” manufactured by Gokoku Dye Co., Ltd., white polyester toner) 0.5 parts by mass, curing agent (“Perhexa HC” manufactured by Nichiyu Co., Ltd.) 1.2% by mass Part, hollow filler (“3M Glass Bubbles S32-HS” manufactured by 3M Japan Co., Ltd., glass balloon, average particle diameter 25 μm; hereinafter abbreviated as “hollow filler (e1-1)”) 3 parts by mass, glass powder (“CF0017-05C06” manufactured by Takara Standard Co., Ltd., glass frit, average particle diameter 6 to 7 μm, refractive index 1.55; hereinafter abbreviated as “glass powder (e2-1)”) 317 parts by mass, internal separation. Mold (zinc stearate) 2 parts by mass, thickener (magnesium oxide) 1.3 parts by mass, and glass fiber ("Chopto Strand ECS03-670" manufactured by Central Glass Fiber Co., Ltd., fiber length 3.0 mm, refraction Ratio 1.55) 23 parts by mass was blended, kneaded with a planetary mixer, and then aged at 40 ° C. for 24 hours to obtain a molding material (1) as BMC.

[Making molded products (artificial marble)]
Compression molding was performed under the following conditions to obtain a molded product (1) as an artificial marble of a flat plate having a size of 300 mm × 300 mm × 7 mm.
Molding temperature: 130 ° C (molded product side), 115 ° C (back surface)
Molding pressure: 10 MPa
Pressurization time: 480 seconds

[Evaluation of whiteness]
The whiteness (L value) of the molded product (1) obtained above was measured using "BYK spectrum-guide 45/0 gloss" manufactured by BYK, and the whiteness was evaluated according to the following criteria.
⊚: L value is 85 or more ○: L value is 80 or more and less than 85 Δ: L value is 75 or more and less than 80 ×: L value is less than 75

[Evaluation of transparency]
The molded product (1) obtained above was visually observed, the visibility of the surface layer surface and the pattern material in the depth direction was confirmed, and the transparency was evaluated according to the following criteria.
⊚: The pattern material can be clearly seen on the surface and inside of the molded product ○: The pattern material can be seen on the surface and inside of the molded product △: The pattern material can be seen a little on the surface and inside of the molded product ×: Only the pattern material on the surface of the molded product can be seen

[Evaluation of gloss]
For the molded product (1) obtained above, the value obtained by measuring the reflectance of 0 to 2000 GU at an incident angle of 20 ° using "BYK Gardener micro-TRI-gloss" manufactured by BYK Co., Ltd. is a 20 ° gloss value. The gloss was evaluated according to the following criteria.
⊚: 20 ° gloss value is 80 or more ○: 20 ° gloss value is 75 or more and less than 80 Δ: 20 ° gloss value is 70 or more and less than 75 ×: 20 ° gloss value is less than 70

[Evaluation of image quality]
With respect to the molded product (1) obtained above, the image sharpness (mapping property) DOI was measured using "Rhopoint IQ-s" manufactured by Konica Minolta Co., Ltd., and the mapping property was evaluated according to the following criteria.
⊚: DOI is 90 or more and ○: DOI is 80 or more and less than 90 Δ: DOI is 70 or more and less than 80 ×: DOI is less than 70

(Examples 2 to 13: Production and evaluation of molding materials (2) to (13))
Molding materials (2) to (13) and molded products (2) to (13) were produced and various performances were evaluated in the same manner as in Example 1 except that the compounding compositions in Tables 1 to 3 were changed.

(Comparative Examples 1 to 3: Production and evaluation of molding materials (R1) to (R3))
Molding materials (R1) to (R3) and molded products (R1) to (R3) were produced and various performances were evaluated in the same manner as in Example 1 except that the composition was changed to that shown in Table 4. In Comparative Example 1, BMC could not be obtained due to the high viscosity.

The compositions and evaluation results of the molding materials (1) to (13) obtained above are shown in Tables 1 to 3.

Table 4 shows the compositions and evaluation results of the molding materials (R1) to (R3) obtained above.

The raw materials in the table are as follows.
Wet dispersant: "BYK-9010" manufactured by BYK
Low shrinkage agent: "Staphyroid GS-102R" manufactured by Aika Kogyo Co., Ltd .; Crosslinkable polystyrene resin powder / aluminum hydroxide surface-treated product Hollow filler (e1-2): "3M Glass Bubbles S60-" manufactured by 3M Japan Ltd. HS "; glass balloon, average particle size 24 μm
Hollow filler (e1-3): "3M Glass Bubbles K46" manufactured by 3M Japan Ltd .; glass balloon, average particle diameter 40 μm
Other filler (e3-1): "CW-308" manufactured by Sumitomo Chemical Co., Ltd .; aluminum hydroxide, average particle diameter 10 μm, refractive index 1.57
Other fillers (e3-2): "Softon 1200" manufactured by Bikita Powder Industry Co., Ltd .; calcium carbonate, average particle diameter 1.8 μm, refractive index 1.63

It was confirmed that the molded products obtained from the molding materials of Examples 1 to 13 were excellent in whiteness, transparency, gloss, and image quality.

Comparative Example 1 is an example in which the content of the hollow filler (e1) in the inorganic filler (E) is larger than the upper limit of 10% by mass of the present invention, but it is confirmed that the molding material cannot be produced due to the high viscosity. Was done.

Comparative Example 2 is an example in which the hollow filler (e1), which is an essential component of the present invention, is not contained, but it was confirmed that the whiteness of the molded product was insufficient.

Comparative Example 3 is an example in which the glass powder (e2), which is an essential component of the present invention, is not contained, but it was confirmed that the transparency of the molded product was insufficient.

Claims (5)

Inorganic containing polymer component (A) containing unsaturated polyester (a1), unsaturated monomer (B), curing agent (C), thickener (D), hollow filler (e1) and glass powder (e2). A molding material containing the filler (E) and the glass fiber (F) having a fiber length of 1.5 to 6 mm as essential raw materials, and the total amount of the polymer component (A) and the unsaturated monomer (B). The amount of the inorganic filler (E) is 150 to 400 parts by mass and the amount of the hollow filler (e1) in the inorganic filler (E) is 0.3 to 10% by mass with respect to 100 parts by mass. Characteristic molding material. The molding material according to claim 1, wherein the hollow filler (e1) has an average particle size of 50 μm or less. The molding material according to claim 1 or 2, wherein the thickener (D) is magnesium oxide. A molded product using the molding material according to any one of claims 1 to 3. Artificial marble using the molding material according to any one of claims 1 to 3.