WO2019221069A1 - Rubber-modified styrene-based resin composition - Google Patents

Rubber-modified styrene-based resin composition Download PDF

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WO2019221069A1
WO2019221069A1 PCT/JP2019/018966 JP2019018966W WO2019221069A1 WO 2019221069 A1 WO2019221069 A1 WO 2019221069A1 JP 2019018966 W JP2019018966 W JP 2019018966W WO 2019221069 A1 WO2019221069 A1 WO 2019221069A1
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rubber
polybutadiene
resin composition
less
mass
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PCT/JP2019/018966
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French (fr)
Japanese (ja)
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井上　修治
圭太 秋葉
勝典 今野
利春 蔵田
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東洋スチレン株式会社
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Priority to CN201980031154.8A priority Critical patent/CN112105692A/en
Priority to JP2020519629A priority patent/JPWO2019221069A1/en
Publication of WO2019221069A1 publication Critical patent/WO2019221069A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a rubber-modified styrene resin composition.
  • Thermoplastic resins have been used in many products such as food packaging containers, miscellaneous goods, building materials, automotive materials, OA equipment, electronic parts, and home appliance casings, taking advantage of their excellent moldability.
  • thermoplastic resin is flammable, and there was concern about the safety of the product. Then, in order to eliminate this flammability, the flame retardant examination using various flame retardants has been performed conventionally (patent document 1).
  • thermoplastic resins in order to increase the flame retardancy of thermoplastic resins, adding a brominated or phosphorous flame retardant having an excellent flame retardant effect to an aromatic resin typified by a styrene resin will reduce the environmental impact. There is a problem that it occurs.
  • thermoplastic resin containing a flame retardant containing no bromine or phosphorus such as magnesium hydroxide, aluminum hydroxide, or a nitrogen-based flame retardant
  • the flame retardant not only needs to be added in a larger amount than bromine-based or phosphorus-based flame retardant in order to satisfy the flame retardancy, but also tends to cause a problem that impact resistance and heat resistance are lowered.
  • An object of the present invention is to provide a rubber-modified styrene resin composition having excellent flame retardancy.
  • the total calorific value at a cracking furnace temperature of 200 ° C. to 600 ° C. measured based on ASTM D7309 Method A using a microscale combustion calorimeter is 40.0 kJ / g or less, and from 200 ° C. to 425 ° C.
  • a polybutadiene having a ratio (m2 / m1) of the maximum heat release rate (m1) and the maximum heat release rate (m2) from 425 ° C. to 600 ° C. of 6.0 or less is 3.0% by mass or more and 15.0% by mass or less.
  • a rubber-modified styrenic resin composition characterized by (2) The rubber-modified styrene resin according to (1), wherein the polybutadiene has a number average molecular weight of 100,000 to 300,000. (3) The rubber-modified styrene according to (1) or (2), which is obtained by graft polymerization of a styrene monomer having a total of ⁇ -methylstyrene and phenylacetylene of 100 ppm to 300 ppm and the polybutadiene.
  • -Based resin composition characterized by (2) The rubber-modified styrenic resin according to (1), wherein the polybutadiene has a number average molecular weight of 100,000 to 300,000.
  • the resin composition of the present invention is advantageous for use in a field where a flame retardant styrene resin containing no bromine or phosphorus flame retardant is required.
  • Example 3 is a result of MCC measurement of polybutadiene used in Example 2.
  • the microscale combustion calorimeter (MCC) used in the present invention is an apparatus for evaluating the combustion characteristics of combustible materials based on ASTM D7309, and has a cracking furnace and a combustion furnace in the apparatus. . While flowing nitrogen or a mixed gas of nitrogen and oxygen to the cracking furnace where the sample is installed, the temperature is raised at an arbitrary speed, and the cracked gas generated from this is introduced into the combustion furnace, and the cracked gas is burned in the presence of nitrogen and oxygen.
  • the heat release rate (Heat Release Rate, HRR) is calculated from the amount of oxygen consumed.
  • the calorific value of the present invention is a value obtained by multiplying the heat release rate (HRR) at each measurement point by the measurement interval (time) when measured using a microscale combustion calorimeter (MCC).
  • the total calorific value is the total calorific value between 200 ° C. and 600 ° C. of the cracking furnace temperature.
  • the styrenic resin of the present invention is obtained by polymerizing an aromatic vinyl compound monomer, and the rubber-modified styrenic resin is a rubber-modified styrenic resin obtained by adding polybutadiene as a rubbery polymer.
  • the polymerization method it can be produced by a known method, for example, a bulk polymerization method, a bulk / suspension two-stage polymerization method, a solution polymerization method or the like.
  • aromatic vinyl compound monomer known monomers such as styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene can be used, and styrene is preferable.
  • monomers such as acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, and maleic anhydride that can be copolymerized with these aromatic vinyl compound monomers do not impair the performance of the resin composition. It may be used as long as it is moderate.
  • a polymer obtained by adding a crosslinking agent such as divinylbenzene to an aromatic vinyl compound monomer may be used.
  • the total calorific value of polybutadiene must be 40.0 kJ / g or less.
  • the burning rate becomes slow and a resin composition excellent in flame retardancy can be obtained.
  • the total calorific value of polybutadiene exceeds 40.0 kJ / g, there is no flame retardant effect because the combustion rate increases.
  • the ratio (m2 / m1) of the maximum heat release rate (m1) of polybutadiene from 200 ° C. to 425 ° C. and the maximum heat release rate (m2) from 425 ° C. to 600 ° C. is 6.0 or less.
  • the ratio (m2 / m1) of the maximum heat dissipation rate of polybutadiene is 6.0 or less, a resin composition having an excellent combustion balance can be obtained.
  • the ratio of the maximum heat release rate (m2 / m1) exceeds 6.0, the combustion rate is rapidly increased at a predetermined temperature, and there is no flame retardant effect.
  • the number average molecular weight (Mn) of the polybutadiene is preferably 100,000 or more and 300,000 or less.
  • Mn number average molecular weight of polybutadiene
  • a resin composition excellent in flame retardancy can be obtained.
  • the above-mentioned polybutadiene content must be 3.0% by mass or more and 15.0% by mass or less.
  • the polybutadiene content is 3.0% by mass or more and 15.0% by mass or less, a resin composition having an excellent balance between impact resistance and rigidity can be obtained. More preferably, it is 5.0 mass% or more and 15.0 mass% or less.
  • the content of polybutadiene is less than 3.0% by mass, there is no sufficient flame retardant effect. If the content of polybutadiene exceeds 15.0% by mass, the rigidity decreases.
  • the average particle size of the polybutadiene in the rubber-modified styrene resin is preferably from 0.1 ⁇ m to 5.0 ⁇ m, particularly preferably from 1.0 ⁇ m to 4.0 ⁇ m.
  • the average particle size of the polybutadiene is 0.1 ⁇ m or more and 5.0 ⁇ m or less, a significant impact resistance improvement effect is obtained.
  • the total of ⁇ -methylstyrene and phenylacetylene in the styrene monomer is preferably 100 ppm or more and 300 ppm or less.
  • the total of ⁇ -methylstyrene and phenylacetylene in the styrene monomer is 100 ppm or more and 300 ppm or less, a resin composition having excellent flame retardancy upon graft polymerization with polybutadiene can be obtained.
  • the resin composition of the present invention includes various additives within a range not exceeding the gist of the present invention, such as flame retardants, flame retardant aids, dyes and pigments, coloring inhibitors, lubricants, antioxidants, anti-aging agents, Known additives such as light stabilizers, antistatic agents, fillers and compatibilizers, and modifiers such as colorants such as titanium oxide and carbon black can be added.
  • additives such as light stabilizers, antistatic agents, fillers and compatibilizers, and modifiers such as colorants such as titanium oxide and carbon black can be added.
  • These addition methods are not particularly limited, and are known methods, for example, before the start of polymerization of the thermoplastic resin to be used, with respect to the reaction solution in the middle of the polymerization, or after the completion of the polymerization, further, an extruder or a molding It can also be added in the machine.
  • a known mixing technique can be applied to the method for mixing the resin composition of the present invention.
  • a uniform resin composition can be obtained by melt-kneading a mixture preliminarily mixed with a mixing apparatus such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer.
  • a mixing apparatus such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer.
  • melt kneaders include Banbury mixers, kneaders, rolls, single screw extruders, special single screw extruders, and twin screw extruders.
  • an additive such as a flame retardant from the middle of a melt-kneading apparatus such as an extruder.
  • the molding method for obtaining a molded product from the resin composition of the present invention includes injection molding.
  • the rubber-modified styrenic resin used in the examples was produced as follows.
  • the conditions of each reactor were as follows. First reactor: [Number of stirring] 100 rpm, [Reaction temperature] 125 ° C. Second reactor: [Number of stirring] 60 rpm, [Reaction temperature] Adjusted so that a temperature gradient is created from 128 ° C. to 130 ° C. in the flow direction. Third reactor: [Number of stirring] 30 rpm, [Reaction temperature] 128 ° C. Fourth reactor: [Reaction temperature] Adjusted so that a temperature gradient is created from 140 ° C to 168 ° C in the flow direction.
  • Example 1 A raw material solution in which 75.5% by mass of a styrene monomer, 15.4% by mass of ethylbenzene, and 9.1% by mass of polybutadiene are dissolved.
  • the raw material liquid was continuously supplied to the first reactor at a supply rate of 20 L / hr for polymerization, and then charged continuously into the second reactor for polymerization.
  • the rubber-like polymer polybutadiene
  • the dispersion has been completed.
  • the conversion was 27%.
  • the polymerization liquid from the outlet of the second reactor was continuously charged into the third reactor, and the polymerization conversion rate at this time was 45%. Further, the polymerization was allowed to proceed in the fourth reactor until the polymerization conversion reached 82%.
  • the obtained polymerization solution was introduced into a vacuum devolatilization tank with a preheater composed of two stages in series, and after separating unreacted styrene and unreacted ethylbenzene, it was extruded into a strand and cooled, then cut. It was set as a pellet.
  • the resin temperature in the first devolatilization tank is set to 210 ° C.
  • the pressure in the vacuum devolatilization tank is set to 53 kPa
  • the resin temperature in the second devolatilization tank is set to 220 ° C.
  • the pressure in the volatilization tank was 2.7 kPa.
  • 1.5% by mass of liquid paraffin was added to 98.5% by mass of the resin obtained by polymerization, and blended uniformly using a twin screw extruder to obtain a rubber-modified styrene resin.
  • the amounts of phenylacetylene and ⁇ -methylstyrene in the styrene monomer can be determined by a known method, but generally can be determined by gas chromatography. In this example, the measurement was performed under the following conditions.
  • the number average molecular weight (Mn) of polybutadiene was calculated from a molecular weight distribution curve obtained by gel permeation chromatography using tetrahydrofuran as a solvent, using a calibration curve prepared using standard polystyrene as a standard substance.
  • Mn number average molecular weight
  • GPC model Shodex GPC-101 manufactured by Showa Denko Column: PLgel 10 ⁇ m MIXED-B, 300 ⁇ 7.5 mm manufactured by Polymer Laboratories
  • Mobile phase Tetrahydrofuran 1.0 ml / min Sample concentration: 0.2% by mass
  • Temperature Oven 40 ° C, inlet 35 ° C, detector 35 ° C
  • Detector Differential refractometer
  • MCC MCC-3
  • ASTM D7309 Method A the heat release rate [W / g] was measured under the following conditions, and the total temperature at a decomposition furnace temperature of 200 ° C. to 600 ° C. was measured.
  • the calorific value [kJ / g] and the ratio (m2 / m1) of the maximum heat release rate (m1) from 200 ° C. to 425 ° C. and the maximum heat release rate (m2) from 425 ° C. to 600 ° C. were determined.
  • the measurement conditions are as follows.
  • the content of rubber-like polymer (polybutadiene) particles in the obtained rubber-modified styrene resin composition is obtained by the following method.
  • ⁇ Rubber content> 0.4 g of the rubber-modified styrenic resin composition is placed in a 100 ml volumetric flask and precisely weighed (W). After 75 ml of chloroform is added and well dispersed, 20 ml of a solution of 18 g of iodine monochloride dissolved in 1000 ml of carbon tetrachloride is added and stored in a cool dark place. After 8 hours, the mark is adjusted to the mark with chloroform.
  • Rubber-like polymer particle content (% by mass) 10.8 ⁇ xx (BA) / W
  • ⁇ Flame retardance> In accordance with UL94 HB IEC60695-11-10 A, a 1.5 mm thick test piece was held horizontally, a 20 mm flame was indirectly flamed for 30 seconds, and a burning rate of 75 mm between marked lines was evaluated.
  • the test piece for combustion (125 ⁇ 13 ⁇ 1.5 mm) was prepared using an injection molding machine (“J100E-P” manufactured by Nippon Steel Works). At this time, the cylinder temperature of the injection molding machine was 220 ° C., and the mold temperature was 45 ° C.
  • FIG. 1 shows the MCC measurement results of the polybutadiene used in Example 2.
  • styrene monomer is NS styrene monomer
  • polybutadiene number average molecular weight Mn: 7.7 ⁇ 10 4
  • polybutadiene number average molecular weight Mn: 16 ⁇ 10 4
  • Is BR-15HB manufactured by Ube Industries, Ltd. polybutadiene (number average molecular weight Mn: 24 ⁇ 10 4 ) is 730AX manufactured by Asahi Kasei Chemicals, and polybutadiene (number average molecular weight Mn: 32 ⁇ 10 4 ) is PR-040 manufactured by Chimei Corporation. used.
  • the ratio of the maximum heat release rate (m1) from 200 ° C. to 425 ° C. and the maximum heat release rate (m 2) from 425 ° C. to 600 ° C. (m 2 / m 1) It can be seen that the rubber-modified styrene resin containing 3.0% by mass or more and 15.0% by mass or less of polybutadiene having an A of 6.0 or less has a slow combustion rate and excellent flame retardancy and rigidity.
  • the number average molecular weight (Mn) of the polybutadiene used in the graft polymerization is 100,000 or more and 300,000 or less and the total amount of phenylacetylene and ⁇ -methylstyrene in the styrene monomer is 100 ppm or more and 300 ppm or less, the rubber It can be seen that the modified styrene resin has a slow burning rate in the horizontal burning test and improves flame retardancy.
  • the resin composition of the present invention is excellent in flame retardancy, it can be advantageously used in a wide range of fields such as OA equipment, electronic equipment, and miscellaneous goods.

Abstract

Provided is a rubber-modified styrene-based resin composition having excellent flame retardant properties. This rubber-modified styrene-based resin composition contains 3.0-15.0 mass% of a polybutadiene which has a total calorific value of 40.0 kJ/g or less at a cracking furnace temperature of 200-600°C as measured in accordance with ASTM D7309 Method A using a microscale combustion calorimeter, and in which the ratio (m2/m1) of the highest heat release rate (m2) thereof at 425-600°C to the highest heat release rate (m1) at 200-425°C is 6.0 or less.

Description

ゴム変性スチレン系樹脂組成物Rubber-modified styrenic resin composition
　本発明は、ゴム変性スチレン系樹脂組成物に関する。 The present invention relates to a rubber-modified styrene resin composition.
　熱可塑性樹脂はその優れた成形性を生かし、食品包装容器、雑貨、建築材料、自動車材料、ＯＡ機器、電子部品および家電筐体など多くの製品に使用されてきた。 Thermoplastic resins have been used in many products such as food packaging containers, miscellaneous goods, building materials, automotive materials, OA equipment, electronic parts, and home appliance casings, taking advantage of their excellent moldability.
　一方、熱可塑性樹脂は燃え易く、製品としての安全性に不安があった。そこで、この燃え易さを解消するため、従来から種々の難燃剤を用いた難燃化検討が行われてきた（特許文献１）。 On the other hand, the thermoplastic resin is flammable, and there was concern about the safety of the product. Then, in order to eliminate this flammability, the flame retardant examination using various flame retardants has been performed conventionally (patent document 1).
　しかし、熱可塑性樹脂の難燃性を高めるために、スチレン系樹脂を代表とする芳香族系樹脂に対して難燃効果に優れている臭素系やリン系の難燃剤を配合すると、環境負荷が生じるという問題点がある。 However, in order to increase the flame retardancy of thermoplastic resins, adding a brominated or phosphorous flame retardant having an excellent flame retardant effect to an aromatic resin typified by a styrene resin will reduce the environmental impact. There is a problem that it occurs.
　そこで、環境に適合する、臭素やリンを含有しないスチレン系樹脂の難燃性を向上させることが求められている。 Therefore, there is a demand for improving the flame retardancy of styrene-based resins that do not contain bromine or phosphorus that are compatible with the environment.
　そこで、近年では臭素やリンを含有しない難燃剤である水酸化マグネシウム、水酸化アルミニウム、窒素系難燃剤等を熱可塑性樹脂に配合させたものが知られている。しかしながら、前記難燃剤は、難燃性を満たすために臭素系やリン系難燃剤と比べて多量に添加する必要があるだけではなく、耐衝撃性や耐熱性が低下する問題を生じさせやすい。 Therefore, in recent years, a thermoplastic resin containing a flame retardant containing no bromine or phosphorus, such as magnesium hydroxide, aluminum hydroxide, or a nitrogen-based flame retardant, is known. However, the flame retardant not only needs to be added in a larger amount than bromine-based or phosphorus-based flame retardant in order to satisfy the flame retardancy, but also tends to cause a problem that impact resistance and heat resistance are lowered.
特開平８－７３６８４号公報JP-A-8-73684
　本発明は、難燃性に優れたゴム変性スチレン系樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a rubber-modified styrene resin composition having excellent flame retardancy.
　（１）マイクロスケール燃焼熱量計を用いるＡＳＴＭ　Ｄ７３０９　Ｍｅｔｈｏｄ　Ａに基づいて測定される、分解炉温度２００℃から６００℃においての総発熱量が４０．０ｋＪ／ｇ以下であり、２００℃から４２５℃における最大放熱率（ｍ１）と４２５℃から６００℃における最大放熱率（ｍ２）の比（ｍ２／ｍ１）が６．０以下であるポリブタジエンを３．０質量％以上１５．０質量％以下含有することを特徴するゴム変性スチレン系樹脂組成物。
　（２）前記ポリブタジエンの数平均分子量が１０万以上３０万以下であることを特徴とする（１）に記載のゴム変性スチレン樹脂。
　（３）α－メチルスチレンとフェニルアセチレンの合計が１００ｐｐｍ以上３００ｐｐｍ以下のスチレンモノマーと、前記ポリブタジエンと、をグラフト重合して得られることを特徴する（１）又は（２）に記載のゴム変性スチレン系樹脂組成物。 (1) The total calorific value at a cracking furnace temperature of 200 ° C. to 600 ° C. measured based on ASTM D7309 Method A using a microscale combustion calorimeter is 40.0 kJ / g or less, and from 200 ° C. to 425 ° C. A polybutadiene having a ratio (m2 / m1) of the maximum heat release rate (m1) and the maximum heat release rate (m2) from 425 ° C. to 600 ° C. of 6.0 or less is 3.0% by mass or more and 15.0% by mass or less. A rubber-modified styrenic resin composition characterized by
(2) The rubber-modified styrene resin according to (1), wherein the polybutadiene has a number average molecular weight of 100,000 to 300,000.
(3) The rubber-modified styrene according to (1) or (2), which is obtained by graft polymerization of a styrene monomer having a total of α-methylstyrene and phenylacetylene of 100 ppm to 300 ppm and the polybutadiene. -Based resin composition.
　本発明の樹脂組成物は、臭素系やリン系難燃剤を含有しない難燃性スチレン系樹脂を要求される分野での使用が有利になる。 The resin composition of the present invention is advantageous for use in a field where a flame retardant styrene resin containing no bromine or phosphorus flame retardant is required.
実施例２で使用したポリブタジエンのＭＣＣ測定結果である。3 is a result of MCC measurement of polybutadiene used in Example 2.
　本発明において使用するマイクロスケール燃焼熱量計（Ｍｉｃｒｏｓｃａｌｅ　Ｃｏｍｂｕｓｔｉｏｎ　Ｃａｌｏｒｉｍｅｔｅｒ、ＭＣＣ）とは、ＡＳＴＭ　Ｄ７３０９に基づいた可燃物の燃焼特性を評価する装置であり、装置内に分解炉と燃焼炉を有している。サンプルを設置した分解炉に窒素または窒素と酸素の混合気体を流しながら任意の速度で昇温させ、そこから発生した分解ガスを燃焼炉へ導入し、窒素と酸素の存在下で分解ガスを燃焼させて、消費される酸素量から放熱率（Ｈｅａｔ　Ｒｅｌｅａｓｅ　Ｒａｔｅ、ＨＲＲ）が計算される。 The microscale combustion calorimeter (MCC) used in the present invention is an apparatus for evaluating the combustion characteristics of combustible materials based on ASTM D7309, and has a cracking furnace and a combustion furnace in the apparatus. . While flowing nitrogen or a mixed gas of nitrogen and oxygen to the cracking furnace where the sample is installed, the temperature is raised at an arbitrary speed, and the cracked gas generated from this is introduced into the combustion furnace, and the cracked gas is burned in the presence of nitrogen and oxygen. The heat release rate (Heat Release Rate, HRR) is calculated from the amount of oxygen consumed.
　本発明の発熱量とは、マイクロスケール燃焼熱量計（ＭＣＣ）を用いて測定した際、各測定点での放熱率（ＨＲＲ）に測定間隔（時間）を乗じた値である。総発熱量は分解炉温度２００℃から６００℃間の発熱量の合計である。 The calorific value of the present invention is a value obtained by multiplying the heat release rate (HRR) at each measurement point by the measurement interval (time) when measured using a microscale combustion calorimeter (MCC). The total calorific value is the total calorific value between 200 ° C. and 600 ° C. of the cracking furnace temperature.
　本発明のスチレン系樹脂とは芳香族ビニル化合物系単量体を重合して得られるものであり、ゴム状重合体としてポリブタジエンを加えてゴム変性を行ったスチレン系樹脂をゴム変性スチレン系樹脂と呼ぶ。重合方法としては公知の方法、例えば、塊状重合法、塊状・懸濁二段重合法、溶液重合法等により製造することができる。芳香族ビニル化合物系単量体は、スチレン、α－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン等の公知のものが使用できるが、好ましくはスチレンである。また、これらの芳香族ビニル化合物系単量体と共重合可能なアクリロニトリル、（メタ）アクリル酸、（メタ）アクリル酸エステル、無水マレイン酸等の単量体も、樹脂組成物の性能を損なわない程度ものであれば使用しても良い。さらに本発明ではジビニルベンゼン等の架橋剤を芳香族ビニル化合物系単量体に対し添加して重合したものであっても差し支えない。 The styrenic resin of the present invention is obtained by polymerizing an aromatic vinyl compound monomer, and the rubber-modified styrenic resin is a rubber-modified styrenic resin obtained by adding polybutadiene as a rubbery polymer. Call. As the polymerization method, it can be produced by a known method, for example, a bulk polymerization method, a bulk / suspension two-stage polymerization method, a solution polymerization method or the like. As the aromatic vinyl compound monomer, known monomers such as styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene can be used, and styrene is preferable. In addition, monomers such as acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, and maleic anhydride that can be copolymerized with these aromatic vinyl compound monomers do not impair the performance of the resin composition. It may be used as long as it is moderate. Furthermore, in the present invention, a polymer obtained by adding a crosslinking agent such as divinylbenzene to an aromatic vinyl compound monomer may be used.
　上記、ポリブタジエンの総発熱量は４０．０ｋＪ／ｇ以下が必須である。ポリブタジエンの総発熱量が４０．０ｋＪ／ｇ以下だと燃焼速度が遅くなり難燃性に優れた樹脂組成物が得られる。ただし、ポリブタジエンの総発熱量が４０．０ｋＪ／ｇを超えると燃焼速度が速くなるため難燃効果はない。 The total calorific value of polybutadiene must be 40.0 kJ / g or less. When the total calorific value of polybutadiene is 40.0 kJ / g or less, the burning rate becomes slow and a resin composition excellent in flame retardancy can be obtained. However, if the total calorific value of polybutadiene exceeds 40.0 kJ / g, there is no flame retardant effect because the combustion rate increases.
　上記、ポリブタジエンの２００℃から４２５℃における最大放熱率（ｍ１）と４２５℃から６００℃における最大放熱率（ｍ２）の比（ｍ２／ｍ１）が６．０以下であることが必須である。ポリブタジエンの最大放熱率の比（ｍ２／ｍ１）が６．０以下だと燃焼バランスに優れた樹脂組成物が得られる。ただし、最大放熱率の比（ｍ２／ｍ１）が６．０を超えると所定の温度で急速に燃焼速度が速くなり難燃効果はない。 It is essential that the ratio (m2 / m1) of the maximum heat release rate (m1) of polybutadiene from 200 ° C. to 425 ° C. and the maximum heat release rate (m2) from 425 ° C. to 600 ° C. is 6.0 or less. When the ratio (m2 / m1) of the maximum heat dissipation rate of polybutadiene is 6.0 or less, a resin composition having an excellent combustion balance can be obtained. However, when the ratio of the maximum heat release rate (m2 / m1) exceeds 6.0, the combustion rate is rapidly increased at a predetermined temperature, and there is no flame retardant effect.
　上記、ポリブタジエンの数平均分子量（Ｍｎ）は、１０万以上３０万以下が好ましい。ポリブタジエンの数平均分子量（Ｍｎ）が１０万以上３０万以下だと難燃性に優れた樹脂組成物が得られる。 The number average molecular weight (Mn) of the polybutadiene is preferably 100,000 or more and 300,000 or less. When the number average molecular weight (Mn) of polybutadiene is 100,000 or more and 300,000 or less, a resin composition excellent in flame retardancy can be obtained.
　上記、ポリブタジエンの含有量は、３．０質量％以上１５．０質量％以下が必須である。ポリブタジエンの含有量が３．０質量％以上１５．０質量％以下だと耐衝撃性と剛性のバランスに優れた樹脂組成物が得られる。より好ましくは５．０質量％以上１５．０質量％以下である。ただし、ポリブタジエンの含有量が３．０質量％未満だと十分な難燃効果がない。ポリブタジエンの含有量が１５．０質量％を超えると剛性が低下する。 The above-mentioned polybutadiene content must be 3.0% by mass or more and 15.0% by mass or less. When the polybutadiene content is 3.0% by mass or more and 15.0% by mass or less, a resin composition having an excellent balance between impact resistance and rigidity can be obtained. More preferably, it is 5.0 mass% or more and 15.0 mass% or less. However, if the content of polybutadiene is less than 3.0% by mass, there is no sufficient flame retardant effect. If the content of polybutadiene exceeds 15.0% by mass, the rigidity decreases.
　上記、ゴム変性スチレン系樹脂中のポリブタジエンの平均粒子径は、０．１μｍ以上５．０μｍ以下が好ましく、特に好ましくは１．０μｍ以上４．０μｍ以下が好ましい。ポリブタジエンの平均粒子径が０．１μｍ以上５．０μｍ以下だと顕著な耐衝撃性向上効果が得られる。 The average particle size of the polybutadiene in the rubber-modified styrene resin is preferably from 0.1 μm to 5.0 μm, particularly preferably from 1.0 μm to 4.0 μm. When the average particle size of the polybutadiene is 0.1 μm or more and 5.0 μm or less, a significant impact resistance improvement effect is obtained.
　芳香族ビニル化合物系単量体がスチレンである場合、スチレンモノマー中のα－メチルスチレンとフェニルアセチレンの合計は、１００ｐｐｍ以上３００ｐｐｍ以下が好ましい。スチレンモノマー中のα－メチルスチレンとフェニルアセチレンの合計が１００ｐｐｍ以上３００ｐｐｍ以下だとポリブタジエンとグラフト重合した際に難燃性に優れた樹脂組成物が得られる。 When the aromatic vinyl compound monomer is styrene, the total of α-methylstyrene and phenylacetylene in the styrene monomer is preferably 100 ppm or more and 300 ppm or less. When the total of α-methylstyrene and phenylacetylene in the styrene monomer is 100 ppm or more and 300 ppm or less, a resin composition having excellent flame retardancy upon graft polymerization with polybutadiene can be obtained.
　また、本発明の樹脂組成物には、本発明の要旨を超えない範囲で各種添加物、例えば難燃剤、難燃助剤、染顔料、着色防止剤、滑剤、酸化防止剤、老化防止剤、光安定剤、帯電防止剤、充填剤、相溶化剤等の公知の添加剤、酸化チタンやカーボンブラックなどの着色剤などの改質剤を添加できる。これらの添加方法は特に限定される訳では無く、公知の方法、例えば、使用する熱可塑性樹脂の重合開始前、重合途中の反応液に対して、または重合終了後、更には、押出機や成形機においても添加することができる。 Further, the resin composition of the present invention includes various additives within a range not exceeding the gist of the present invention, such as flame retardants, flame retardant aids, dyes and pigments, coloring inhibitors, lubricants, antioxidants, anti-aging agents, Known additives such as light stabilizers, antistatic agents, fillers and compatibilizers, and modifiers such as colorants such as titanium oxide and carbon black can be added. These addition methods are not particularly limited, and are known methods, for example, before the start of polymerization of the thermoplastic resin to be used, with respect to the reaction solution in the middle of the polymerization, or after the completion of the polymerization, further, an extruder or a molding It can also be added in the machine.
　本発明の樹脂組成物の混合方法は、公知の混合技術を適用することが出来る。例えばミキサー型混合機、Ｖ型ブレンダー、及びタンブラー型混合機等の混合装置であらかじめ予備混合しておいた混合物を、溶融混練することで均一な樹脂組成物とすることが出来る。溶融混練機に特段の制限は無い。好適な溶融混練機として、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等がある。更に押出機等の溶融混練装置の途中から難燃剤等の添加剤を別途に添加する方法がある。 A known mixing technique can be applied to the method for mixing the resin composition of the present invention. For example, a uniform resin composition can be obtained by melt-kneading a mixture preliminarily mixed with a mixing apparatus such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer. There are no particular restrictions on the melt kneader. Suitable melt kneaders include Banbury mixers, kneaders, rolls, single screw extruders, special single screw extruders, and twin screw extruders. Furthermore, there is a method of separately adding an additive such as a flame retardant from the middle of a melt-kneading apparatus such as an extruder.
　本発明の樹脂組成物から成形品を得る成形法には射出成形等がある。 The molding method for obtaining a molded product from the resin composition of the present invention includes injection molding.
　以下に本発明を実施例及び比較例によって詳しく説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　実施例で使用したゴム変性スチレン系樹脂は以下のように製造した。 The rubber-modified styrenic resin used in the examples was produced as follows.
　（１）ゴム変性スチレン系樹脂の製造
　下記第１反応器から第４反応器を直列に接続して重合工程を構成した。 (1) Production of rubber-modified styrenic resin A polymerization process was configured by connecting the following first to fourth reactors in series.
　第１反応器：容積２５Ｌの攪拌翼付完全混合型反応器
　第２反応器：容積３９Ｌの攪拌翼付プラグフロー反応器
　第３反応器：容積５０Ｌの攪拌翼付プラグフロー反応器
　第４反応器：容積５０Ｌのスタティックミキサー付プラグフロー反応器 1st reactor: 25 L capacity complete mixing reactor with stirring blades 2nd reactor: 39 L capacity plug flow reactor with stirring blades 3rd reactor: 50 L capacity plug flow reactor with stirring blades 4th reactor : 50L capacity plug flow reactor with static mixer
　各反応器の条件は以下の通りとした。
　第１反応器：［攪拌数］１００ｒｐｍ、［反応温度］１２５℃
　第２反応器：［攪拌数］６０ｒｐｍ、［反応温度］流れ方向に１２８℃から１３０℃まで温度勾配がつくように調整
　第３反応器：［攪拌数］３０ｒｐｍ、［反応温度］１２８℃
　第４反応器：［反応温度］流れ方向に１４０℃から１６８℃まで温度勾配がつくように調整 The conditions of each reactor were as follows.
First reactor: [Number of stirring] 100 rpm, [Reaction temperature] 125 ° C.
Second reactor: [Number of stirring] 60 rpm, [Reaction temperature] Adjusted so that a temperature gradient is created from 128 ° C. to 130 ° C. in the flow direction. Third reactor: [Number of stirring] 30 rpm, [Reaction temperature] 128 ° C.
Fourth reactor: [Reaction temperature] Adjusted so that a temperature gradient is created from 140 ° C to 168 ° C in the flow direction.
　また、実施例１の原料としては、以下のものを用いた。
　スチレン単量体７５．５質量％、エチルベンゼン１５．４質量％、ポリブタジエン９．１質量％を溶解させた原料液。 Moreover, the following were used as a raw material of Example 1.
A raw material solution in which 75.5% by mass of a styrene monomer, 15.4% by mass of ethylbenzene, and 9.1% by mass of polybutadiene are dissolved.
　まず、原料液を２０Ｌ／ｈｒの供給速度で第１反応器に連続的に供給し重合した後、第２反応器に連続的に装入して重合した。第１反応器の出口では、いまだゴム状重合体（ポリブタジエン）が分散粒子化（相反転）していない状態で、第２反応器の出口では分散粒子化が終了した状態となり、このときの重合転化率は２７％であった。次いで、第２反応器の出口からの重合液を第３反応器に連続的に装入し、このときの重合転化率は４５％であった。さらに第４反応器にて重合転化率が８２％になるまで重合を進行させた。得られた重合液を直列に２段より構成される予熱器付き真空脱揮槽に導入し、未反応スチレン及び未反応エチルベンゼンを分離した後、ストランド状に押し出しして冷却した後、切断してペレットとした。なお、１段目の脱揮槽内の樹脂温度は２１０℃に設定し、真空脱揮槽の圧力は５３ｋＰａとし、２段目の脱揮槽内の樹脂温度は２２０℃に設定し、真空脱揮槽の圧力は２．７ｋＰａとした。次に、重合で得られた樹脂９８．５質量％に対して流動パラフィンを１．５質量％添加し、二軸押出機を用いて均一にブレンドしゴム変性スチレン系樹脂を得た。 First, the raw material liquid was continuously supplied to the first reactor at a supply rate of 20 L / hr for polymerization, and then charged continuously into the second reactor for polymerization. At the outlet of the first reactor, the rubber-like polymer (polybutadiene) has not yet been dispersed into particles (phase inversion), and at the outlet of the second reactor, the dispersion has been completed. The conversion was 27%. Subsequently, the polymerization liquid from the outlet of the second reactor was continuously charged into the third reactor, and the polymerization conversion rate at this time was 45%. Further, the polymerization was allowed to proceed in the fourth reactor until the polymerization conversion reached 82%. The obtained polymerization solution was introduced into a vacuum devolatilization tank with a preheater composed of two stages in series, and after separating unreacted styrene and unreacted ethylbenzene, it was extruded into a strand and cooled, then cut. It was set as a pellet. The resin temperature in the first devolatilization tank is set to 210 ° C., the pressure in the vacuum devolatilization tank is set to 53 kPa, the resin temperature in the second devolatilization tank is set to 220 ° C. The pressure in the volatilization tank was 2.7 kPa. Next, 1.5% by mass of liquid paraffin was added to 98.5% by mass of the resin obtained by polymerization, and blended uniformly using a twin screw extruder to obtain a rubber-modified styrene resin.
　スチレン単量体中のフェニルアセチレン及びα－メチルスチレンの量は公知の方法で求めることができるが、一般的にはガスクロマトグラフ法により求めることができる。本実施例では、下記の条件で測定した。
　＜ＧＣ＞
ＧＣ機種　　　：島津製ガスクマトグラフ　ＧＣ－２０１４
検出器　　　　：ＦＩＤ
カラム　　　　：ＳＰＢ－１（無極性）
カラム温度　　：４０℃（５分保持）－昇温速度（１０℃／ｍｉｎ）→３００℃
カラムサイズ　：０．５３ｍｍ×３０ｍ　膜厚１．５μｍ
注入口温度　　：２５０℃
検出器温度　　：３００℃
注入量　　　　：０．２μＬ
注入法　　　　：スプリットレス The amounts of phenylacetylene and α-methylstyrene in the styrene monomer can be determined by a known method, but generally can be determined by gas chromatography. In this example, the measurement was performed under the following conditions.
<GC>
GC model: Shimadzu Gas Kumatomograph GC-2014
Detector: FID
Column: SPB-1 (Nonpolar)
Column temperature: 40 ° C. (held for 5 minutes) -temperature increase rate (10 ° C./min)→300° C.
Column size: 0.53 mm x 30 m Film thickness 1.5 μm
Inlet temperature: 250 ° C
Detector temperature: 300 ° C
Injection volume: 0.2 μL
Injection method: Splitless
　ポリブタジエンの数平均分子量（Ｍｎ）の測定はテトラヒドロフランを溶媒としたゲルパーミエーションクロマトグラフィーにより得られた分子量分布曲線から、標準ポリスチレンを標準物質として作成した検量線を用いて計算した。
　＜ＧＰＣ＞
ＧＰＣ機種：昭和電工社製Ｓｈｏｄｅｘ　ＧＰＣ－１０１
カラム　　：ポリマーラボラトリーズ社製ＰＬｇｅｌ　１０μｍ　ＭＩＸＥＤ－Ｂ，３００×７．５ｍｍ
移動相　　：テトラヒドロフラン　１．０ｍｌ／ｍｉｎ
試料濃度　：０．２質量％
温度　　　：オーブン４０℃、注入口３５℃、検出器３５℃
検出器　　：示差屈折計 The number average molecular weight (Mn) of polybutadiene was calculated from a molecular weight distribution curve obtained by gel permeation chromatography using tetrahydrofuran as a solvent, using a calibration curve prepared using standard polystyrene as a standard substance.
<GPC>
GPC model: Shodex GPC-101 manufactured by Showa Denko
Column: PLgel 10 μm MIXED-B, 300 × 7.5 mm manufactured by Polymer Laboratories
Mobile phase: Tetrahydrofuran 1.0 ml / min
Sample concentration: 0.2% by mass
Temperature: Oven 40 ° C, inlet 35 ° C, detector 35 ° C
Detector: Differential refractometer
　ポリブタジエンは、ＭＣＣ（ＤＥＴＡＫ製「ＭＣＣ－３」）を用い、ＡＳＴＭ　Ｄ７３０９　Ｍｅｔｈｏｄ　Ａに基づいて、以下に示す条件で放熱率［Ｗ／ｇ］を測定し、分解炉温度２００℃から６００℃における総発熱量［ｋＪ／ｇ］及び、２００℃から４２５℃における最大放熱率（ｍ１）と４２５℃から６００℃における最大放熱率（ｍ２）の比（ｍ２／ｍ１）をそれぞれ求めた。測定条件は以下の通りである。
　＜ＭＣＣ＞
サンプル重量　：３．０ｍｇ
規格　　　　　：ＡＳＴＭ　Ｄ７３０９　Ｍｅｔｈｏｄ　Ａ
分解炉昇温速度：１．０℃／ｓｅｃ
分解炉到達温度：７５０℃
燃焼炉温度　　：９００℃
分解炉雰囲気　：窒素（嫌気条件）
燃焼炉雰囲気　：酸素２０％、窒素８０％
流量　　　　　：酸素２０ｃｃ／ｍｉｎ、窒素８０ｃｃ／ｍｉｎ For polybutadiene, MCC (“MCC-3” manufactured by DETAK) was used, and based on ASTM D7309 Method A, the heat release rate [W / g] was measured under the following conditions, and the total temperature at a decomposition furnace temperature of 200 ° C. to 600 ° C. was measured. The calorific value [kJ / g] and the ratio (m2 / m1) of the maximum heat release rate (m1) from 200 ° C. to 425 ° C. and the maximum heat release rate (m2) from 425 ° C. to 600 ° C. were determined. The measurement conditions are as follows.
<MCC>
Sample weight: 3.0mg
Standard: ASTM D7309 Method A
Decomposition furnace heating rate: 1.0 ° C / sec
Decomposition furnace temperature: 750 ° C
Combustion furnace temperature: 900 ° C
Decomposition furnace atmosphere: Nitrogen (anaerobic condition)
Combustion furnace atmosphere: 20% oxygen, 80% nitrogen
Flow rate: Oxygen 20cc / min, nitrogen 80cc / min
　得られたゴム変性スチレン系樹脂組成物中のゴム状重合体（ポリブタジエン）粒子の含有率は、以下の方法により得られるものである。
　＜ゴム含有率＞
　ゴム変性スチレン系樹脂組成物０．４ｇを１００ｍｌのメスフラスコに入れて精秤する（Ｗ）。クロロホルム７５ｍｌを加えてよく分散させた後、一塩化ヨウ素１８ｇを１０００ｍｌの四塩化炭素に溶かした溶液２０ｍｌを加えて冷暗所に保存し、８時間後にクロロホルムで標線に合わせる。これを２５ｍｌ採取し、ヨウ化カリウム１０ｇを水８００ｍｌ、エタノール２００ｍｌの混合液に溶かした溶液６０ｍｌを加え、チオ硫酸ナトリウム１０ｇを１０００ｍｌの水に溶かした溶液（モル濃度ｘ）で滴定する。本試験Ａｍｌ、空試験Ｂｍｌとし、ゴム状重合体粒子の含有率（質量％）は以下の式により求められる。
　　　ゴム状重合体粒子含有率（質量％）＝１０．８×ｘ×（Ｂ－Ａ）／Ｗ The content of rubber-like polymer (polybutadiene) particles in the obtained rubber-modified styrene resin composition is obtained by the following method.
<Rubber content>
0.4 g of the rubber-modified styrenic resin composition is placed in a 100 ml volumetric flask and precisely weighed (W). After 75 ml of chloroform is added and well dispersed, 20 ml of a solution of 18 g of iodine monochloride dissolved in 1000 ml of carbon tetrachloride is added and stored in a cool dark place. After 8 hours, the mark is adjusted to the mark with chloroform. 25 ml of this was collected, 60 ml of a solution prepared by dissolving 10 g of potassium iodide in a mixed solution of 800 ml of water and 200 ml of ethanol was added, and titrated with a solution (molar concentration x) of 10 g of sodium thiosulfate dissolved in 1000 ml of water. This test Aml and blank test Bml are used, and the content (% by mass) of the rubber-like polymer particles is obtained by the following formula.
Rubber-like polymer particle content (% by mass) = 10.8 × xx (BA) / W
　＜曲げ弾性率（剛性）＞
　ゴム変性スチレン系樹脂組成物に関して射出成形機を用いて試験片を作成し、ＪＩＳ　Ｋ－７１７１により求めた。 <Bending elastic modulus (rigidity)>
With respect to the rubber-modified styrenic resin composition, a test piece was prepared using an injection molding machine and determined according to JIS K-7171.
　＜難燃性＞
　ＵＬ９４のＨＢ　ＩＥＣ６０６９５－１１－１０　Ａに準拠し、厚さ１．５ｍｍの試験片を水平に保持し、２０ｍｍ炎を３０秒間接炎し、標線間７５ｍｍの燃焼速度を評価した。尚、燃焼用試験片（１２５×１３×１．５ｍｍ）は、射出成形機（日本製鋼所社製「Ｊ１００Ｅ－Ｐ」）を用いて作製した。この際、射出成形機のシリンダー温度は２２０℃、金型温度は４５℃とした。 <Flame retardance>
In accordance with UL94 HB IEC60695-11-10 A, a 1.5 mm thick test piece was held horizontally, a 20 mm flame was indirectly flamed for 30 seconds, and a burning rate of 75 mm between marked lines was evaluated. The test piece for combustion (125 × 13 × 1.5 mm) was prepared using an injection molding machine (“J100E-P” manufactured by Nippon Steel Works). At this time, the cylinder temperature of the injection molding machine was 220 ° C., and the mold temperature was 45 ° C.
　グラフト重合時に使用するポリブタジエンの数平均分子量（Ｍｎ）、スチレン単量体中のフェニルアセチレン及びα－メチルスチレンの合計量、ゴム含有率を変えて評価した結果（実施例２から５、比較例１から４）を下記表１に示す。また、図１に実施例２で使用したポリブタジエンのＭＣＣ測定結果を示す。 Results of evaluation by changing the number average molecular weight (Mn) of polybutadiene used during graft polymerization, the total amount of phenylacetylene and α-methylstyrene in the styrene monomer, and the rubber content (Examples 2 to 5, Comparative Example 1) To 4) are shown in Table 1 below. FIG. 1 shows the MCC measurement results of the polybutadiene used in Example 2.
　なお、原料としてスチレン単量体はＮＳスチレンモノマー社製、ポリブタジエン（数平均分子量Ｍｎ：７．７×１０4）は宇部興産社製ＭＢＲ－５００、ポリブタジエン（数平均分子量Ｍｎ：１６×１０4）は宇部興産社製ＢＲ－１５ＨＢ、ポリブタジエン（数平均分子量Ｍｎ：２４×１０4）は旭化成ケミカルズ社製７３０ＡＸ、ポリブタジエン（数平均分子量Ｍｎ：３２×１０4）はチーメイ社製ＰＲ－０４０のものを使用した。 As raw materials, styrene monomer is NS styrene monomer, polybutadiene (number average molecular weight Mn: 7.7 × 10 4 ) is Ube Industries MBR-500, polybutadiene (number average molecular weight Mn: 16 × 10 4 ). Is BR-15HB manufactured by Ube Industries, Ltd., polybutadiene (number average molecular weight Mn: 24 × 10 4 ) is 730AX manufactured by Asahi Kasei Chemicals, and polybutadiene (number average molecular weight Mn: 32 × 10 4 ) is PR-040 manufactured by Chimei Corporation. used.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の実施例より、総発熱量が４０．０ｋＪ／ｇ以下且つ２００℃から４２５℃における最大放熱率（ｍ１）と４２５℃から６００℃における最大放熱率（ｍ２）の比（ｍ２／ｍ１）が６．０以下であるポリブタジエンを、３．０質量％以上１５．０質量％以下含有するゴム変性スチレン樹脂は、燃焼速度が遅く難燃性と剛性に優れていることがわかる。また、グラフト重合時に使用するポリブタジエンの数平均分子量（Ｍｎ）が１０万以上３０万以下、スチレン単量体中のフェニルアセチレン及びα－メチルスチレンの合計量が１００ｐｐｍ以上３００ｐｐｍ以下であれば、そのゴム変性スチレン樹脂は水平燃焼試験の燃焼速度が遅くなり難燃性が向上することがわかる。 From the examples in Table 1, the ratio of the maximum heat release rate (m1) from 200 ° C. to 425 ° C. and the maximum heat release rate (m 2) from 425 ° C. to 600 ° C. (m 2 / m 1) It can be seen that the rubber-modified styrene resin containing 3.0% by mass or more and 15.0% by mass or less of polybutadiene having an A of 6.0 or less has a slow combustion rate and excellent flame retardancy and rigidity. If the number average molecular weight (Mn) of the polybutadiene used in the graft polymerization is 100,000 or more and 300,000 or less and the total amount of phenylacetylene and α-methylstyrene in the styrene monomer is 100 ppm or more and 300 ppm or less, the rubber It can be seen that the modified styrene resin has a slow burning rate in the horizontal burning test and improves flame retardancy.
　一方、比較例より、本発明の規定を満足しないポリブタジエンを含有するゴム変性スチレン樹脂（比較例１，２）、ポリブタジエンの含有量が本発明の規定を満足しないゴム変性スチレン樹脂（比較例３，４）は難燃性に劣る。 On the other hand, from Comparative Examples, rubber-modified styrene resins containing polybutadiene that do not satisfy the provisions of the present invention (Comparative Examples 1 and 2), rubber-modified styrene resins that do not satisfy the provisions of the present invention (Comparative Examples 3 and 3). 4) is inferior in flame retardancy.
　本発明の樹脂組成物は、難燃性に優れているため、ＯＡ機器、電子機器、雑貨等の幅広い分野での利用が有利になる。 Since the resin composition of the present invention is excellent in flame retardancy, it can be advantageously used in a wide range of fields such as OA equipment, electronic equipment, and miscellaneous goods.

Claims (3)

  1. 　マイクロスケール燃焼熱量計を用いるＡＳＴＭ　Ｄ７３０９　Ｍｅｔｈｏｄ　Ａに基づいて測定される、分解炉温度２００℃から６００℃においての総発熱量が４０．０ｋＪ／ｇ以下であり、２００℃から４２５℃における最大放熱率（ｍ１）と４２５℃から６００℃における最大放熱率（ｍ２）の比（ｍ２／ｍ１）が６．０以下であるポリブタジエンを３．０質量％以上１５．０質量％以下含有することを特徴とするゴム変性スチレン系樹脂組成物。 Measured based on ASTM D7309 Method A using a micro-scale combustion calorimeter, the total heat generation at a cracking furnace temperature of 200 ° C. to 600 ° C. is 40.0 kJ / g or less, and the maximum heat release rate at 200 ° C. to 425 ° C. A polybutadiene having a ratio (m2 / m1) of (m1) to a maximum heat release rate (m2) from 425 ° C. to 600 ° C. of 6.0 or less is 3.0% by mass or more and 15.0% by mass or less. A rubber-modified styrenic resin composition.
  2. 　前記ポリブタジエンの数平均分子量が１０万以上３０万以下であることを特徴とする請求項１に記載のゴム変性スチレン系樹脂組成物。 The rubber-modified styrene resin composition according to claim 1, wherein the polybutadiene has a number average molecular weight of 100,000 or more and 300,000 or less.
  3. 　α－メチルスチレンとフェニルアセチレンの合計が１００ｐｐｍ以上３００ｐｐｍ以下のスチレンモノマーと、前記ポリブタジエンと、をグラフト重合して得られることを特徴とする請求項１又は２に記載のゴム変性スチレン系樹脂組成物。 The rubber-modified styrenic resin composition according to claim 1 or 2, which is obtained by graft polymerization of a styrene monomer having a total of α-methylstyrene and phenylacetylene of 100 ppm to 300 ppm and the polybutadiene. .
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JP2004075865A (en) * 2002-08-20 2004-03-11 Idemitsu Petrochem Co Ltd Rubber-modified styrene resin composition for blow molding, and its molded article
JP2017002237A (en) * 2015-06-12 2017-01-05 東洋スチレン株式会社 Rubber modified styrene resin composition and molded body using the same

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JP5437606B2 (en) * 2008-08-06 2014-03-12 東洋スチレン株式会社 Rubber-modified styrenic resin composition, and sheet and container using the same
JP2013108032A (en) * 2011-11-24 2013-06-06 Toyo Styrene Co Ltd Styrenic flame retardant resin composition

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Publication number Priority date Publication date Assignee Title
JP2004075865A (en) * 2002-08-20 2004-03-11 Idemitsu Petrochem Co Ltd Rubber-modified styrene resin composition for blow molding, and its molded article
JP2017002237A (en) * 2015-06-12 2017-01-05 東洋スチレン株式会社 Rubber modified styrene resin composition and molded body using the same

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