JP5541522B2 - Molding material, molded product, flooring and method for producing molded product - Google Patents

Description

  The present invention relates to a molded product that can be used for, for example, a building interior member such as a flooring material or a wall material, and a molding material that is used for manufacturing the molded product.

  Since fiber reinforced plastic has conventionally had excellent corrosion resistance and boiling resistance, is lightweight, and can be used for the manufacture of a molded product having a complicated shape with high strength and high rigidity, for example, a bathroom member such as a bathtub, It is widely used for industrial parts such as panel tanks and ships.

  As the resin used for the conventional fiber reinforced plastic, generally, a resin that can form a cured product having a glass transition temperature of about 80 ° C. to 125 ° C. is often used. Since it is hard, for example, when it is used as a flooring material in a bathroom, a hard impression (texture) may be given.

  On the other hand, as said resin, what can form the hardened | cured material with a comparatively soft texture has been reported in recent years, for example, contains urethane acrylate, epoxy acrylate, and a copolymerizable monomer by specific weight ratio. A soft resin composition is known (for example, see Patent Document 1).

  However, the fiber reinforced plastic obtained using the soft resin composition has relatively good flexibility and hot water resistance, but is still not sufficient.

  Further, as a molding material, a material that is solid in shape and has no surface stickiness is required to facilitate handling of the molding material.

  However, since the soft resin composition cannot maintain a solid shape or has a sticky surface, the soft resin composition is difficult to handle during molding and may not be sufficient in terms of handling properties.

  In this way, it has both good flexibility and excellent hot water resistance, and it is easy to handle as a solid at room temperature, and it can be easily melted by heating and used for manufacturing molded products of various shapes. In fact, it has not been found yet.

Japanese Patent Laid-Open No. 11-199639

  The problem to be solved by the present invention is a molding material, molded product, flooring, and molding, which have both excellent flexibility and excellent hot water resistance as compared with conventional molded products, and also have excellent handling properties. The present invention relates to a method for manufacturing a product.

  As a result of studying to solve the above-mentioned problems, the inventors of the present invention based on a thermosetting resin (A) capable of forming a cured product having a relatively low glass transition, a specific filler (B) and reinforcing fibers ( It has been found that the subject of the present invention can be solved if it is a molding material using a combination of C) and a specific thickener (D) in a predetermined amount.

  That is, the present invention relates to a thermosetting resin composition capable of forming a cured product having a glass transition temperature of −40 ° C. to 40 ° C. comprising a thermosetting resin (a1) and a polymerizable unsaturated monomer (a2). A molding material comprising (A), a filler (B) surface-treated with a silane coupling agent, a reinforcing fiber (C), and a thickener (D) containing acrylic resin powder. The filler (B) is contained in an amount of 15% by mass to 160% by mass with respect to the total amount of the thermosetting resin composition (A), and the reinforcing fiber (C) is contained in the thermosetting resin composition (A). 5% by mass to 90% by mass with respect to the total amount and 10% by mass to 60% by mass of the thickener (D) with respect to the total amount of the thermosetting resin composition (A). A molding material characterized by the above and a molded article and a flooring obtained by molding the molding material It is intended.

  Moreover, this invention relates to the manufacturing method of the molded article which shape | molds the said molding material by the press molding method in the range of 100-160 degreeC.

  If it is the molding material of the present invention, since it has both excellent flexibility and superior hot water resistance compared to conventional molded products, and also has excellent handling properties, the molded product has a complicated shape. Can be used for various purposes including building materials such as flooring and wall materials.

  The molding material of the present invention is a thermosetting resin composition capable of forming a cured product having a glass transition temperature of −40 ° C. to 40 ° C. composed of a thermosetting resin (a1) and a polymerizable unsaturated monomer (a2). A product (A), a filler (B) surface-treated with a silane coupling agent, a reinforcing fiber (C), a thickener (D) containing an acrylic resin powder, and, if necessary, other A molding material containing an additive, wherein the filler (B) is contained in an amount of 15% by mass to 160% by mass with respect to the total amount of the thermosetting resin composition (A), and the reinforcing fiber (C) 5 mass%-90 mass% is contained with respect to the whole quantity of the said thermosetting resin composition (A), and the said thickener (D) is with respect to the whole quantity of the said thermosetting resin composition (A). 10 mass%-60 mass% is contained, It is characterized by the above-mentioned.

  In the present invention, the thermosetting resin composition (A), the filler (B), the reinforcing fiber (C), and the thickener (D) may be used in combination at the specific use ratio. is important.

  Specifically, the filler (B) is used in an amount of 15% by mass to 160% by mass with respect to the total amount of the thermosetting resin composition (A) used in the present invention, and the reinforcing fiber (C) is 5 mass% to 90 mass% is used with respect to the total amount of the thermosetting resin composition (A), and the thickener (D) is 10 with respect to the total amount of the thermosetting resin composition (A). It is important to use mass% to 60 mass%.

Here, in the molding material in which any one of the use ratios (B) to (D) is out of the above range, the reinforcing fiber (C) and the thermosetting resin composition (A) are sufficiently mixed. May not be possible, resulting in poor appearance and deterioration of hot water resistance. In addition, with the molding material, it is impossible to obtain a molded product having a soft texture, and the handling property is significantly reduced, so that the manufacturing efficiency of the molded product may be reduced.
On the other hand, when a thermosetting resin composition capable of forming a cured product having a glass transition temperature of about 80 ° C. to 100 ° C. is used instead of the thermosetting resin composition (A). A molded product such as a fiber reinforced plastic can be produced without using the filler (B) or the like at the predetermined ratio. However, since such a molded product is hard and rigid, for example, when used for a flooring or the like, a flexible texture may be impaired.
Therefore, in order to obtain a molded article having both a soft texture and hot water resistance based on the thermosetting resin composition (A), the filler (B), the reinforcing fiber (C), and the increase It is essential to use a combination of the sticking agent (D) in the above ratio.

First, the said thermosetting resin composition (A) is demonstrated.
As said thermosetting resin composition (A), the hardened | cured material which has a glass transition temperature of -40 degreeC-40 degreeC among what consists of a thermosetting resin (a1) and a polymerizable unsaturated monomer (a2). Can be used. The glass transition temperature is a temperature of a cured product obtained by curing the thermosetting resin composition.
As said thermosetting resin composition (A), even if it uses individually 1 type of thermosetting resin which can form the hardened | cured material which has the glass transition temperature of the said range as said thermosetting resin (a1). Two or more thermosetting resins may be used in combination.
The thermosetting resin composition (A) is a combination of two or more thermosetting resins capable of forming a cured product having a glass transition temperature outside the range of −40 ° C. to 40 ° C., and the polymerizable property. By using the unsaturated monomer (a2), a mixture that can form a cured product having a glass transition temperature of −40 ° C. to 40 ° C. is also included.
Explaining with specific examples, unsaturated polyester resin 1 capable of forming a cured product having a glass transition temperature of −45 ° C., and unsaturated polyester resin 2 capable of forming a cured product having a glass transition temperature of 80 ° C. Among the mixture of the resin mixture used in combination with the polymerizable unsaturated monomer (a2), the thermosetting resin mixture blended at a ratio at which the glass transition temperature of the cured product can be −20 ° C. is It is included in the thermosetting resin composition (A) which is an invention specific matter.

  By using the thermosetting resin composition capable of forming a cured product having a relatively low glass transition temperature as described above, it is possible to impart a soft texture to the obtained molded product.

  Here, in the molding material obtained by using the thermosetting resin composition having a glass transition temperature of −45 ° C. instead of the thermosetting resin composition (A), molding with sufficient hot water resistance You may not be able to get goods. Moreover, in the molding material obtained by using the thermosetting resin composition having a glass transition temperature of 45 ° C., a molded product having a flexible texture may not be obtained. The glass transition temperature of the thermosetting resin composition (A) is such that 0.5 parts by weight of 6% by weight cobalt naphthenate and 55% by weight methyl ethyl ketone peroxide are added to 100 parts by weight of the thermosetting resin composition (A). 1 part by weight was added, stirred, and allowed to cure at room temperature for 15 hours. After curing at 120 ° C. for 2 hours, a cured product was obtained by a DMA method at a heating rate of 5 ° C./min and a frequency of 1 hertz. It is a value measured under the conditions. The same applies to the embodiments.

  As said thermosetting resin (a1), unsaturated polyester resin, urethane acrylate resin, vinyl ester resin, an epoxy resin etc. can be used individually or in combination of 2 or more, for example.

  Among these, from the viewpoint of obtaining a cured product excellent in flexibility, (thermal) water resistance and curability, a thermosetting resin containing one or more selected from the group consisting of unsaturated polyester resins and urethane acrylate resins is used. It is preferable to do.

  In addition, from the viewpoint of further improving flexibility and hot water resistance, it is preferable to use a combination of the unsaturated polyester resin and the urethane acrylate resin, and specifically, the mass of [unsaturated polyester resin / urethane acrylate resin]. It is preferable to use within a range of 90/10 to 20/80.

  As said unsaturated polyester resin, what was obtained by making a polyhydric alcohol and polyhydric carboxylic acid react by a conventionally well-known method can be used, for example. The unsaturated polyester resin may be dissolved in advance in a polymerizable monomer (a2) such as a vinyl monomer such as styrene or a (meth) acryl monomer.

  As the polyhydric alcohol and polyhydric carboxylic acid, those conventionally known can be used. Specifically, as the polyhydric alcohol, for example, ethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, polypropylene glycol and the like can be used. Moreover, as said polyvalent carboxylic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, a phthalic acid etc. can be used, for example.

  As the unsaturated polyester resin, it is preferable to use what is generally called a soft unsaturated polyester resin from the viewpoint of obtaining a molded product having a more flexible texture. Specifically, diethylene glycol or 1,6- It is preferable to use one obtained by reacting hexanediol with adipic acid or the like.

  The urethane acrylate resin has a (meth) acryloyl group at the molecular end or side chain, and has a urethane bond in the molecule, for example, a hydroxyl group and a polymerizable unsaturated double bond-containing compound, It can be produced by reacting a polyol with a polyisocyanate. The urethane acrylate resin may be previously dissolved in a copolymerizable monomer such as a (meth) acryl monomer.

  Examples of the compound containing a hydroxyl group and a polymerizable unsaturated double bond include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Propylene glycol mono (meth) acrylate or the like can be used.

  Examples of the polyol include neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A ethylene oxide adduct glycols and adipic acid Saturated polyester polyols obtained from dehydration condensation reactions such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, or polyethylene glycol, polypropylene glycols obtained from ring opening reaction of ethylene oxide or propylene oxide, or caprolactone Polycaprylolactone obtained from the ring-opening reaction can be used.

  Examples of the polyisocyanate include aromatic and / or aliphatic polyisocyanate compounds, such as tolylene diisocyanate, diphenylmethanidisocyanate, hydrogenated diphenylmethanidisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated. Xylylene diisocyanate and the like can be used.

  The thermosetting resin (a1) may be previously dissolved in the polymerizable unsaturated monomer (a2).

  Examples of the polymerizable unsaturated monomer (a2) include vinyl monomers such as styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic monomers such as 2-ethylhexyl can be used. Among them, it is preferable to use butyl methacrylate or styrene for improving flexibility, water resistance, and hot water resistance of the obtained molded product.

  The polymerizable unsaturated monomer (a2) is preferably used in a range of 30% by mass to 65% by mass with respect to the total amount of the thermosetting resin composition (A) used in the present invention, and 40% by mass. It is more preferable to use in the range of% -55 mass%.

Next, the filler (B) used in the present invention will be described.
As the filler (B) used in the present invention, it is important to use a conventionally known filler whose surface has been surface-treated with a silane coupling agent. Here, even if a filler such as aluminum hydroxide that has not been subjected to the surface treatment is used, the effect of improving hot water resistance or the like may not be obtained.

  Specifically, as the filler (B), the surface of a filler such as aluminum hydroxide or calcium carbonate is used for vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy It is preferable to use one that has been surface-treated with a silane coupling agent such as silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane.

  Moreover, in this invention, it is important to use the said filler (B) in 15 mass%-160 mass% with respect to the whole quantity of the thermosetting resin composition (A) of this invention. Here, when the amount of the filler (B) is less than 15% by weight, the handling property of the molding material is significantly lowered, and it may be difficult to produce a complex molded product, If it exceeds 160% by mass, the flexible texture of the resulting molded product may be impaired.

  Therefore, as said filler (B), it is preferable to use in 15 mass%-160 mass% with respect to the whole quantity of the thermosetting resin composition (A) of this invention, and 20 mass%-140 mass. % Is more preferable for obtaining a molded product having both excellent flexibility and heat resistance.

Next, the reinforcing fiber (C) used in the present invention will be described.
As the reinforcing fiber (C), for example, glass fiber, carbon fiber, organic fiber polyester, vinylon, nylon, polylactic acid, natural fiber jute, hemp, bamboo, kenaf, or the like can be used. Of these, glass fiber is preferably used for reasons such as (warm) water resistance and economy.

  Moreover, in this invention, it is important to use the said reinforced fiber (C) in 5 mass%-90 mass% with respect to the whole quantity of the thermosetting resin composition (A) of this invention. Here, when the amount of the reinforcing fiber (C) is less than 5% by weight, the strength of the obtained molded product may be reduced. On the other hand, when the amount exceeds 90% by mass, the resulting molded product is flexible. The texture may be impaired.

  Accordingly, the reinforcing fiber (C) is preferably used in the range of 5% by mass to 90% by mass with respect to the total amount of the thermosetting resin composition (A) of the present invention, and 8% by mass to 75% by mass. % Is more preferable for obtaining a molded product having both excellent flexibility and heat resistance.

Next, the thickener (D) used by this invention is demonstrated.
As the thickener (D), for example, conventionally known acrylic resin powder can be used.
As said acrylic resin powder, what is obtained by superposing | polymerizing (meth) acrylic monomers, such as (meth) acrylic-acid alkylester, can be used, for example, (meth) acrylic-acid methyl is superposed | polymerized. It is preferable to use the resulting acrylic resin powder.

  In this invention, it is important to use the said thickener (D) in the range of 10 mass%-60 mass% with respect to the whole quantity of the thermosetting resin composition (A) used by this invention. Here, when the amount of the thickener (D) is less than 10% by weight, the handling property of the molding material is remarkably lowered, and it may be difficult to produce a complex molded product. If it exceeds 60 mass%, the resulting cured product may have poor appearance and reduced hot water resistance.

  Therefore, the thickener (D) is preferably used in the range of 10% by mass to 60% by mass with respect to the total amount of the thermosetting resin composition (A) used in the present invention. The use in the range of 55% by mass is more preferable for obtaining a molded product having both excellent flexibility and hot water resistance.

  In addition to the thermosetting resin composition (A), the filler (B), the reinforcing fiber (C), and the thickener (D), the molding material of the present invention can be used as necessary. The component may be contained.

  Moreover, as said other component, the hydrophilizing agent containing unsaturated polyester resin (E) which has hydrophilic performance, a polyoxyethylene monostearate, etc. can be used. Among these, it is preferable to use an unsaturated polyester resin (E) having hydrophilic performance in order to impart a long-lasting hydrophilic effect to the obtained molded article.

  What can be contained in the concept of the said thermosetting resin (A) can also be used for the unsaturated polyester resin (E) which has the hydrophilic performance which can be used as the said hydrophilizing agent. Therefore, when using the unsaturated polyester resin (E) having hydrophilic performance that can be included in the concept of the thermosetting resin (A), polymerization is performed with the thermosetting resin containing the unsaturated polyester resin (E). It is necessary to adjust so that the glass transition temperature of the hardened | cured material obtained by hardening | curing the thermosetting resin composition containing a polymerizable unsaturated monomer may become the range of -40 degreeC-40 degreeC.

  The unsaturated polyester resin (E) having hydrophilic performance is preferably used in a range where the glass transition temperature of the cured product formed by the thermosetting resin composition (A) is −40 ° C. to 40 ° C. Specifically, it is preferably used in the range of 1.0% by mass to 15.0% by mass with respect to the total amount of the thermosetting resin composition (A) of the present invention.

  Moreover, as said other component, various additives, such as a polymerization inhibitor, a hardening | curing agent, a coloring agent, a flame retardant, a mold release agent, a ultraviolet absorber, a thermoplastic resin, can be used, for example.

  Examples of the polymerization inhibitor that can be used include hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, and copper chloride. .

  The curing agent is, for example, a thermosetting agent made of a diacyl peroxide type, a peroxy ester type, a ketone peroxide type, an alkyl perester type, a carbonate type compound, an ultraviolet curing agent, or an electron beam curing agent. One or more selected can be used.

  Examples of the colorant include inorganic pigments such as titanium white and carbon black, and organic pigments such as phthalocyanine blue and quinacridone red.

  Examples of the flame retardant include chlorinated paraffins, phosphate esters, antimony trioxide, and brominated flame retardants.

  As the internal mold release agent, for example, higher fatty acids such as stearic acid, higher fatty acid salts such as stearic zinc, alkyl phosphates, or a mixture of a surfactant and a copolymer can be used.

  The thermoplastic resin may be used for improving fracture toughness. For example, polystyrene, a copolymer of styrene and (meth) acrylate, a styrene-conjugated diene block copolymer, styrene-hydrogenated. A conjugated diene block copolymer or the like can be used.

  The molding material of the present invention has the hydrophilic performance as necessary, with the thermosetting resin composition (A), the filler (B), the reinforcing fiber (C), and the thickener (D). It can manufacture by mixing, stirring, and impregnating other components, such as unsaturated polyester resin (E).

  The molding material of the present invention obtained by the above method can be molded into a desired shape by, for example, a press molding method, an injection molding method, or a continuous molding method, and adopting the press molding method has a large and complicated shape. It is preferable because a molded product is easily obtained. The press molding is preferably performed under a temperature condition of 100 to 160 ° C.

  As mentioned above, since the molded article obtained using the molding material of the present invention is excellent in flexibility and hot water resistance, it can be used for a surface layer of a building member such as a flooring material or a wall material. Especially, it is suitable to use suitably for the flooring and wall material of the bathroom for which a soft texture is calculated | required when a hand, a leg | foot, etc. touch.

  In addition, by using the unsaturated polyester resin (E) having the hydrophilic performance described above, a molded product having an easy and drying effect can be obtained. It can be suitably used for bathroom flooring and wall materials.

When the molded product of the present invention is used for a wall material, a floor material, or a surface layer thereof, an embossed pattern or the like may be provided on the surface of the molded product.
Moreover, when using the said molded article for a wall material, a flooring, and those surface layers, it is preferable that the thickness of the said molded article is the range of 0.5-5.0 mm.

  Hereinafter, the present invention will be described with reference to examples and comparative examples.

[Example 1]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 90 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 10 parts by mass, 13 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 6 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -3.3 ° C.

  1.3 parts by mass of the above mixture and BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals manufactured by Kayaku Akzo Co., Ltd.] 1.1 parts by mass, parabenzoquinone (PBQ) 0. The compound was obtained by mixing and stirring with 05 parts by mass and mixing with 160 parts by mass of CW-308B [aluminum hydroxide average particle diameter 8 μm surface-treated with a silane coupling agent manufactured by Sumitomo Chemical Co., Ltd.]. . After mixing the obtained compound and 47 parts by mass of Zefiac F-320 [Thickener made of acrylic resin powder manufactured by Gantz Kasei Co., Ltd.], 10 parts by mass of glass fiber was impregnated and heated at 45 ° C. for 24 hours. The molding material 1 was obtained by heating.

[Example 2]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 80 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 20 parts by mass, 1.3 parts by mass of an unsaturated polyester resin having hydrophilic properties and styrene (solid content 64.0% by mass) and 10 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was −27.3 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts by mass, parabenzoquinone (PBQ) 0. A compound is obtained by mixing and stirring with 1 part by mass and mixing with 50 parts by mass of BF-013STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm]. It was. The obtained compound was mixed with Zefiac F-320 [Thickener of polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.] 25 parts by mass, and then impregnated with 75 parts by mass of glass fiber at 45 ° C. The molding material 2 was obtained by heating for 24 hours.

Example 3
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 70 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 30 parts by mass, 4 parts by mass of a unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass), and 19 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was −22.3 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals manufactured by Kayaku Akzo Co., Ltd.] 1.1 parts by mass, parabenzoquinone (PBQ) 0. A compound is obtained by mixing and stirring with 05 parts by mass and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle size 1 μm]. It was. After mixing the obtained compound and 38 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Ganz Kasei Co., Ltd.], the mixture was impregnated with 60 parts by mass of glass fiber at 45 ° C. The molding material 3 was obtained by heating for 24 hours.

Example 4
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts by mass, parabenzoquinone (PBQ) 0. A compound is obtained by mixing and stirring with 1 part by mass and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm]. It was. After mixing the obtained compound and 45 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], impregnation with 60 parts by mass of glass fiber, at 45 ° C. The molding material 4 was obtained by heating for 24 hours.

Example 5
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 30 parts by mass and VDP-800 [mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 70 parts by mass, 6 parts by mass of a unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 22 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was 8.0 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals manufactured by Kayaku Akzo Co., Ltd.] 1.1 parts by mass, parabenzoquinone (PBQ) 0. The compound was obtained by mixing and stirring with 05 parts by mass and mixing with 130 parts by mass of CW-308B (aluminum hydroxide average particle diameter 8 μm surface-treated with a silane coupling agent manufactured by Sumitomo Chemical Co., Ltd.). . After mixing the obtained compound and 35 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], the mixture was impregnated with 30 parts by mass of glass fiber at 45 ° C. The molding material 5 was obtained by heating for 24 hours.

Example 6
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 20 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 80 parts by mass, 10 parts by mass of an unsaturated polyester resin having hydrophilic properties and styrene (solid content 64.0% by mass) and 25 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was 19.6 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals manufactured by Kayaku Akzo Co., Ltd.] 1.1 parts by mass, parabenzoquinone (PBQ) 0. Mixing and stirring with 05 parts by mass, a compound is obtained by mixing with BF-013STM [30 parts by mass of aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter of 1 μm]. It was. The resulting compound was mixed with Zefiac F-320 [Thickener of polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.] 60 parts by mass, and then impregnated with 90 parts by mass of glass fiber at 45 ° C. The molding material 6 was obtained by heating for 24 hours.

[Comparative Example 1]
Sandoma PS-281 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 60% by mass, glass transition temperature 110 ° C. of cured product] 100 parts by mass, unsaturated polyester having hydrophilic performance A mixture of 4 parts by mass of a resin and styrene mixture (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was 105.0 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Keijiku Akzo Co., Ltd. curing agent] 2.0 parts by mass, parabenzoquinone (PBQ) 0. A compound is obtained by mixing and stirring with 05 parts by mass and mixing with 100 parts by mass of BF-013STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm]. It was. After mixing the obtained compound and 45 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], impregnation with 60 parts by mass of glass fiber, at 45 ° C. The comparative molding material 1 was obtained by heating for 24 hours.

[Comparative Example 2]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -14.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts by mass, parabenzoquinone (PBQ) 0. Mixed with 05 parts by mass and stirred, mixed with 95 parts by mass of B-103 [Nippon Light Metal Co., Ltd., untreated aluminum hydroxide, surface-treated with a silane coupling agent, average particle size of 8 μm] To get a compound. After mixing the obtained compound and 45 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], impregnation with 60 parts by mass of glass fiber, at 45 ° C. The comparative molding material 2 was obtained by heating for 24 hours.

[Comparative Example 3]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts, parabenzoquinone (PBQ) 0.1 The compound was obtained by mixing and stirring with 10 parts by mass of BF-013STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter of 1 μm] with 10 parts by mass. . After mixing the obtained compound and 45 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], impregnation with 60 parts by mass of glass fiber, at 45 ° C. The comparative molding material 3 was obtained by heating for 24 hours.

[Comparative Example 4]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts, parabenzoquinone (PBQ) 0.1 The compound was obtained by mixing and stirring with 200 parts by mass of BF-013STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle size 1 μm] with 200 parts by mass. . After mixing the obtained compound and 45 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], impregnation with 60 parts by mass of glass fiber, at 45 ° C. The comparative molding material 4 was obtained by heating for 24 hours.

[Comparative Example 5]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts, parabenzoquinone (PBQ) 0.1 A compound was obtained by mixing and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm] with 95 parts by mass. . After mixing the obtained compound and Zefiac F-320 [Thickener of polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.] 45 parts by mass, the mixture was impregnated with 3 parts by mass of glass fiber at 45 ° C. The comparative molding material 5 was obtained by heating for 24 hours.

[Comparative Example 6]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts, parabenzoquinone (PBQ) 0.1 A compound was obtained by mixing and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm] with 95 parts by mass. . The resulting compound was mixed with Zefiac F-320 [Thickener of polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.] 45 parts by mass, and then impregnated with 120 parts by mass of glass fiber at 45 ° C. The comparative molding material 6 was obtained by heating for 24 hours.

[Comparative Example 7]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts, parabenzoquinone (PBQ) 0.1 A compound was obtained by mixing and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm] with 95 parts by mass. . The obtained compound was mixed with 10 parts by mass of Zefiac F-320 [Methyl methacrylate polymer powder thickener manufactured by Gantz Kasei Co., Ltd.] and then impregnated with 60 parts by mass of glass fiber at 45 ° C. The comparative molding material 7 was obtained by heating for 24 hours.

[Comparative Example 8]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] , PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts, parabenzoquinone (PBQ) 0.1 A compound was obtained by mixing and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm] with 95 parts by mass. . After mixing the obtained compound and 90 parts by mass of Zefiac F-320 [Thickening agent for polymer powder of methyl methacrylate manufactured by Gantz Kasei Co., Ltd.], the mixture was impregnated with 60 parts by mass of glass fiber at 45 ° C. The comparative molding material 8 was obtained by heating for 24 hours.

[Comparative Example 9]
As thermosetting resin composition (A), Sandoma PS-600 [a mixture of unsaturated polyester resin and styrene manufactured by DH Material Co., Ltd., solid content 56.5% by mass, glass transition temperature of cured product; 34.7 ° C.] 50 parts by mass and VDP-800 [a mixture of urethane acrylate resin and styrene manufactured by DH Material Co., Ltd., solid content 69.0% by mass, glass transition temperature of cured product; 36.3 ° C.] A mixture of 50 parts by mass, 4 parts by mass of an unsaturated polyester resin having hydrophilic performance and styrene (solid content 64.0% by mass) and 15 parts by mass of n-butyl methacrylate was used. The glass transition temperature of the cured product obtained by curing the mixture was -4.2 ° C.

  1.3 parts by mass of the mixture, BYK-P9080 [internal mold release agent manufactured by Big Chemie Japan Co., Ltd.], and 0.4 parts by mass of BYK-9076 [separation inhibitor manufactured by Big Chemy Japan Co., Ltd.] PCN0F309S-W [Tokyo Ink Co., Ltd. sheet molding compound colorant] 15 parts by mass, Kaya-Carbon AIC-75 [Chemicals made by Kayaku Akzo Co., Ltd.] 2.2 parts by mass, parabenzoquinone (PBQ) 0. A compound is obtained by mixing and stirring with 1 part by mass and mixing with 95 parts by mass of BF-013 STM [aluminum hydroxide surface-treated with a silane coupling agent manufactured by Nippon Light Metal Co., Ltd., average particle diameter 1 μm]. It was. After mixing the obtained compound and 3 parts by mass of magnesium oxide, 60 parts by mass of glass fiber was impregnated and heated at 45 ° C. for 24 hours to obtain a comparative molding material 9.

[Method of manufacturing cured product]
The molding materials obtained in the examples and comparative examples were pressed using a mold with dimensions of 300 mm in length and 300 mm in width, with a mold temperature of 150 ° C., a lower mold of 140 ° C., a pressure of 100 tons, and a curing time of 6 minutes. By curing, a plate-shaped cured product having a length of 300 mm × width of 300 mm × thickness of 2 mm was obtained.

[Method for evaluating formability]
A case where a flat plate-shaped cured product could not be produced by the above-mentioned method, or a case where a cured product was produced but a remarkable appearance defect occurred was evaluated as “x”. On the other hand, what was able to manufacture the hardened | cured material of the flat shape of length 300mm x width 300mm x thickness 2mm by the said method was evaluated as "(circle)".

[Handling evaluation method]
After the molding materials obtained in the examples and comparative examples were heated at 45 ° C. for 24 hours, “X” indicates that the stickiness of the surface was extremely difficult to handle, the solid shape could be maintained, the surface stickiness, etc. The case where there was almost no was marked as “◯”.

[Evaluation method of flexibility (tensile modulus)]
Tensile test specimens were prepared from the cured product obtained by the above press molding method based on JIS K 6911 and measured at a speed of 1 mm / min using Shimadzu Autograph AG-I 20KN. Asked.
In addition, when the hardened | cured material could not be formed because moldability was inadequate, evaluation was not performed but "-" was described in the table | surface.

[Method for evaluating flexibility (flexibility)]
The plate-shaped cured product having a length of 300 mm, a width of 300 mm, and a thickness of 2 mm obtained by the above method was bent by applying force by hand. The plate-shaped cured product that was bent until 90 ° was evaluated as “◯”, and the cured product was cracked or completely cracked before reaching 90 °, or the cured product was 90 ° by hand force. Those that could not be bent until were evaluated as “x”. In addition, when the hardened | cured material could not be formed because moldability was inadequate, evaluation was not performed but "-" was described in the table | surface.

[Method for evaluating hot water resistance]
The cured product obtained above was immersed in hot water at 80 ° C. for 300 hours. After immersion, the presence or absence of swelling was visually observed on the surface of the cured product.
The case where swelling occurred on the surface of the cured product was evaluated as x, and the case where no swelling was observed and the appearance was not changed from that before immersion was evaluated as ◯.
In addition, when the hardened | cured material could not be formed because moldability was inadequate, evaluation was not performed but "-" was described in the table | surface.

[Drying evaluation method]
The cured product obtained above was fixed in a state tilted by 15 ° with respect to the horizontal plane. After 1 liter of water was applied to the surface of the cured product, the case where no water droplets adhered to the surface of the cured product was evaluated as ◯, and the case where water droplets remained remained was evaluated as x.
In addition, when the hardened | cured material could not be formed because moldability was inadequate, evaluation was not performed but "-" was described in the table | surface.

Claims (11)

  A thermosetting resin composition (A) capable of forming a cured product comprising a thermosetting resin (a1) and a polymerizable unsaturated monomer (a2) having a glass transition temperature of −40 ° C. to 40 ° C., and silane A molding material containing a filler (B) surface-treated with a coupling agent, a reinforcing fiber (C), and a thickener (D) containing an acrylic resin powder, the filler (B ) Is contained in an amount of 15% by mass to 160% by mass with respect to the total amount of the thermosetting resin composition (A), and the reinforcing fiber (C) is 5% with respect to the total amount of the thermosetting resin composition (A). It is characterized in that it is contained in an amount of from 10% to 90% by mass and the thickener (D) is contained in an amount of 10% to 60% by mass with respect to the total amount of the thermosetting resin composition (A). Molding material to be.   The molding material according to claim 1, wherein the thermosetting resin (a1) contains one or more selected from the group consisting of an unsaturated polyester resin and a urethane acrylate resin.   The molding material according to claim 1, wherein the filler (B) is a surface treatment of one or more selected from the group consisting of aluminum hydroxide and calcium carbonate with a silane coupling agent.   The molding material according to claim 1, wherein the reinforcing fibers (C) are glass fibers.   The molding material according to claim 1, wherein the thickener (D) is an acrylic resin powder obtained by polymerizing methyl methacrylate.   The molding material of Claim 1 whose said polymerizable unsaturated monomer (a2) is a (meth) acryl monomer or styrene.   The molding material of Claim 6 whose content of the said polymerizable unsaturated monomer (a2) is 6-25 mass% with respect to the whole quantity of the said molding material. A molded product obtained by molding the molding material according to any one of claims 1 to 7 . A flooring comprising the molded product according to claim 8 . The molded article according to claim 8 , wherein the tensile elastic modulus is in the range of 1000 to 5000 MPa. The molding material according to any one of claims 1 to 7 production method of a molded article molded by press molding in the range of 100 to 160 ° C..