JP2021004279A - Fiber-reinforced molding material and molding including the same - Google Patents

Abstract

To provide a fiber-reinforced molding material that does not contain a halogen compound or an antimony compound, has excellent moldability, and gives a molding having excellent flame retardancy by a convenient work process, and a molding thereof.SOLUTION: A fiber-reinforced molding material contains a novolac type phenolic resin (A), a divinylbenzene compound (B), aluminum hydroxide (C), a poly(meth)acrylic ester compound (D), and a reinforced fiber (E). Relative to 100 pts.mass of the total of the novolac type phenolic resin (A) and the divinylbenzene compound (B), the aluminum hydroxide (C) is 110-240 pts.mass, and the poly(meth)acrylic ester compound (D) is 0.3-33 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a fiber reinforced molding material and a molded product using the same.

Sheet molding compound (SMC) is formed by impregnating glass fibers with a paste containing a thermosetting resin, an inorganic filler, a thickener, a curing agent, etc. to form a sheet, which is aged and semi-cured. It is a material. A molded product can be obtained by heating and pressure molding this SMC with a mold. Such molded products utilize characteristics such as excellent durability, water resistance, mechanical strength, and flame retardancy to provide bathroom equipment, water tanks, septic tanks, building materials, flooring materials, electrical parts, vehicle materials, etc. However, high flame retardancy is required for building materials, vehicle materials, aircraft materials, and the like.

As a method for obtaining flame retardancy, there is a method of adding a halogen compound such as a chlorine-containing compound or a bromine-containing compound, or an antimony compound such as antimony trioxide. However, it has been pointed out that it is not preferable to use it from the viewpoint of environmental protection, and a flame retardant mechanism containing no halogen compound and antimony compound is required.

On the other hand, as a thermosetting resin which is a main component of SMC, an unsaturated polyester resin has been generally used in the past, but it has been studied to use a phenol resin for the purpose of imparting high flame retardancy. Among them, it is said that the use of a resol type phenol resin which is liquid at room temperature is preferable (for example, Patent Documents 1 to 3).

However, such a resole-type phenol resin has a problem that water is desorbed as a by-product by causing dehydration condensation by heating and progressing curing, and this desorption of water is SMC molding. Since it sometimes causes blister and warp, it is necessary to provide a degassing step for removing water during molding.

Therefore, there has been a demand for a material that does not contain a halogen compound and an antimony compound and can obtain a molded product having excellent flame retardancy by a simple work process.

Japanese Unexamined Patent Publication No. 3-189110 Japanese Unexamined Patent Publication No. 2004-182964 JP-A-2007-169457

The problem to be solved by the present invention is to provide a fiber-reinforced molding material which does not contain a halogen compound and an antimony compound, has excellent moldability, and can obtain a molded product having excellent flame retardancy by a simple work process, and a molded product thereof. It is to be.

The present inventors can solve the above-mentioned problems with a fiber-reinforced molding material containing a novolak-type phenol resin, a divinylbenzene compound, aluminum hydroxide, a poly (meth) acrylic acid ester compound, and reinforcing fibers in a specific composition ratio. The present invention was completed.

That is, a fiber-reinforced molding material containing a novolak-type phenol resin (A), a divinylbenzene compound (B), aluminum hydroxide (C), a poly (meth) acrylic acid ester compound (D), and reinforcing fibers (E). The aluminum hydroxide (C) is 110 to 240 parts by mass with respect to a total of 100 parts by mass of the novolak type phenol resin (A) and the divinylbenzene compound (B), and the poly (meth) acrylic is used. The present invention relates to a fiber-reinforced molding material characterized in that the acid ester compound is 0.3 to 33 parts by mass, and a molded product using the same.

Since the molded product obtained from the fiber-reinforced molded material of the present invention is excellent in flame retardancy and the like, it is an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, a housing equipment member, a sports member, a light vehicle member, and a building. It can be suitably used for civil engineering members, housings for OA equipment, and the like.

The fiber-reinforced molding material of the present invention comprises a novolak-type phenol resin (A), a divinylbenzene compound (B), aluminum hydroxide (C), a poly (meth) acrylic acid ester compound (D), and a reinforcing fiber (E). The fiber-reinforced molding material contained is 110 to 240 parts by mass of the aluminum hydroxide (C) with respect to 100 parts by mass of the total of the novolak type phenol resin (A) and the divinylbenzene compound (B). , The poly (meth) acrylic acid ester compound (D) is 0.3 to 33 parts by mass.

In the present invention, "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid, and "(meth) acrylate" means one or both of acrylate and methacrylate.

The novolak-type phenol resin (A) is not particularly limited, but since it is excellent in compatibility with the divinylbenzene compound (B), the ortho-para ratio of the methylene bond that crosslinks the aromatic ring is 3 or more. preferable. Here, the ortho-para ratio is the sum of the number of methylene bonds crosslinked between the para positions with respect to the hydroxyl group of the aromatic ring and 1/2 of the number of methylene bonds crosslinked between the ortho and para positions. It is the ratio of the sum of the number of methylene bonds crosslinked between the ortho positions and 1/2 of the number of methylene bonds crosslinked between the ortho positions and the para positions. The novolak type phenol resin (A) can be used alone or in combination of two or more.

The number average molecular weight of the novolak type phenol resin (A) is preferably 200 to 2,000, more preferably 300 to 1,000.

In the novolak type phenol resin (A), for example, a formaldehyde supply substance and a phenol compound are reacted in the presence of a catalyst so that the molar ratio thereof is 0.5 to 1.0, if necessary. Obtained by

Examples of the formaldehyde supply substance include an aqueous formaldehyde solution and paraformaldehyde. These formaldehyde supply substances may be used alone or in combination of two or more.

Examples of the phenol compound include bisphenol compounds such as phenol, bisphenol F, bisphenol A, and bisphenol AF, alkyl-substituted phenol compounds such as cresol and p-terriary butylphenol, halogenophenol compounds such as bromophenol, and phenolic compounds such as resorcin. Examples thereof include aromatic hydrocarbons containing two or more hydroxyl groups, naphthol compounds such as 1-naphthol, 2-naphthol, 1,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene. These phenol compounds may be used alone or in combination of two or more.

Examples of the catalyst include metal salts such as zinc acetate and manganese borate, and metal oxides such as lead oxide and zinc oxide. These catalysts can be used alone or in combination of two or more.

Further, in the production of the novolak type phenol resin (A), furfural, urea, melamine, acetoguanamine, benzoguanamine and the like can be used in combination, if necessary.

The above reaction may be carried out in the presence of an organic solvent, or an organic solvent may be added to the obtained reaction product, but since a resin having a large ortho-para ratio is easily obtained, it is possible to obtain a resin in the presence of an organic solvent. It is preferable to do so.

As the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene are preferable.

The novolak type phenol resin (A) preferably has the residual amount of the catalyst reduced by washing with water or the like, and preferably 0.005 ppm or less.

Examples of the divinylbenzene compound (B) include divinylbenzene, alkyldivinylbenzene, and halogen substitutions thereof, but divinylbenzene is preferable because it is more excellent in reactivity and workability. These divinylbenzene compounds (B) can be used alone or in combination of two or more.

The mass ratio (A / B) of the novolak-type phenol resin (A) and the divinylbenzene compound (B) is in the range of 40/60 to 70/30 because the balance between moldability and flame retardancy is better. Is preferable.

Further, as the vinyl compound capable of reacting with the novolak type phenol resin (A), other vinyl compounds other than the divinylbenzene compound (B) can be contained. Examples of other vinyl compounds include aromatic vinyl compounds such as styrene, methylstyrene, ethylstyrene, and monobromostyrene, (meth) acrylic acid methyl ester, (meth) acrylic acid stearyl ester, (meth) acrylic acid, and N. Examples thereof include aliphatic vinyl compounds such as −methylol (meth) acrylamide and γ-mercaptopropyltrimethoxysilane. These other vinyl compounds may be used alone or in combination of two or more.

Since the aluminum hydroxide (C) can impart flame retardancy to the molded product while maintaining good moldability, the total amount of the novolak type phenol resin (A) and the divinylbenzene compound is 100 parts by mass. It is important that the amount is 110 to 240 parts by mass, but 120 to 220 parts by mass is more preferable because the balance between moldability and flame retardancy is further improved.

Examples of the poly (meth) acrylic acid ester compound (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , N-Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate and other (co) polymers, but because they have a better thickening effect. , Methyl poly (meth) acrylate is preferable, and those in the form of particles are preferable. These poly (meth) acrylic acid ester compounds (D) may be used alone or in combination of two or more.

The poly (meth) acrylic acid ester compound (D) is composed of the novolak type phenol resin (A) and the divinylbenzene compound (B) from the viewpoint of the balance between the thickening effect and the appearance and strength of the obtained molded product. It is important that the amount is 0.3 to 33 parts by mass with respect to 100 parts by mass in total, but it is more preferably 0.8 to 25 parts by mass.

Examples of the reinforcing fiber (E) include organic fibers such as glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, boron fiber, metal fiber, aramid fiber, vinylon fiber, and tetron fiber, but the height is higher. Glass fiber or carbon fiber is preferable because a molded product having high strength and high elasticity can be obtained. These reinforcing fibers (E) can be used alone or in combination of two or more.

The shape of the reinforcing fiber (E) is not particularly limited, and examples thereof include short fibers, long fibers, yarns, mats, and sheets.

The content of the reinforcing fiber (E) in the components of the molding material of the present invention is preferably in the range of 10 to 60% by mass, preferably 20 to 40% by mass, because the mechanical strength of the obtained molded product is further improved. The range of is more preferable.

The components of the fiber-reinforced molding material of the present invention include a novolak-type phenol resin (A), a divinylbenzene compound (B), aluminum hydroxide (C), a poly (meth) acrylic acid ester compound (D), and reinforcing fibers ( Those other than E) may be used, for example, a thermosetting resin other than the novolak type phenol resin (A), a thermoplastic resin, a curing accelerator, a polymerization inhibitor, a filler, a low shrinkage agent, and a mold release. It can contain an agent, a thickener, a thickener, a pigment, an antioxidant, a plasticizer, a flame retardant, an antibacterial agent, an ultraviolet stabilizer, a reinforcing material, a photocuring agent and the like.

Examples of the thermosetting resin include vinyl ester resin, vinyl urethane resin, unsaturated polyester resin, acrylic resin, epoxy resin, phenol resin, melamine resin, furan resin and the like. In addition, these thermosetting resins can be used alone or in combination of two or more.

Examples of the thermoplastic resin include polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, urethane resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, polybutadiene resin, polyisoprene resin, and copolymerization thereof. Examples thereof include those modified by the above. In addition, these thermoplastic resins can be used alone or in combination of two or more.

Examples of the curing accelerator include metal chlorides such as aluminum chloride and stannous chloride, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, organic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, acetic acid and embroidery. Organic carboxylic acids such as acids and maleic acids, phosphite esters such as phosphomonophenyl, ester compounds derived from sulfuric acid and organic sulfonic acids, salts such as methyl p-toluenesulfonic acid and ammonium chloride, benzyl chloride, Examples thereof include latent catalysts typified by chloromethylstyrene, benzoyl chloride, and sulfonium salts of metal halides. These curing accelerators can be used alone or in combination of two or more.

The curing accelerator is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the novolak type phenol resin (A) because the balance between curability and the performance of the obtained molded product is further improved. ..

Examples of the filler include inorganic compounds and organic compounds, which can be used to adjust physical properties such as strength of molded products.

Examples of the inorganic compound include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, burlite, baryta, silica, silica sand, dolomite limestone, gypsum, aluminum fine powder, hollow balloon, and the like. Examples thereof include alumina, glass powder, talc, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and iron powder.

Examples of the organic compound include natural polysaccharide powders such as cellulose and chitin, synthetic resin powders, and the like, and synthetic resin powders are composed of hard resins, soft rubbers, elastomers, polymers (copolymers), and the like. Particles having a multilayer structure such as organic powder or core-shell type can be used. Specific examples thereof include particles made of butadiene rubber and / or acrylic rubber, urethane rubber, silicon rubber and the like, polyimide resin powder, fluororesin powder, phenol resin powder and the like. These fillers can be used alone or in combination of two or more.

The fiber-reinforced molding material of the present invention is a sheet molding compound (hereinafter, abbreviated as "SMC") or a bulk molding compound (hereinafter, "BMC") from the viewpoint of excellent productivity and moldability having design diversity. It is abbreviated as).

As a method for producing the SMC, the novolak type phenol resin (A), the divinylbenzene compound (B), using a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, and an extruder is used. Each component such as the aluminum hydroxide (C) and the poly (meth) acrylic acid ester compound (D) is mixed and dispersed, and the obtained resin composition is spread on a carrier film placed on the top and bottom to a uniform thickness. The reinforcing fibers (E) are sandwiched between the resin compositions on the carrier films placed above and below the reinforcing fibers (E), and then the whole is passed between the impregnated rolls and pressure is applied to the reinforcing fibers (E). ) Is impregnated with the resin composition, and then rolled up or folded into a zigzag fold. Further, it is preferable to carry out aging at a temperature of 25 to 60 ° C. after this. As the carrier film, a polyethylene film, a polypropylene film, a polyethylene-polypropylene laminate film, polyethylene terephthalate, nylon or the like can be used.

As the method for producing the BMC, the novolak type phenol resin (A) is produced by using a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, or an extruder in the same manner as the method for producing the SMC. , The divinylbenzene compound (B), the aluminum hydroxide (C), the poly (meth) acrylic acid ester compound (D), and other components were mixed and dispersed, and the reinforcing fibers (the reinforcing fibers) were added to the obtained resin composition. Examples thereof include a method of mixing and dispersing E). Further, it is preferable to ripen at a temperature of 25 to 60 ° C. like SMC.

The molded product of the present invention can be obtained from the fiber-reinforced molding material, but from the viewpoint of excellent productivity and excellent design diversity, heat compression molding of SMC or BMC is preferable as the molding method.

In the heat compression molding, for example, a predetermined amount of a molding material such as SMC or BMC is weighed, put into a mold heated to 100 to 200 ° 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 maintaining a molding pressure of 0.1 to 30 MPa, and then the molded product is taken out to obtain a molded product. The heating conditions and pressurizing conditions can be changed step by step.

Since the molded product obtained from the fiber-reinforced molded material of the present invention is excellent in appearance, bending strength, flexural modulus, etc., it is an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, a housing equipment member, a sports member. , Light vehicle members, building civil engineering members, housings for OA equipment, etc. can be suitably used.

The present invention will be described in more detail below with reference to specific examples. The ortho-para ratio of the phenol resin was determined by 13C-NMR measurement.

(Synthesis Example 1: Synthesis of Novolac Phenol Formaldehyde (A-1))
940 g (10 mol) of phenol, 281 g (7.5 mol) of 80% by mass paraformaldehyde, and 470 g of xylene were added to a four-necked 2L flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel to start stirring. 4.7 g of zinc acetate dihydrate was added as a catalyst, and the temperature was raised to the reflux temperature. After reacting under reflux for 5 hours, distillation was started to remove water and xylene as a solvent, and the temperature was raised to 130 ° C. After holding at 130 ° C. for 1 hour, the temperature was raised to 150 ° C. while distilling. Further, after partially removing free phenol under reduced pressure, the precipitated catalyst was taken out while filtering to obtain a solid novolak type phenol resin (A-1) having a melting point of 58 ° C. The ortho-para ratio of this novolak type phenol resin (A-1) was 6.6.

(Preparation Example 1: Preparation of mixed solution (1))
100 parts by mass of divinylbenzene was dissolved in 100 parts by mass of the obtained novolak-type phenol resin (A-1) at 50 ° C. to obtain a mixture (1) of the novolak-type phenol resin and divinylbenzene. ..

(Preparation Example 2: Preparation of mixed solution (2))
85 parts by mass of divinylbenzene was dissolved in 115 parts by mass of the obtained novolak-type phenol resin (A-1) at 50 ° C. to obtain a mixture (2) of the novolak-type phenol resin and divinylbenzene. ..

(Example 1: Preparation and evaluation of fiber-reinforced molding material (1))
The mixture (1) obtained in Preparation Example 1 was added to 100 parts by mass (50 parts by mass of novolak type phenol resin, 50 parts by mass of divinylbenzene) with aluminum hydroxide (“B103” manufactured by Nippon Light Metal Co., Ltd., hereinafter “aluminum hydroxide (C)”. -1) ”) 200 parts by mass, polymethacrylic acid ester organic fine particles (manufactured by Aika Kogyo Co., Ltd.,“ Zefiac F-303 ”, hereinafter referred to as“ poly (meth) acrylic acid ester compound (D-1) ” (Abbreviation.) 10 parts by mass and 6 parts by mass of a curing accelerator (a mixture of 2 parts by mass of xylene-4-sulfonic acid hydrate and 4 parts by mass of cresol) were mixed to obtain a resin composition (1).

The resin composition (1) obtained above was applied onto a PP film and cut into 1 inch (25 mm) glass fiber roving (“RS 480PB-549 AC” manufactured by Nitto Boseki Co., Ltd., hereinafter, reinforcing fiber (E-). 1) is abbreviated as 1) is prepared so that the fiber content is 23% by mass, and the resin composition is similarly dropped from the air onto the coated resin so that the fiber content is non-directional and the thickness is uniform. After sandwiching the glass fiber with the film coated with (1) and impregnating the glass fiber with a resin, the glass fiber was left in a thermostat at 45 ° C. for 24 hours to obtain a sheet-shaped fiber-reinforced molding material (1).

[Manufacturing of molded products]
The sheet-shaped fiber-reinforced molding material (1) obtained above was peeled from the film, cut into 20 cm × 20 cm, set in the center of a flat plate mold of 23 × 23 cm ² , and pressed at a press pressure of 15 MPa. Temperature upper mold 125 ° C / lower mold 115 ° C, press time 15 minutes, then press mold temperature upper mold 155 ° C / lower mold 145 ° C, press time 15 minutes, then press mold temperature upper mold 185 ° C / lower mold 175 ° C. , A flat plate-shaped molded product (1) having a thickness of 1.5 mm was obtained by molding with a pressing time of 30 minutes.

[Evaluation of moldability]
The appearance of the molded product (1) obtained above was observed, and the moldability was evaluated according to the following criteria.
◯: The fluidity of the molding material is good, and no defects such as surface roughness are observed in the molded product.
Δ: The fluidity of the molding material is good, but defects such as surface roughness are observed in a part of the molded product.
X: The fluidity of the molding material is poor, and the molded product cannot be obtained according to the mold.

[Evaluation of flame retardancy]
The obtained molded product (1) was cut into 125 mm × 13 mm × 1.5 mm, and measured in accordance with the 20 mm vertical combustion test (IEC60695-11-10B, ASTM D3801) of the UL94 combustion test, and the flame retardancy was measured. Was evaluated.

(Example 2: Preparation and evaluation of fiber-reinforced molding material (2))
A fiber-reinforced molding material (2) was produced in the same manner as in Example 1 except that 10 parts by mass of the poly (meth) acrylic acid ester compound (D-1) used in Example 1 was changed to 1 part by mass. , Moldability and flame retardancy were evaluated.

(Example 3: Preparation and evaluation of fiber-reinforced molding material (3))
A fiber-reinforced molding material (3) was produced in the same manner as in Example 1 except that 10 parts by mass of the poly (meth) acrylic acid ester compound (D-1) used in Example 1 was changed to 20 parts by mass. , Moldability and flame retardancy were evaluated.

(Example 4: Preparation and evaluation of fiber-reinforced molding material (4))
A fiber-reinforced molding material (4) was produced in the same manner as in Example 1 except that 200 parts by mass of aluminum hydroxide (C-1) used in Example 1 was changed to 120 parts by mass. The flammability was evaluated.

(Example 5: Preparation and evaluation of fiber-reinforced molding material (5))
A fiber-reinforced molding material (5) was produced in the same manner as in Example 1 except that 200 parts by mass of aluminum hydroxide (C-1) used in Example 1 was changed to 210 parts by mass. The flammability was evaluated.

(Example 6: Preparation and evaluation of fiber-reinforced molding material (6))
Except that 100 parts by mass of the mixture (1) used in Example 1 was changed to 100 parts by mass of the mixture (2) and 200 parts by mass of aluminum hydroxide (C-1) was changed to 180 parts by mass, the same as in Example 1. In the same manner, a fiber-reinforced molding material (6) was prepared and its moldability and flame retardancy were evaluated.

(Example 7: Preparation and evaluation of fiber-reinforced molding material (7))
The fiber-reinforced molding material (7) was used in the same manner as in Example 1 except that 10 parts by mass of the poly (meth) acrylic acid ester compound (D-1) used in Example 1 was changed to 0.5 parts by mass. It was prepared and evaluated for moldability and flame retardancy.

(Example 8: Preparation and evaluation of fiber reinforced molding material (8))
A fiber-reinforced molding material (8) was produced in the same manner as in Example 1 except that 10 parts by mass of the poly (meth) acrylic acid ester compound (D-1) used in Example 1 was changed to 30 parts by mass. , Moldability and flame retardancy were evaluated.

(Example 9: Preparation and evaluation of fiber-reinforced molding material (9))
A fiber-reinforced molding material (9) was produced in the same manner as in Example 1 except that 200 parts by mass of aluminum hydroxide (C-1) used in Example 1 was changed to 230 parts by mass. The flammability was evaluated.

(Comparative Example 1: Preparation and Evaluation of Fiber Reinforced Molding Material (R1))
The fiber-reinforced molding material (R1) was used in the same manner as in Example 1 except that 10 parts by mass of the poly (meth) acrylic acid ester compound (D-1) used in Example 1 was changed to 0.1 parts by mass. It was prepared and the moldability was evaluated. Since the moldability was poor, the flame retardancy was not evaluated.

(Comparative Example 2: Preparation and Evaluation of Fiber Reinforced Molding Material (R2))
A fiber-reinforced molding material (R2) was prepared in the same manner as in Example 1 except that 10 parts by mass of the poly (meth) acrylic acid ester compound (D-1) used in Example 1 was changed to 35 parts by mass. , Moldability was evaluated. Since the moldability was poor, the flame retardancy was not evaluated.

(Comparative Example 3: Preparation and Evaluation of Fiber Reinforced Molding Material (R3))
A fiber-reinforced molding material (R3) was produced in the same manner as in Example 1 except that 200 parts by mass of aluminum hydroxide (C-1) used in Example 1 was changed to 100 parts by mass. The flammability was evaluated.

(Comparative Example 4: Preparation and Evaluation of Fiber Reinforced Molding Material (R4))
A fiber-reinforced molding material (R4) was produced in the same manner as in Example 1 except that 200 parts by mass of aluminum hydroxide (C-1) used in Example 1 was changed to 250 parts by mass, and the moldability was evaluated. did. Since the moldability was poor, the flame retardancy was not evaluated.

The compositions and evaluation results of the fiber-reinforced molding materials (1) to (9) obtained above are shown in Tables 1 and 2.

Table 3 shows the compositions and evaluation results of the fiber-reinforced molding materials (R1) to (R4) obtained above.

It was confirmed that the fiber-reinforced molding materials of the present invention of Examples 1 to 9 were excellent in moldability, and the obtained molded product was excellent in flame retardancy.

On the other hand, in Comparative Example 1, the lower limit of the present invention is the poly (meth) acrylic acid ester compound (D-1) with respect to a total of 100 parts by mass of the novolak type phenol resin (A) and the divinylbenzene compound (B). Although it is an example less than 0.3 parts by mass, it was confirmed that the moldability was insufficient.

In Comparative Example 2, the poly (meth) acrylic acid ester compound (D-1) with respect to a total of 100 parts by mass of the novolak type phenol resin (A) and the divinylbenzene compound (B) is 33 mass by mass, which is the upper limit of the present invention. Although there are more examples than parts, it was confirmed that the moldability was insufficient.

Comparative Example 3 is an example in which aluminum hydroxide (C-1) is less than 110 parts by mass, which is the lower limit of the present invention, with respect to a total of 100 parts by mass of the novolak type phenol resin (A) and the divinylbenzene compound (B). However, it was confirmed that the flame retardancy was insufficient.

Comparative Example 4 is an example in which aluminum hydroxide (C-1) is more than 230 parts by mass, which is the upper limit of the present invention, with respect to a total of 100 parts by mass of the novolak type phenol resin (A) and the divinylbenzene compound (B). However, it was confirmed that the moldability was insufficient.

Claims (5)

A fiber-reinforced molding material containing a novolak-type phenol formaldehyde (A), a divinylbenzene compound (B), aluminum hydroxide (C), a poly (meth) acrylic acid ester compound (D), and reinforcing fibers (E). The aluminum hydroxide (C) is 110 to 240 parts by mass with respect to a total of 100 parts by mass of the novolak type phenol resin (A) and the divinylbenzene compound (B), and the poly (meth) acrylic acid ester. A fiber reinforced molding material, characterized in that the compound is 0.3 to 33 parts by mass. The fiber-reinforced molding material according to claim 1, wherein the ortho-para ratio of the methylene bond that crosslinks the aromatic ring of the novolak-type phenol resin (A) is 3 or more. The fiber-reinforced molding material according to claim 1 or 2, wherein the novolak-type phenol resin (A) has a number average molecular weight of 300 to 2,000. The fiber reinforced molding according to any one of claims 1 to 3, wherein the mass ratio (A / B) of the novolak type phenol resin (A) to the divinylbenzene compound (B) is 40/60 to 70/30. material. A molded product using the fiber-reinforced molding material according to any one of claims 1 to 4.