WO2021111885A1 - Sheet molding compound and molded article thereof - Google Patents

Sheet molding compound and molded article thereof Download PDF

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Publication number
WO2021111885A1
WO2021111885A1 PCT/JP2020/043116 JP2020043116W WO2021111885A1 WO 2021111885 A1 WO2021111885 A1 WO 2021111885A1 JP 2020043116 W JP2020043116 W JP 2020043116W WO 2021111885 A1 WO2021111885 A1 WO 2021111885A1
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Prior art keywords
mass
parts
resin
molding compound
sheet molding
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PCT/JP2020/043116
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French (fr)
Japanese (ja)
Inventor
山本　修平
英樹 塩根
欧 柴田
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Dic株式会社
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Priority to JP2021521543A priority Critical patent/JPWO2021111885A1/en
Publication of WO2021111885A1 publication Critical patent/WO2021111885A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/34—Feeding the material to the mould or the compression means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/18—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length in the form of a mat, e.g. sheet moulding compound [SMC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles

Definitions

  • the present invention relates to a sheet molding compound and a molded product thereof.
  • the sheet molding compound is a molding material in which glass fibers are impregnated with a paste mixed with a thermosetting resin, an inorganic filler, a thickener, a curing agent, etc. to form a sheet, and aged and semi-cured. ..
  • a molded product can be obtained by heating and pressure molding this sheet molding compound 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.
  • thermosetting resin composition containing a thermosetting resin, a polymerizable unsaturated monomer, aluminum hydroxide, a phosphorus-based flame retardant, and a fiber reinforcing material.
  • Compounds have been proposed (see, for example, Patent Document 1).
  • this sheet molding compound has a problem that the resin impregnation property into the glass fiber is deteriorated and the mechanical strength is lowered because the compound viscosity is high because the amount of the filler added is large.
  • An object to be solved by the present invention is to provide a sheet molding compound capable of obtaining a molded product having excellent resin impregnation property and excellent strength such as flame retardancy, appearance, and bending strength.
  • the present inventors have determined that a sheet molding compound containing a specific resin component, a red phosphorus flame retardant, aluminum hydroxide, a polymerization initiator, magnesium oxide and reinforcing fibers in a specific mass ratio solves the above-mentioned problems.
  • the heading, the present invention was completed.
  • the red phosphorus flame retardant (B) is 1 to 50 parts by mass
  • the aluminum hydroxide (C) is 60 parts by mass with respect to 100 parts by mass of the resin component (A).
  • the present invention relates to a sheet molding compound characterized by having a weight of up to 220 parts by mass.
  • the seat molding compound of the present invention can obtain a molded product having excellent resin impregnation property and excellent strength such as flame retardancy, appearance, and bending strength, it is possible to obtain an automobile member, a railroad vehicle member, an aerospace machine member, and a ship. It can be suitably used for a member, a housing equipment member, a sports member, a light vehicle member, a building civil engineering member, a housing of an OA device, or the like.
  • the sheet molding compound of the present invention (hereinafter, may be abbreviated as "SMC") is a resin component (A) containing an unsaturated polyester resin (a1), a red phosphorus flame retardant (B), and aluminum hydroxide (hereinafter, abbreviated as "SMC”).
  • the resin component (A) of the present invention contains an unsaturated polyester resin (a1) as an essential component, but contains a polymerizable unsaturated monomer (a2), a low shrinkage agent (a3), and the like. be able to.
  • the unsaturated polyester resin (a1) in the resin component (A) has a high viscosity, it should be diluted with the polymerizable unsaturated monomer (a2) before being mixed with other components. Is preferable, and it is preferable to dilute it to 30 to 60% by mass.
  • the polymerizable unsaturated monomer (a2) is a vinyl monomer such as styrene or ⁇ -methylstyrene; a single amount of (meth) acrylate ester such as methyl (meth) acrylate or butyl (meth) acrylate.
  • the body etc. can be mentioned.
  • these polymerizable unsaturated monomers can be used alone or in combination of two or more.
  • (meth) acrylic acid represents either or both of "acrylic acid” and “methacrylic acid”.
  • the mass ratio (a1 / a2) of the unsaturated polyester resin (a1) to the polymerizable unsaturated monomer (a2) is 40 because SMC is easy to produce and is excellent in curing reactivity at high temperature. / 60-60 / 40% by mass is preferable.
  • Examples of the low shrinkage agent (a3) include nylon resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, and a resin obtained by modifying these by copolymerization or the like.
  • Examples thereof include thermoplastic resins such as. Among these, polystyrene resin, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-olefin copolymer, and poly (meth) acrylic acid ester are preferable.
  • These low shrinkage agents can be used alone or in combination of two or more.
  • the low shrinkage agent (a3) in the resin component (A) is preferably 2 to 20% by mass because of its good heat compression moldability and the appearance of the obtained molded product.
  • the content of the red phosphorus flame retardant (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the resin component (A), but the red phosphorus flame retardant (B) is dispersed in the resin. 2 to 20 parts by mass is preferable because it has good properties and sufficient flame retardancy can be obtained.
  • the red phosphorus flame retardant (B) is preferably one in which the particle surface is coated with a resin because the safety and the dispersibility when mixed with the resin component are further improved.
  • the content of the aluminum hydroxide (C) is 60 to 220 parts by mass with respect to 100 parts by mass of the resin component (A), but 110 because the strength such as the bending strength of the molded product is further improved. To 150 parts by mass is preferable.
  • the polymerization initiator (D) 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 perester compound, and a per carbonate are used. Examples include compounds, which can be appropriately selected according to the molding conditions. These polymerization initiators can be used alone or in combination of two or more. These polymerization initiators are preferably contained in an amount of 0.4 to 4 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a1).
  • the content of magnesium oxide (E) is 0. 0 with respect to 100 parts by mass of the unsaturated polyester resin (a1). 1 to 5 parts by mass is preferable, and 0.3 to 3 parts by mass is more preferable.
  • the reinforcing fiber (F) examples 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 price 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 length of the reinforcing fiber (F) is preferably in the range of 10 to 60 mm from the viewpoint of the cut property of the glass fiber itself and the impregnation property with the resin component (A). Further, reinforcing fibers having different lengths may be mixed.
  • the content of the reinforcing fiber (F) in the components of the SMC of the present invention is preferably in the range of 10 to 60% by mass, preferably in the range of 20 to 40% by mass, because the mechanical strength of the obtained molded product is further improved. Is more preferable.
  • the components of the SMC of the present invention include the above-mentioned resin component (A), red phosphorus flame retardant (B), aluminum hydroxide (C), polymerization initiator (D), magnesium oxide (E) and reinforcing fiber (F).
  • a thermosetting resin other than the unsaturated polyester resin (a1) a thermoplastic resin, a curing accelerator, a polymerization inhibitor, a filler, a low shrinkage agent, and a mold release agent.
  • Thickener, thickener, pigment, antioxidant, plasticizer, flame retardant, antibacterial agent, ultraviolet stabilizer, reinforcing material, photocuring agent and the like can be contained.
  • thermosetting resin examples include vinyl ester resin, vinyl urethane resin, unsaturated polyester resin, acrylic resin, epoxy resin, phenol resin, melamine resin, furan resin and the like. Further, these thermosetting resins can be used alone or in combination of two or more.
  • thermoplastic resin examples 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.
  • the curing accelerator examples 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.
  • 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 examples 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, sulfonium salts of metal halides, and the like. 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 resin component (A) because the balance between curability and the performance of the obtained molded product is further improved.
  • the filler includes an inorganic compound and an organic compound, and can be used to adjust physical properties such as strength of a molded product.
  • 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, cold talc, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and iron powder.
  • organic compound examples 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.
  • a resin component (A), a red phosphorus flame retardant (B), and a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, and an extruder are used.
  • a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, and an extruder.
  • Each component such as aluminum hydroxide (C), polymerization initiator (D), magnesium oxide (E) is mixed and dispersed, and the obtained resin composition has a uniform thickness on a carrier film placed on the upper and lower sides.
  • the reinforcing fibers (F) are sandwiched between the resin compositions on the carrier films installed above and below, and then the whole is passed between the impregnating rolls, and pressure is applied to the resin on the reinforcing fibers (F).
  • Examples thereof include a method of impregnating the composition and then winding it into a roll or folding it into a zigzag fold. Further, it is preferable to carry out aging at a temperature of 25 to 60 ° C. after this.
  • the carrier film a polyethylene film, a polypropylene film, a polyethylene-polypropylene laminate film, polyethylene terephthalate, nylon or the like can be used.
  • the molded product of the present invention can be obtained from the SMC, but from the viewpoint of excellent productivity and excellent design diversity, heat compression molding is preferable as the molding method.
  • a predetermined amount of SMC is weighed, put into a mold heated to 100 to 200 ° C., molded by a compression molding machine, SMC is molded, and 0.1 to 30 MPa.
  • a manufacturing method is used in which the SMC is cured by maintaining the molding pressure of the above, and then the molded product is taken out to obtain the molded product.
  • the heating conditions and pressurizing conditions can be changed step by step.
  • the SMC of the present invention can obtain a molded product having excellent resin impregnation property and excellent strength such as flame retardancy, appearance, and bending strength, an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, and the like. It can be suitably used for housing equipment members, sports members, light vehicle members, building civil engineering members, housings for OA equipment, and the like.
  • Example 1 Preparation and evaluation of SMC (1)
  • PS-281S manufactured by DC Material Co., Ltd.
  • the resin composition (1) obtained above was applied onto a PP film.
  • glass fiber roving (“PB-549” manufactured by Nitto Spinning Co., Ltd.) cut into 1 inch (about 25 mm) is prepared so that the fiber content is 28% by mass, and the thickness becomes uniform without fiber directionality.
  • the resin composition (1) coated on the PP film is uniformly dropped from the air, sandwiched between the films coated with the same resin composition (1), the glass fibers are impregnated with the resin, and then the temperature is kept constant at 45 ° C. It was left inside for 24 hours to obtain SMC (1).
  • the SMC (1) obtained above was cut into 25 cm x 25 cm and set in the center of a 30 cm x 30 cm flat plate die, and the upper die temperature of the press die was 145 ° C., the lower die temperature was 130 ° C., and the press pressure. Molding was performed at 10 MPa and a press time of 6 minutes to obtain a flat plate-shaped molded product (1-1) having a thickness of 1.5 mm and a flat plate-shaped molded product (1-2) having a thickness of 4 mm.
  • Example 2 Preparation and evaluation of SMC (2)
  • C-1 and C-2 used in Example 1, 50 parts by mass of aluminum hydroxide (C-1) and aluminum hydroxide (C-2).
  • SMC (2) and a molded product were produced and evaluated in various ways by operating in the same manner as in Example 1 except that the weight was changed to 50 parts by mass.
  • Example 3 Preparation and evaluation of SMC (3)
  • C-1 and C-2 used in Example 1
  • SMC (3) and a molded product were produced by the same operation as in Example 1 except that the weight was changed to 90 parts by mass, and various evaluations were performed.
  • Example 4 Preparation and evaluation of SMC (4)
  • SMC (4) and a molded product were produced by operating in the same manner as in Example 1 except that 5 parts by mass of the red phosphorus flame retardant used in Example 1 was changed to 2 parts by mass of the red phosphorus flame retardant. Then, various evaluations were performed.
  • Table 1 shows the evaluation results of SMC (1) to (4) obtained above.
  • Table 2 shows the evaluation results of SMC (R1) to (R3) obtained above.
  • Comparative Example 1 is an example in which the content of aluminum hydroxide (C) with respect to 100 parts by mass of the resin component (A) is less than 60 parts by mass, which is the lower limit of the present invention, but the flame retardancy of the molded product is high. It was inadequate.
  • Comparative Example 2 is an example in which the content of aluminum hydroxide (C) with respect to 100 parts by mass of the resin component (A) is larger than 220 parts by mass, which is the upper limit of the present invention, but the resin impregnation property and the appearance of the molded product are improved. It was inferior and the strength of the molded product was insufficient.
  • Comparative Example 3 is an example in which the red phosphorus flame retardant (B) is not contained, but the flame retardancy is poor.

Abstract

Provided is a sheet molding compound comprising: a resin component (A) containing an unsaturated polyester resin (a1); a red phosphorus-based flame retardant (B); aluminum hydroxide (C); a polymerization initiator (D); magnesium oxide (E); and reinforcing fibers (F), the sheet molding compound being characterized by containing, per 100 parts by mass of the resin component (A), 1-50 parts by mass of the red phosphorus-based flame retardant (B) and 60-220 parts by mass of the aluminum hydroxide (C). This sheet molding compound excels in resin impregnating properties, and can be used to obtain a molded article that excels in flame retardance, appearance, and strengths such as bending strength. Therefore, this sheet molding compound can be suitably used in automobile members, railway vehicle members, aerospace machinery members, ship members, housing equipment members, sports members, non-motorized vehicle members, construction and civil engineering members, and cases for OA devices, etc.

Description

シートモールディングコンパウンド及びその成形品Sheet molding compound and its molded products
　本発明は、シートモールディングコンパウンド及びその成形品に関する。 The present invention relates to a sheet molding compound and a molded product thereof.
　シートモールディングコンパウンドは、熱硬化性樹脂、無機充填剤、増粘剤、硬化剤等を混ぜたペーストをガラス繊維に含浸させてシート状とし、熟成処理を行って、半硬化させた成形材料である。このシートモールディングコンパウンドを金型によって加熱・加圧成形することで、成形品が得られる。このような成形品は、優れた耐久性や耐水性、機械強度、難燃性等の特性を利用して、浴室機器や貯水槽、浄化槽、建築材、床材、電気部品、車両用材料等として幅広く用いられているが、建築用材料や車両用材料、航空機材料等においては、高い難燃性が求められている。 The sheet molding compound is a molding material in which glass fibers are impregnated with a paste mixed with a thermosetting resin, an inorganic filler, a thickener, a curing agent, etc. to form a sheet, and aged and semi-cured. .. A molded product can be obtained by heating and pressure molding this sheet molding compound 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.
　このような状況下、熱硬化性樹脂と、重合性不飽和単量体と、水酸化アルミニウムと、リン系難燃剤と、繊維補強材とを含有する熱硬化性樹脂組成物を用いたシートモールディングコンパウンドが提案されている（例えば、特許文献１参照。）。しかしながら、このシートモールディングコンパウンドは、フィラー添加量が多いことからコンパウンド粘度が高くなるため、ガラス繊維への樹脂含浸性が悪化して機械的強度が低下するという問題があった。 Under such circumstances, sheet molding using a thermosetting resin composition containing a thermosetting resin, a polymerizable unsaturated monomer, aluminum hydroxide, a phosphorus-based flame retardant, and a fiber reinforcing material. Compounds have been proposed (see, for example, Patent Document 1). However, this sheet molding compound has a problem that the resin impregnation property into the glass fiber is deteriorated and the mechanical strength is lowered because the compound viscosity is high because the amount of the filler added is large.
特開２０１３－８７１３３号公報Japanese Unexamined Patent Publication No. 2013-87133
　本発明が解決しようとする課題は、樹脂含浸性に優れ、難燃性、外観、及び曲げ強さ等の強度に優れる成形品が得られるシートモールディングコンパウンドを提供することである。 An object to be solved by the present invention is to provide a sheet molding compound capable of obtaining a molded product having excellent resin impregnation property and excellent strength such as flame retardancy, appearance, and bending strength.
　本発明者等は、特定の樹脂成分、赤リン系難燃剤、水酸化アルミニウム、重合開始剤、酸化マグネシウム及び強化繊維を特定の質量比率で含有するシートモールディングコンパウンドが、上記課題を解決することを見出し、本発明を完成した。 The present inventors have determined that a sheet molding compound containing a specific resin component, a red phosphorus flame retardant, aluminum hydroxide, a polymerization initiator, magnesium oxide and reinforcing fibers in a specific mass ratio solves the above-mentioned problems. The heading, the present invention was completed.
　すなわち、不飽和ポリエステル樹脂（ａ１）を含む樹脂成分（Ａ）、赤リン系難燃剤（Ｂ）、水酸化アルミニウム（Ｃ）、重合開始剤（Ｄ）、酸化マグネシウム（Ｅ）及び強化繊維（Ｆ）を含有するシートモールディングコンパウンドであって、前記樹脂成分（Ａ）１００質量部に対し、前記赤リン系難燃剤（Ｂ）が１～５０質量部であり、前記水酸化アルミニウム（Ｃ）が６０～２２０質量部であることを特徴とするシートモールディングコンパウンドに関する。 That is, a resin component (A) containing an unsaturated polyester resin (a1), a red phosphorus flame retardant (B), aluminum hydroxide (C), a polymerization initiator (D), magnesium oxide (E) and reinforcing fibers (F). ), The red phosphorus flame retardant (B) is 1 to 50 parts by mass, and the aluminum hydroxide (C) is 60 parts by mass with respect to 100 parts by mass of the resin component (A). The present invention relates to a sheet molding compound characterized by having a weight of up to 220 parts by mass.
　本発明のシートモールディングコンパウンドは、樹脂含浸性に優れ、難燃性、外観、及び曲げ強さ等の強度に優れる成形品が得られることから、自動車部材、鉄道車両部材、航空宇宙機部材、船舶部材、住宅設備部材、スポーツ部材、軽車両部材、建築土木部材、ＯＡ機器等の筐体等に好適に用いることができる。 Since the seat molding compound of the present invention can obtain a molded product having excellent resin impregnation property and excellent strength such as flame retardancy, appearance, and bending strength, it is possible to obtain an automobile member, a railroad vehicle member, an aerospace machine member, and a ship. It can be suitably used for a member, a housing equipment member, a sports member, a light vehicle member, a building civil engineering member, a housing of an OA device, or the like.
　本発明のシートモールディングコンパウンド（以下、「ＳＭＣ」と略記する場合がある。）は、不飽和ポリエステル樹脂（ａ１）を含む樹脂成分（Ａ）、赤リン系難燃剤（Ｂ）、水酸化アルミニウム（Ｃ）、重合開始剤（Ｄ）、酸化マグネシウム（Ｅ）及び強化繊維（Ｆ）を含有するＳＭＣであって、前記樹脂成分（Ａ）１００質量部に対し、前記赤リン系難燃剤（Ｂ）が１～５０質量部であり、前記水酸化アルミニウム（Ｃ）が６０～２２０質量部であるものである。 The sheet molding compound of the present invention (hereinafter, may be abbreviated as "SMC") is a resin component (A) containing an unsaturated polyester resin (a1), a red phosphorus flame retardant (B), and aluminum hydroxide (hereinafter, abbreviated as "SMC"). An SMC containing C), a polymerization initiator (D), magnesium oxide (E) and reinforcing fibers (F), wherein the red phosphorus flame retardant (B) is based on 100 parts by mass of the resin component (A). Is 1 to 50 parts by mass, and the aluminum hydroxide (C) is 60 to 220 parts by mass.
　本発明の樹脂成分（Ａ）は、不飽和ポリエステル樹脂（ａ１）を必須成分として含有するものであるが、重合性不飽和単量体（ａ２）、低収縮化剤（ａ３）等を含有することができる。 The resin component (A) of the present invention contains an unsaturated polyester resin (a1) as an essential component, but contains a polymerizable unsaturated monomer (a2), a low shrinkage agent (a3), and the like. be able to.
前記樹脂成分（Ａ）中の前記不飽和ポリエステル樹脂（ａ１）は、高粘度であることから、他の成分と混合する前に前記重合性不飽和単量体（ａ２）で希釈しておくことが好ましく、３０～６０質量％に希釈しておくことが好ましい。 Since the unsaturated polyester resin (a1) in the resin component (A) has a high viscosity, it should be diluted with the polymerizable unsaturated monomer (a2) before being mixed with other components. Is preferable, and it is preferable to dilute it to 30 to 60% by mass.
　前記重合性不飽和単量体（ａ２）としては、スチレン、α－メチルスチレン等のビニル単量体；（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステル単量体などが挙げられる。また、これらの重合性不飽和単量体は、単独で用いることも２種以上併用することもできる。 The polymerizable unsaturated monomer (a2) is a vinyl monomer such as styrene or α-methylstyrene; a single amount of (meth) acrylate ester such as methyl (meth) acrylate or butyl (meth) acrylate. The body etc. can be mentioned. In addition, these polymerizable unsaturated monomers can be used alone or in combination of two or more.
　本発明において「（メタ）アクリル酸」の表記は、「アクリル酸」及び「メタクリル酸」のいずれか一方または両方を表すものである。 In the present invention, the notation of "(meth) acrylic acid" represents either or both of "acrylic acid" and "methacrylic acid".
前記不飽和ポリエステル樹脂（ａ１）と前記重合性不飽和単量体（ａ２）との質量比（ａ１／ａ２）は、ＳＭＣが作製し易く、且つ高温時の硬化反応性に優れることから、４０／６０～６０／４０質量％が好ましい。 The mass ratio (a1 / a2) of the unsaturated polyester resin (a1) to the polymerizable unsaturated monomer (a2) is 40 because SMC is easy to produce and is excellent in curing reactivity at high temperature. / 60-60 / 40% by mass is preferable.
　前記低収縮化剤（ａ３）としては、例えば、ナイロン樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリカーボネート樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ポリスチレン樹脂、アクリル樹脂、およびこれらを共重合等により変性した樹脂などの熱可塑性樹脂が挙げられる。これらの中でも、ポリスチレン樹脂、スチレン－アクリル酸共重合体、スチレン－酢酸ビニル共重合体、スチレン－ブタジエン共重合体、スチレン－オレフィン共重合体、ポリ（メタ）アクリル酸エステルが好ましい。これらの低収縮化剤は、単独で用いることも、２種以上を併用することもできる。 Examples of the low shrinkage agent (a3) include nylon resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polypropylene resin, polyethylene resin, polystyrene resin, acrylic resin, and a resin obtained by modifying these by copolymerization or the like. Examples thereof include thermoplastic resins such as. Among these, polystyrene resin, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-olefin copolymer, and poly (meth) acrylic acid ester are preferable. These low shrinkage agents can be used alone or in combination of two or more.
前記樹脂成分（Ａ）中の前記低収縮化剤（ａ３）は、加熱圧縮成形性及び得られる成形品の外観が良好であることから、２～２０質量％が好ましい。 The low shrinkage agent (a3) in the resin component (A) is preferably 2 to 20% by mass because of its good heat compression moldability and the appearance of the obtained molded product.
前記赤リン系難燃剤（Ｂ）の含有量は、前記樹脂成分（Ａ）１００質量部に対し、１～５０質量部であるが、樹脂中への前記赤リン系難燃剤（Ｂ）の分散性が良好で、且つ十分な難燃性が得られることから、２～２０質量部が好ましい。 The content of the red phosphorus flame retardant (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the resin component (A), but the red phosphorus flame retardant (B) is dispersed in the resin. 2 to 20 parts by mass is preferable because it has good properties and sufficient flame retardancy can be obtained.
前記赤リン系難燃剤（Ｂ）は、安全性及び樹脂成分と混合した際の分散性がより向上することから、粒子表面が樹脂で被覆されたものが好ましい。 The red phosphorus flame retardant (B) is preferably one in which the particle surface is coated with a resin because the safety and the dispersibility when mixed with the resin component are further improved.
　前記水酸化アルミニウム（Ｃ）の含有量は、前記樹脂成分（Ａ）１００質量部に対し、６０～２２０質量部であるが、成形品の曲げ強さ等の強度がより向上することから、１１０～１５０質量部が好ましい。 The content of the aluminum hydroxide (C) is 60 to 220 parts by mass with respect to 100 parts by mass of the resin component (A), but 110 because the strength such as the bending strength of the molded product is further improved. To 150 parts by mass is preferable.
　前記重合開始剤（Ｄ）は、特に限定されないが、有機過酸化物が好ましく、例えば、ジアシルパーオキサイド化合物、パーオキシエステル化合物、ハイドロパーオキサイド化合物、ケトンパーオキサイド化合物、アルキルパーエステル化合物、パーカーボネート化合物等が挙げられ、成形条件に応じて適宜選択できる。これらの重合開始剤は、単独で用いることも２種以上併用することもできる。これらの重合開始剤は、前記不飽和ポリエステル樹脂（ａ１）１００質量部に対して、０．４～４質量部含有することが好ましい。 The polymerization initiator (D) 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 perester compound, and a per carbonate are used. Examples include compounds, which can be appropriately selected according to the molding conditions. These polymerization initiators can be used alone or in combination of two or more. These polymerization initiators are preferably contained in an amount of 0.4 to 4 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a1).
前記酸化マグネシウム（Ｅ）の含有量は、ハンドリング性、高温時の流動性、及び保存安定性のバランスがより向上することから、前記不飽和ポリエステル樹脂（ａ１）１００質量部に対して、０．１～５質量部が好ましく、０．３～３質量部がより好ましい。 Since the balance of handleability, fluidity at high temperature, and storage stability is further improved, the content of magnesium oxide (E) is 0. 0 with respect to 100 parts by mass of the unsaturated polyester resin (a1). 1 to 5 parts by mass is preferable, and 0.3 to 3 parts by mass is more preferable.
　前記強化繊維（Ｆ）としては、例えば、ガラス繊維、炭素繊維、炭化ケイ素繊維、アルミナ繊維、ボロン繊維、金属繊維、アラミド繊維、ビニロン繊維、テトロン繊維等の有機繊維などが挙げられるが、より高強度、高弾性の成形品が得られることから、ガラス繊維又は炭素繊維好ましい。これらの強化繊維（Ｅ）は単独で用いることも、２種以上併用することもできる。 Examples of the reinforcing fiber (F) 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 price 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.
前記強化繊維（Ｆ）の長さとしては、ガラス繊維自体のカット性や樹脂成分（Ａ）との含浸性の観点から、１０～６０ｍｍ長さの範囲が好ましい。また、異なる長さの強化繊維を混合させても良い。 The length of the reinforcing fiber (F) is preferably in the range of 10 to 60 mm from the viewpoint of the cut property of the glass fiber itself and the impregnation property with the resin component (A). Further, reinforcing fibers having different lengths may be mixed.
　本発明のＳＭＣの成分中の前記強化繊維（Ｆ）の含有率は、得られる成形品の機械強度がより向上することから、１０～６０質量％の範囲が好ましく、２０～４０質量％の範囲がより好ましい。 The content of the reinforcing fiber (F) in the components of the SMC of the present invention is preferably in the range of 10 to 60% by mass, preferably in the range of 20 to 40% by mass, because the mechanical strength of the obtained molded product is further improved. Is more preferable.
　本発明のＳＭＣの成分としては、上記した樹脂成分（Ａ）、赤リン系難燃剤（Ｂ）、水酸化アルミニウム（Ｃ）、重合開始剤（Ｄ）、酸化マグネシウム（Ｅ）及び強化繊維（Ｆ）以外のものを使用してもよく、例えば、前記不飽和ポリエステル樹脂（ａ１）以外の熱硬化性樹脂、熱可塑性樹脂、硬化促進剤、重合禁止剤、充填剤、低収縮剤、離型剤、増粘剤、減粘剤、顔料、酸化防止剤、可塑剤、難燃剤、抗菌剤、紫外線安定剤、補強材、光硬化剤等を含有することができる。 The components of the SMC of the present invention include the above-mentioned resin component (A), red phosphorus flame retardant (B), aluminum hydroxide (C), polymerization initiator (D), magnesium oxide (E) and reinforcing fiber (F). ) May be used, for example, a thermosetting resin other than the unsaturated polyester resin (a1), a thermoplastic resin, a curing accelerator, a polymerization inhibitor, a filler, a low shrinkage agent, and a mold release agent. , Thickener, thickener, pigment, antioxidant, plasticizer, flame retardant, antibacterial agent, ultraviolet stabilizer, reinforcing material, photocuring agent and the like can be contained.
　前記熱硬化性樹脂としては、例えば、ビニルエステル樹脂、ビニルウレタン樹脂、不飽和ポリエステル樹脂、アクリル樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、フラン樹脂等が挙げられる。また、これらの熱硬化性樹脂は、単独で用いることも２種以上併用することもできる。 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. Further, these thermosetting resins can be used alone or in combination of two or more.
　前記熱可塑性樹脂としては、例えば、ポリアミド樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリカーボネート樹脂、ウレタン樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ポリスチレン樹脂、アクリル樹脂、ポリブタジエン樹脂、ポリイソプレン樹脂およびこれらを共重合等により変性させたものが挙げられる。また、これらの熱可塑性樹脂は、単独で用いることも２種以上併用することもできる。 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.
　前記硬化促進剤としては、例えば、塩化アルミニウム、塩化第一錫等の金属塩化物、硫酸、塩酸、リン酸等の無機酸、ベンゼンスルホン酸、パラトルエンスルホン酸等の有機スルホン酸、酢酸、しゅう酸、マレイン酸等の有機カルボン酸、亜リンモノフェニル等の亜リン酸エステル、硫酸や有機スルホン酸から誘導されるエステル化合物、ｐ－トルエンスルホン酸メチルや、塩化アンモニウム等の塩、塩化ベンジル、クロロメチルスチレン、塩化ベンゾイル、ハロゲン化金属のスルフォニウム塩等で代表される潜在性触媒などが挙げられる。これら硬化促進剤は、単独で用いることも２種以上併用することもできる。 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, sulfonium salts of metal halides, and the like. These curing accelerators can be used alone or in combination of two or more.
　前記硬化促進剤は、硬化性及び得られる成形品の性能のバランスがより向上することから、前記樹脂成分（Ａ）１００質量部に対して、０．５～１０質量部の範囲が好ましい。 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 resin component (A) because the balance between curability and the performance of the obtained molded product is further improved.
　前記充填剤としては、無機化合物、有機化合物があり、成形品の強度等の物性を調整するために使用できる。 The filler includes an inorganic compound and an organic compound, and can be used to adjust physical properties such as strength of a molded product.
　前記無機化合物としては、例えば、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、マイカ、タルク、カオリン、クレー、セライト、アスベスト、バーライト、バライタ、シリカ、ケイ砂、ドロマイト石灰石、石こう、アルミニウム微粉、中空バルーン、アルミナ、ガラス粉、寒水石、酸化ジルコニウム、三酸化アンチモン、酸化チタン、二酸化モリブデン、鉄粉等が挙げられる。 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, cold talc, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and iron powder.
　前記有機化合物としては、セルロース、キチン等の天然多糖類粉末や、合成樹脂粉末等があり、合成樹脂粉末としては、硬質樹脂、軟質ゴム、エラストマーまたは重合体（共重合体）などから構成される有機物の粉体やコアシェル型などの多層構造を有する粒子を使用できる。具体的には、ブタジエンゴムおよび／またはアクリルゴム、ウレタンゴム、シリコンゴム等からなる粒子、ポリイミド樹脂粉末、フッ素樹脂粉末、フェノール樹脂粉末などが挙げられる。これらの充填剤は、単独で用いることも、２種以上を併用することもできる。 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.
　本発明のＳＭＣの製造方法としては、通常のミキサー、インターミキサー、プラネタリーミキサー、ロール、ニーダー、押し出し機などの混合機を用いて、樹脂成分（Ａ）、赤リン系難燃剤（Ｂ）、水酸化アルミニウム（Ｃ）、重合開始剤（Ｄ）、酸化マグネシウム（Ｅ）等の各成分を混合・分散し、得られた樹脂組成物を上下に設置されたキャリアフィルムに均一な厚さになるように塗布し、強化繊維（Ｆ）を前記上下に設置されたキャリアフィルム上の樹脂組成物で挟み込み、次いで、全体を含浸ロールの間に通して、圧力を加えて強化繊維（Ｆ）に樹脂組成物を含浸させた後、ロール状に巻き取る又はつづら折りに畳む方法等が挙げられる。さらに、この後に２５～６０℃の温度で熟成を行うことが好ましい。キャリアフィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエチレンとポリプロピレンのラミネートフィルム、ポリエチレンテレフタレート、ナイロン等を用いることができる。 As a method for producing the SMC of the present invention, a resin component (A), a red phosphorus flame retardant (B), and a mixer such as a normal mixer, an intermixer, a planetary mixer, a roll, a kneader, and an extruder are used. Each component such as aluminum hydroxide (C), polymerization initiator (D), magnesium oxide (E) is mixed and dispersed, and the obtained resin composition has a uniform thickness on a carrier film placed on the upper and lower sides. Then, the reinforcing fibers (F) are sandwiched between the resin compositions on the carrier films installed above and below, and then the whole is passed between the impregnating rolls, and pressure is applied to the resin on the reinforcing fibers (F). Examples thereof include a method of impregnating the composition and then winding it into a roll or folding it 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.
本発明の成形品は、前記ＳＭＣより得られるが、生産性に優れる点とデザイン多様性に優れる観点からその成形方法としては、加熱圧縮成形が好ましい。 The molded product of the present invention can be obtained from the SMC, but from the viewpoint of excellent productivity and excellent design diversity, heat compression molding is preferable as the molding method.
　前記加熱圧縮成形としては、例えば、ＳＭＣを所定量計量し、１００～２００℃に加熱した金型に投入し、圧縮成形機にて型締めを行い、ＳＭＣを賦型させ、０．１～３０ＭＰａの成形圧力を保持することによって、ＳＭＣを硬化させ、その後成形品を取り出し成形品を得る製造方法が用いられる。なお、加熱条件や加圧条件は段階的に変更することもできる。 In the heat compression molding, for example, a predetermined amount of SMC is weighed, put into a mold heated to 100 to 200 ° C., molded by a compression molding machine, SMC is molded, and 0.1 to 30 MPa. A manufacturing method is used in which the SMC is cured by maintaining the molding pressure of the above, and then the molded product is taken out to obtain the molded product. The heating conditions and pressurizing conditions can be changed step by step.
　本発明のＳＭＣは、樹脂含浸性に優れ、難燃性、外観、及び曲げ強さ等の強度に優れる成形品が得られることから、自動車部材、鉄道車両部材、航空宇宙機部材、船舶部材、住宅設備部材、スポーツ部材、軽車両部材、建築土木部材、ＯＡ機器等の筐体等に好適に用いることができる。 Since the SMC of the present invention can obtain a molded product having excellent resin impregnation property and excellent strength such as flame retardancy, appearance, and bending strength, an automobile member, a railroad vehicle member, an aerospace machine member, a ship member, and the like. It can be suitably used for housing equipment members, sports members, light vehicle members, building civil engineering members, housings for OA equipment, and the like.
　以下に本発明を具体的な実施例を挙げてより詳細に説明する。 The present invention will be described in more detail below with specific examples.
（実施例１：ＳＭＣ（１）の作製及び評価）
　不飽和ポリエステル樹脂４８質量部とスチレン３２質量部との混合物（ディーアイシーマテリアル株式会社製「ＰＳ－２８１Ｓ」）８０質量部に、ポリスチレン樹脂５．２質量部とスチレン９．８質量部との混合物（ディーアイシーマテリアル株式会社製「ＰＳ－９５４Ｎ」）１５質量部、スチレン５質量部、重合禁止剤（共同薬品工業株式会社製「Ｋ－ＮＯＸ－ＢＨＴ」；ジブチルヒドロキシトルエン）０．２質量部、
水酸化アルミニウム（Ｃ－１）（日本軽金属株式会社製「Ｂ－１０３」）６５質量部、水酸化アルミニウム（Ｃ－２）（日本軽金属株式会社製「Ｂ－１５３」）６５質量部、赤リン系難燃剤（燐化学工業株式会社製「ノーバレッド１２０ＵＦＡ」）５質量部、重合開始剤（化薬ヌーリオン株式会社製「トリゴノックス２２－７０Ｅ」）１．２質量部、及び酸化マグネシウム０．８質量部をディゾルバーにより混合し、樹脂組成物（１）を得た。 (Example 1: Preparation and evaluation of SMC (1))
A mixture of 48 parts by mass of unsaturated polyester resin and 32 parts by mass of styrene (“PS-281S” manufactured by DC Material Co., Ltd.) 80 parts by mass, and a mixture of 5.2 parts by mass of polystyrene resin and 9.8 parts by mass of styrene. ("PS-954N" manufactured by DIC Material Co., Ltd.) 15 parts by mass, 5 parts by mass of styrene, 0.2 parts by mass of a polymerization inhibitor ("K-NOX-BHT" manufactured by Kyodo Yakuhin Kogyo Co., Ltd .; dibutyl hydroxytoluene),
Aluminum hydroxide (C-1) (“B-103” manufactured by Nippon Light Metal Co., Ltd.) 65 parts by mass, Aluminum hydroxide (C-2) (“B-153” manufactured by Nippon Light Metal Co., Ltd.) 65 parts by mass, red phosphorus 5 parts by mass of flame retardant ("Nova Red 120UFA" manufactured by Rinkagaku Kogyo Co., Ltd.), 1.2 parts by mass of polymerization initiator ("Trigonox 22-70E" manufactured by Kayaku Akzo Corporation), and 0.8 mass by mass of magnesium oxide The parts were mixed with a dissolver to obtain a resin composition (1).
上記で得た樹脂組成物（１）をＰＰフィルム上に塗布した。次いで、１インチ（約２５ｍｍ）にカットしたガラス繊維ロービング（日東紡績株式会社製「ＰＢ－５４９」）を繊維含有率が２８質量％になるよう準備し、繊維方向性が無く厚みが均一になるよう、上記ＰＰフィルム上に塗布した樹脂組成物（１）上に空中から均一落下させ、同じ樹脂組成物（１）を塗布したフィルムで挟み込みガラス繊維に樹脂を含浸させた後、４５℃恒温機中に２４時間放置し、ＳＭＣ（１）を得た。 The resin composition (1) obtained above was applied onto a PP film. Next, glass fiber roving (“PB-549” manufactured by Nitto Spinning Co., Ltd.) cut into 1 inch (about 25 mm) is prepared so that the fiber content is 28% by mass, and the thickness becomes uniform without fiber directionality. As described above, the resin composition (1) coated on the PP film is uniformly dropped from the air, sandwiched between the films coated with the same resin composition (1), the glass fibers are impregnated with the resin, and then the temperature is kept constant at 45 ° C. It was left inside for 24 hours to obtain SMC (1).
［樹脂含浸性の評価］
上記で得られたＳＭＣ（１）をカットし、断面を観察することで、樹脂のガラス繊維に対する含浸性を下記の基準により評価した。
○：一様に含浸しているもの
△：未含浸箇所が一部確認されるもの
×：未含浸箇所が至る所に確認されるもの [Evaluation of resin impregnation]
By cutting the SMC (1) obtained above and observing the cross section, the impregnation property of the resin with respect to the glass fiber was evaluated according to the following criteria.
◯: Uniformly impregnated △: Some unimpregnated parts are confirmed ×: Unimpregnated parts are confirmed everywhere
［成形品の作製］
　上記で得られたＳＭＣ（１）を２５ｃｍ×２５ｃｍにカットしたものを、３０ｃｍ×３０ｃｍの平板金型の中央にセットし、プレス金型の上型温度１４５℃、下型温度１３０℃、プレス圧力１０ＭＰａ、プレス時間６分で成形し、厚さ１．５ｍｍの平板状の成形品（１－１）及び厚さ４ｍｍの平板状の成形品（１－２）を得た。 [Manufacturing of molded products]
The SMC (1) obtained above was cut into 25 cm x 25 cm and set in the center of a 30 cm x 30 cm flat plate die, and the upper die temperature of the press die was 145 ° C., the lower die temperature was 130 ° C., and the press pressure. Molding was performed at 10 MPa and a press time of 6 minutes to obtain a flat plate-shaped molded product (1-1) having a thickness of 1.5 mm and a flat plate-shaped molded product (1-2) having a thickness of 4 mm.
［外観の評価］
　上記で得られた成形品（１－２）の表面を観察し、以下の基準により外観を評価した。
　○：フクレ、白化等の異常がないもの
　×：フクレ、白化等の異常があるもの [Appearance evaluation]
The surface of the molded product (1-2) obtained above was observed, and the appearance was evaluated according to the following criteria.
◯: No abnormality such as blistering or whitening ×: Abnormality such as blistering or whitening
［難燃性の評価］
　上記で得られた成形品（１－１）を１２５ｍｍ×１３ｍｍ×１．５ｍｍにカットし、ＵＬ９４燃焼試験のうち２０ｍｍ垂直燃焼試験（ＩＥＣ６０６９５－１１－１０Ｂ，ＡＳＴＭ　Ｄ３８０１）に準拠して測定を行い、難燃性を評価した。 [Evaluation of flame retardancy]
The molded product (1-1) obtained above is cut into 125 mm × 13 mm × 1.5 mm, and measured according to the 20 mm vertical combustion test (IEC60695-11-10B, ASTM D3801) of the UL94 combustion tests. , Flame retardancy was evaluated.
［曲げ強さ及び曲げ弾性率の評価］
　ＪＩＳ　Ｋ７０７４に準拠して、上記で得られた成形品（１－２）を８０ｍｍ×２５ｍｍ×４ｍｍとなるようにカットし、株式会社島津製作所製「オートグラフＡＧ－Ｉ」を使用して三点曲げ試験（支点間距離６４ｍｍ）を行い、曲げ強度及び曲げ弾性率を評価した。 [Evaluation of flexural strength and flexural modulus]
In accordance with JIS K7074, the molded product (1-2) obtained above is cut to a size of 80 mm x 25 mm x 4 mm, and three points are used using "Autograph AG-I" manufactured by Shimadzu Corporation. A bending test (distance between fulcrums 64 mm) was performed to evaluate bending strength and flexural modulus.
［耐衝撃性の評価］
ＪＩＳ　Ｋ　７０６１に準拠して、上記で得られた成形品（１－２）を８０ｍｍ×１０ｍｍ×４ｍｍとなるようにカットし、株式会社東洋精機製作所製「デジタル衝撃試験機ＤＧ－ＵＢ」を使用してシャルピー衝撃値を測定し、耐衝撃性を評価した。 [Evaluation of impact resistance]
In accordance with JIS K 7061, the molded product (1-2) obtained above is cut to a size of 80 mm x 10 mm x 4 mm, and "Digital Impact Tester DG-UB" manufactured by Toyo Seiki Seisakusho Co., Ltd. is used. Then, the Charpy impact value was measured and the impact resistance was evaluated.
（実施例２：ＳＭＣ（２）の作製及び評価）
実施例１で用いた水酸化アルミニウム（Ｃ－１）６５質量部及び水酸化アルミニウム（Ｃ－２）６５質量部を、水酸化アルミニウム（Ｃ－１）５０質量部及び水酸化アルミニウム（Ｃ－２）５０質量部に変更した以外は、実施例１と同様に操作することにより、ＳＭＣ（２）及び成形品を作製し、各種評価を行った。 (Example 2: Preparation and evaluation of SMC (2))
65 parts by mass of aluminum hydroxide (C-1) and 65 parts by mass of aluminum hydroxide (C-2) used in Example 1, 50 parts by mass of aluminum hydroxide (C-1) and aluminum hydroxide (C-2). ) SMC (2) and a molded product were produced and evaluated in various ways by operating in the same manner as in Example 1 except that the weight was changed to 50 parts by mass.
（実施例３：ＳＭＣ（３）の作製及び評価）
実施例１で用いた水酸化アルミニウム（Ｃ－１）６５質量部及び水酸化アルミニウム（Ｃ－２）６５質量部を、水酸化アルミニウム（Ｃ－１）９０質量部及び水酸化アルミニウム（Ｃ－２）９０質量部に変更した以外は、実施例１と同様に操作することにより、ＳＭＣ（３）及び成形品を作製し、各種評価を行った。 (Example 3: Preparation and evaluation of SMC (3))
65 parts by mass of aluminum hydroxide (C-1) and 65 parts by mass of aluminum hydroxide (C-2) used in Example 1, 90 parts by mass of aluminum hydroxide (C-1) and aluminum hydroxide (C-2). ) SMC (3) and a molded product were produced by the same operation as in Example 1 except that the weight was changed to 90 parts by mass, and various evaluations were performed.
（実施例４：ＳＭＣ（４）の作製及び評価）
実施例１で用いた赤リン系難燃剤５質量部を、赤リン系難燃剤２質量部に変更した以外は、実施例１と同様に操作することにより、ＳＭＣ（４）及び成形品を作製し、各種評価を行った。 (Example 4: Preparation and evaluation of SMC (4))
SMC (4) and a molded product were produced by operating in the same manner as in Example 1 except that 5 parts by mass of the red phosphorus flame retardant used in Example 1 was changed to 2 parts by mass of the red phosphorus flame retardant. Then, various evaluations were performed.
（比較例１：ＳＭＣ（Ｒ１）の作製及び評価）
実施例１で用いた水酸化アルミニウム（Ｃ－１）６５質量部及び水酸化アルミニウム（Ｃ－２）６５質量部を、水酸化アルミニウム（Ｃ－１）２５質量部及び水酸化アルミニウム（Ｃ－２）２５質量部に変更し、炭酸カルシウム８０質量部を添加した以外は、実施例１と同様に操作することにより、ＳＭＣ（Ｒ１）及び成形品を作製し、各種評価を行った。 (Comparative Example 1: Preparation and Evaluation of SMC (R1))
65 parts by mass of aluminum hydroxide (C-1) and 65 parts by mass of aluminum hydroxide (C-2) used in Example 1, 25 parts by mass of aluminum hydroxide (C-1) and aluminum hydroxide (C-2) ) 25 parts by mass and 80 parts by mass of calcium carbonate were added, but the same operation as in Example 1 was carried out to prepare SMC (R1) and a molded product, and various evaluations were performed.
（比較例２：ＳＭＣ（Ｒ２）の作製及び評価）
実施例１で用いた水酸化アルミニウム（Ｃ－１）６５質量部及び水酸化アルミニウム（Ｃ－２）６５質量部を、水酸化アルミニウム（Ｃ－１）１２０質量部及び水酸化アルミニウム（Ｃ－２）１２０質量部に変更した以外は、実施例１と同様に操作することにより、ＳＭＣ（Ｒ２）及び成形品を作製し、各種評価を行った。 (Comparative Example 2: Preparation and Evaluation of SMC (R2))
65 parts by mass of aluminum hydroxide (C-1) and 65 parts by mass of aluminum hydroxide (C-2) used in Example 1, 120 parts by mass of aluminum hydroxide (C-1) and aluminum hydroxide (C-2). ) SMC (R2) and molded products were produced and evaluated in various ways by operating in the same manner as in Example 1 except that the weight was changed to 120 parts by mass.
（比較例３：ＳＭＣ（Ｒ３）の作製及び評価）
実施例１で用いた赤リン系難燃剤５質量部を使用しなかった以外は、実施例１と同様に操作することにより、ＳＭＣ（Ｒ３）及び成形品を作製し、各種評価を行った。 (Comparative Example 3: Preparation and Evaluation of SMC (R3))
SMC (R3) and molded products were prepared and evaluated in the same manner as in Example 1 except that 5 parts by mass of the red phosphorus flame retardant used in Example 1 was not used.
　上記で得られたＳＭＣ（１）～（４）の評価結果を表１に示す。 Table 1 shows the evaluation results of SMC (1) to (4) obtained above.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記で得られたＳＭＣ（Ｒ１）～（Ｒ３）の評価結果を表２に示す。 Table 2 shows the evaluation results of SMC (R1) to (R3) obtained above.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１～４のＳＭＣ（１）～（４）は、樹脂含浸性に優れ、外観、難燃性、曲げ強さ、曲げ弾性率、及び耐衝撃性に優れる成形品が得られることが確認された。 It was confirmed that the SMCs (1) to (4) of Examples 1 to 4 were excellent in resin impregnation property, and a molded product having excellent appearance, flame retardancy, flexural strength, flexural modulus, and impact resistance could be obtained. Was done.
　一方、比較例１は、樹脂成分（Ａ）１００質量部に対する水酸化アルミニウム（Ｃ）の含有量が、本願発明の下限である６０質量部より少ない例であるが、成形品の難燃性が不十分であった。 On the other hand, Comparative Example 1 is an example in which the content of aluminum hydroxide (C) with respect to 100 parts by mass of the resin component (A) is less than 60 parts by mass, which is the lower limit of the present invention, but the flame retardancy of the molded product is high. It was inadequate.
　比較例２は、樹脂成分（Ａ）１００質量部に対する水酸化アルミニウム（Ｃ）の含有量が、本願発明の上限である２２０質量部より多い例であるが、樹脂含浸性及び成形品の外観に劣り、成形品の強度が不十分であった。 Comparative Example 2 is an example in which the content of aluminum hydroxide (C) with respect to 100 parts by mass of the resin component (A) is larger than 220 parts by mass, which is the upper limit of the present invention, but the resin impregnation property and the appearance of the molded product are improved. It was inferior and the strength of the molded product was insufficient.
　比較例３は、赤リン系難燃剤（Ｂ）を含まない例であるが、難燃性が不良であった。 Comparative Example 3 is an example in which the red phosphorus flame retardant (B) is not contained, but the flame retardancy is poor.

Claims (4)

  1. 　不飽和ポリエステル樹脂（ａ１）を含む樹脂成分（Ａ）、赤リン系難燃剤（Ｂ）、水酸化アルミニウム（Ｃ）、重合開始剤（Ｄ）、酸化マグネシウム（Ｅ）及び強化繊維（Ｆ）を含有するシートモールディングコンパウンドであって、前記樹脂成分（Ａ）１００質量部に対し、前記赤リン系難燃剤（Ｂ）が１～５０質量部であり、前記水酸化アルミニウム（Ｃ）が６０～２２０質量部であることを特徴とするシートモールディングコンパウンド。 Resin component (A) containing unsaturated polyester resin (a1), red phosphorus flame retardant (B), aluminum hydroxide (C), polymerization initiator (D), magnesium oxide (E) and reinforcing fiber (F). The sheet molding compound contained is such that the red phosphorus flame retardant (B) is 1 to 50 parts by mass and the aluminum hydroxide (C) is 60 to 220 parts by mass with respect to 100 parts by mass of the resin component (A). A sheet molding compound characterized by being a part by mass.
  2. 　前記樹脂成分（Ａ）１００質量部に対し、前記酸化マグネシウム（Ｅ）が０．１～５質量部である請求項１記載のシートモールディングコンパウンド。 The sheet molding compound according to claim 1, wherein the magnesium oxide (E) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin component (A).
  3. 　前記強化繊維（Ｆ）の含有率が、１５～４０質量％である請求項１又は２記載のシートモールディングコンパウンド。 The sheet molding compound according to claim 1 or 2, wherein the content of the reinforcing fiber (F) is 15 to 40% by mass.
  4. 　請求項１～３いずれか１項記載のシートモールディングコンパウンドから得られる成形品。 A molded product obtained from the sheet molding compound according to any one of claims 1 to 3.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50110483A (en) * 1974-02-12 1975-08-30
JPS5616513A (en) * 1979-07-20 1981-02-17 Hitachi Ltd Polyester resin composition for casting
JPH0867771A (en) * 1994-08-31 1996-03-12 Dainippon Ink & Chem Inc Flame-retardant molding material
JPH11256017A (en) * 1998-03-10 1999-09-21 Hitachi Chem Co Ltd Resin composition for molding material and production of molding
JP2005154457A (en) * 2003-11-20 2005-06-16 Hitachi Housetec Co Ltd Sheet molding compound
JP2006131759A (en) * 2004-11-05 2006-05-25 Showa Highpolymer Co Ltd Sheet molding compound (smc)
WO2019198641A1 (en) * 2018-04-12 2019-10-17 ジャパンコンポジット株式会社 Unsaturated polyester resin composition, molding material, molded article, and battery pack case of electric vehicle

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50110483A (en) * 1974-02-12 1975-08-30
JPS5616513A (en) * 1979-07-20 1981-02-17 Hitachi Ltd Polyester resin composition for casting
JPH0867771A (en) * 1994-08-31 1996-03-12 Dainippon Ink & Chem Inc Flame-retardant molding material
JPH11256017A (en) * 1998-03-10 1999-09-21 Hitachi Chem Co Ltd Resin composition for molding material and production of molding
JP2005154457A (en) * 2003-11-20 2005-06-16 Hitachi Housetec Co Ltd Sheet molding compound
JP2006131759A (en) * 2004-11-05 2006-05-25 Showa Highpolymer Co Ltd Sheet molding compound (smc)
WO2019198641A1 (en) * 2018-04-12 2019-10-17 ジャパンコンポジット株式会社 Unsaturated polyester resin composition, molding material, molded article, and battery pack case of electric vehicle

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