JP2009132778A - Thermoplastic resin composition - Google Patents
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本発明は熱可塑性樹脂組成物に関するものである。詳しくは、衝撃強度、耐熱性、加工性、外観の均一性のバランスに優れたポリ乳酸樹脂を含む熱可塑性樹脂組成物に関するものである。 The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition containing a polylactic acid resin having an excellent balance of impact strength, heat resistance, workability, and appearance uniformity.
近年、地球的規模での環境問題として、石油化学製品の使用増加による石油資源の将来性が危ぶまれている。例えば、ポリ乳酸樹脂は植物であるとうもろこしや芋類を原料として得られる乳酸からなる樹脂であり、石油を原料としない環境対応型の樹脂として知られている。しかしながら、ポリ乳酸樹脂は、ノッチ付き衝撃強度および、耐熱性に劣るといった欠点がある。
一方、ＡＢＳ樹脂は優れた物性バランスおよび成形加工性を有しており、広範な分野に利用されているが、原料は石油資源に依存している。これら両者の欠点を補うことを目的に下記の従来技術が提案されているが、衝撃強度、耐熱性、加工性、外観の均一性の諸物性を全て満足することはできず、改良が望まれている。
On the other hand, ABS resin has an excellent balance of physical properties and moldability and is used in a wide range of fields, but the raw material depends on petroleum resources. The following prior arts have been proposed for the purpose of compensating both of these drawbacks, but they cannot satisfy all physical properties such as impact strength, heat resistance, workability, and uniformity of appearance, and improvements are desired. ing.
本発明は、上記課題を解決するために成されたもので、衝撃強度、耐熱性、加工性、外観の均一性のバランスに優れたポリ乳酸樹脂を含む熱可塑性樹脂組成物を提供することを目的とするものである。 The present invention has been made to solve the above problems, and provides a thermoplastic resin composition containing a polylactic acid resin having an excellent balance of impact strength, heat resistance, workability, and appearance uniformity. It is the purpose.
すなわち本発明は、ポリ乳酸樹脂（Ｌ）５〜６０重量部、ゴム含有グラフト共重合体（Ｇ）１０〜７０重量部、ポリカーボネート樹脂（Ｃ）５〜５０重量部、α−メチルスチレン−アクリロニトリル共重合体（Ａ）１０〜８０重量部からなる熱可塑性樹脂組成物（ただし、（Ｌ）、（Ｇ）、（Ｃ）、（Ａ）の合計は１００重量部である）であって、ゴム含有グラフト共重合体（Ｇ）のグラフト重合に用いる単量体のうち、７０重量％以上が（メタ）アクリル酸エステル系単量体であることを特徴とする熱可塑性樹脂組成物を提供するものである。 That is, the present invention relates to polylactic acid resin (L) 5 to 60 parts by weight, rubber-containing graft copolymer (G) 10 to 70 parts by weight, polycarbonate resin (C) 5 to 50 parts by weight, α-methylstyrene-acrylonitrile copolymer. A thermoplastic resin composition comprising 10 to 80 parts by weight of the polymer (A) (however, the total of (L), (G), (C) and (A) is 100 parts by weight), and contains a rubber Among the monomers used for graft polymerization of the graft copolymer (G), a thermoplastic resin composition is provided wherein 70% by weight or more is a (meth) acrylate monomer. is there.
本発明における熱可塑性樹脂組成物は、衝撃強度、耐熱性、加工性、外観の均一性のバランスに優れ、特に石油資源消費の抑制にも貢献できる環境対応型材料として、車両分野、家電分野、建材分野、サニタリー分野等に広く用いることができる。 The thermoplastic resin composition according to the present invention has an excellent balance of impact strength, heat resistance, processability, and uniformity of appearance, and particularly as an environmentally friendly material that can contribute to the suppression of petroleum resource consumption. It can be widely used in the field of building materials and sanitary.
以下、本発明の熱可塑性樹脂組成物につき詳細に説明する。
本発明において、ポリ乳酸樹脂（Ｌ）は熱可塑性樹脂組成物の必須成分を構成する。市販されているポリ樹脂としては、例えば三井化学（株）製 商品名：レイシア、ユニチカ（株）製 商品名：テラマック等が挙げられるが、これらに限定されるものではない。
Hereinafter, the thermoplastic resin composition of the present invention will be described in detail.
In the present invention, the polylactic acid resin (L) constitutes an essential component of the thermoplastic resin composition. Examples of the commercially available polyresin include, but are not limited to, product names: Lacia, manufactured by Mitsui Chemicals, Inc., and product names: Terramac, manufactured by Unitika Ltd.
本発明におけるゴム含有グラフト共重合体（Ｇ）とは、ゴム状重合体にビニル系単量体を重合して得られるものであり、該ゴム状重合体としては、ポリブタジエン、ポリイソプレン、ブタジエンースチレン共重合体、イソプレン−スチレン共重合体、ブタジエン−アクリロニトリル共重合体、ブタジエン−イソプレン−スチレン共重合体、ポリクロロプレンなどのジエン系ゴム、エチレン−プロピレン共重合体、エチレン−プロピレン−非共役ジエン共重合体、エチレン−ブテン−１−非共役ジエン共重合体、ポリブチルアクリレート系ゴム、ポリオルガノシロキサン系ゴム、さらにはこれらの２種以上のゴムからなる複合ゴム等が挙げられ、一種又は二種以上用いることができる。これらのうち、特に共役ジエン系ゴムが衝撃強度発現性の観点から、ポリブチルアクリレート系ゴムが衝撃強度と外観均一性のバランスの観点から好ましい。
ゴム含有グラフト共重合体の製造に好適に用いられるビニル系単量体としては、（メタ）アクリル酸エステル系単量体、スチレン系単量体、シアン化ビニル系単量体が挙げられるが、本発明においては、これらビニル系単量体の７０重量％以上が（メタ）アクリル酸エステル系単量体であることが必要である。（メタ）アクリル酸エステル系単量体が７０重量％未満では外観の均一性が低下する。（メタ）アクリル酸エステル系単量体としては、メチルアクリレート、メチルメタアクリレート、プロピルアクリレート、プロピルメタアクリレート、ブチルアクリレート、ブチルメタアクリレート等が挙げられ、特にメチルメタクリレートが好ましい。更には、ビニル系単量体の内、８０重量％以上がメチルメタクリレートおよび／またはメチルアクリレートであることが好ましい。
スチレン系単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、一種又は二種以上用いることができる。特にスチレン、α−メチルスチレンが好ましい。
シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル等が挙げられる。特にアクリロニトリルが好ましい。
また、上記ビニル系単量体と共に無水マレイン酸、マレイン酸ジメチル等の不飽和酸系単量体、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミドなどのマレイミド系単量体などを用いることも可能である。
上記のゴム含有グラフト共重合体を構成するゴム状重合体とビニル系単量体の割合については特に制限はないが、好ましくはゴム状重合体１５〜６５重量％および（メタ）アクリル酸エステル系単量体を７０重量％以上含むビニル系単量体３５〜８５重量％である。
また、ゴム含有グラフト共重合体の重合方法についても特に制限はなく、乳化重合、懸濁重合、塊状重合、溶液重合またはこれらの組み合わせにより製造することができるが、高温高湿環境下における経時安定性維持の観点から、ゴム含有グラフト共重合体に含有されるアルカリ金属の含有量が０．０１重量％以下であることが好ましい。
The rubber-containing graft copolymer (G) in the present invention is obtained by polymerizing a vinyl monomer to a rubber-like polymer. Examples of the rubber-like polymer include polybutadiene, polyisoprene, and butadiene. Diene rubber such as styrene copolymer, isoprene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-isoprene-styrene copolymer, polychloroprene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene Examples thereof include copolymers, ethylene-butene-1-nonconjugated diene copolymers, polybutyl acrylate rubbers, polyorganosiloxane rubbers, and composite rubbers composed of two or more of these rubbers. More than one species can be used. Of these, conjugated diene rubber is particularly preferable from the viewpoint of impact strength development, and polybutyl acrylate rubber is preferable from the viewpoint of balance between impact strength and appearance uniformity.
Examples of vinyl monomers suitably used for the production of rubber-containing graft copolymers include (meth) acrylic acid ester monomers, styrene monomers, and vinyl cyanide monomers. In the present invention, it is necessary that 70% by weight or more of these vinyl monomers are (meth) acrylic acid ester monomers. When the (meth) acrylic acid ester monomer is less than 70% by weight, the uniformity of the appearance is deteriorated. Examples of the (meth) acrylic acid ester monomer include methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate, and methyl methacrylate is particularly preferable. Further, 80% by weight or more of the vinyl monomer is preferably methyl methacrylate and / or methyl acrylate.
Examples of the styrenic monomer include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Particularly preferred is acrylonitrile.
Moreover, it is also possible to use an unsaturated acid monomer such as maleic anhydride and dimethyl maleate, a maleimide monomer such as N-phenylmaleimide, N-cyclohexylmaleimide, and the like together with the vinyl monomer. .
Although there is no restriction | limiting in particular about the ratio of the rubber-like polymer which comprises said rubber-containing graft copolymer, and a vinyl-type monomer, Preferably 15-65 weight% of rubber-like polymers and (meth) acrylic acid ester type | system | group It is 35 to 85% by weight of a vinyl monomer containing 70% by weight or more of monomers.
The polymerization method of the rubber-containing graft copolymer is not particularly limited, and can be produced by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof, but is stable over time in a high temperature and high humidity environment. From the viewpoint of maintaining the property, the content of alkali metal contained in the rubber-containing graft copolymer is preferably 0.01% by weight or less.
本発明におけるα−メチルスチレン−アクリロニトリル共重合体（Ａ）の組成割合としては、特にα−メチルスチレン６０〜８０重量％およびアクリロニトリル２０〜４０重量％であることが好ましい。
また、α−メチルスチレン−アクリロニトリル共重合体（Ａ）の重合方法についても特に制限はなく、乳化重合、懸濁重合、塊状重合、溶液重合またはこれらの組み合わせにより製造することができる。
The composition ratio of the α-methylstyrene-acrylonitrile copolymer (A) in the present invention is particularly preferably 60 to 80% by weight of α-methylstyrene and 20 to 40% by weight of acrylonitrile.
Moreover, there is no restriction | limiting in particular also about the polymerization method of (alpha) -methylstyrene acrylonitrile copolymer (A), It can manufacture by emulsion polymerization, suspension polymerization, block polymerization, solution polymerization, or these combination.
本発明において、ポリカーボネート樹脂（Ｃ）は熱可塑性樹脂組成物の必須成分を構成する。市販されているポリカーボネート樹脂としては、例えば住友ダウ（株）製 商品名：カリバー、帝人化成（株）製 商品名：パンライト、三菱エンジニアリングプラスチックス（株）製 ユーピロン等が挙げられるが、これらに限定されるものではない。 In the present invention, the polycarbonate resin (C) constitutes an essential component of the thermoplastic resin composition. Examples of the commercially available polycarbonate resin include Sumitomo Dow Co., Ltd. trade name: Caliber, Teijin Chemicals Co., Ltd. trade name: Panlite, Mitsubishi Engineering Plastics Co., Ltd. Iupilon, etc. It is not limited.
本発明の熱可塑性樹脂組成物は、ポリ乳酸樹脂（Ｌ）５〜６０重量部、ゴム含有グラフト共重合体（Ｇ）１０〜７０重量部、ポリカーボネート樹脂（Ｃ）５〜５０重量部、α−メチルスチレン−アクリロニトリル共重合体（Ａ）１０〜８０重量部からなるものである（ただし、（Ｌ）、（Ｇ）、（Ｃ）、（Ａ）の合計は１００重量部である。）。
ポリ乳酸樹脂（Ｌ）の配合比率が５重量部未満では、原料の殆どを石油資源に依存しているという環境負荷は低減されず、６０重量部を超えると耐熱性が低下する。好ましくは１０〜５０重量部、更に好ましくは１５〜４５重量部である。
ゴム含有グラフト共重合体（Ｇ）の配合比率が１０重量部未満では衝撃強度が劣り、７０重量部を超えると加工性や耐熱性が低下する。好ましくは１５〜６５重量部、更に好ましくは２０〜６０重量部である。
ポリカーボネート樹脂（Ｃ）の配合比率が５重量部未満では耐熱性が劣り、５０重量部を超えると衝撃強度が低下する。好ましくは５〜４５重量部、更に好ましくは１０〜４０重量部である。
α−メチルスチレン−アクリロニトリル共重合体（Ａ）の配合比率が１０重量部未満では耐熱性が劣り、８０重量部を超えると衝撃強度が低下する。好ましくは１５〜７０重量部、更に好ましくは２０〜６０重量部である。
The thermoplastic resin composition of the present invention comprises 5 to 60 parts by weight of a polylactic acid resin (L), 10 to 70 parts by weight of a rubber-containing graft copolymer (G), 5 to 50 parts by weight of a polycarbonate resin (C), α- It consists of 10-80 parts by weight of a methylstyrene-acrylonitrile copolymer (A) (however, the total of (L), (G), (C), (A) is 100 parts by weight).
When the blending ratio of the polylactic acid resin (L) is less than 5 parts by weight, the environmental load that most of the raw materials depend on petroleum resources is not reduced, and when it exceeds 60 parts by weight, the heat resistance is lowered. Preferably it is 10-50 weight part, More preferably, it is 15-45 weight part.
When the blending ratio of the rubber-containing graft copolymer (G) is less than 10 parts by weight, the impact strength is inferior, and when it exceeds 70 parts by weight, workability and heat resistance are lowered. Preferably it is 15-65 weight part, More preferably, it is 20-60 weight part.
When the blending ratio of the polycarbonate resin (C) is less than 5 parts by weight, the heat resistance is inferior, and when it exceeds 50 parts by weight, the impact strength is lowered. Preferably it is 5-45 weight part, More preferably, it is 10-40 weight part.
When the blending ratio of the α-methylstyrene-acrylonitrile copolymer (A) is less than 10 parts by weight, the heat resistance is poor, and when it exceeds 80 parts by weight, the impact strength is lowered. Preferably it is 15-70 weight part, More preferably, it is 20-60 weight part.
また、本発明における熱可塑性樹脂組成物には、上記各成分の他に、その物性を損なわない限りにおいて、その目的に応じて樹脂の混合時、成形時等に安定剤、顔料、染料、補強剤（タルク、マイカ、クレー、ガラス繊維等）、着色剤（カーボンブラック、酸化チタン等）、紫外線吸収剤、酸化防止剤、難燃剤、滑剤、離型剤、可塑剤、帯電防止剤、無機および有機系抗菌剤等の公知の添加剤を配合することができる。 In addition to the above components, the thermoplastic resin composition according to the present invention includes stabilizers, pigments, dyes, reinforcements at the time of resin mixing and molding depending on the purpose, as long as the physical properties are not impaired. Agent (talc, mica, clay, glass fiber, etc.), colorant (carbon black, titanium oxide, etc.), UV absorber, antioxidant, flame retardant, lubricant, mold release agent, plasticizer, antistatic agent, inorganic and Known additives such as organic antibacterial agents can be blended.
本発明における熱可塑性樹脂組成物の混合方法としては、バンバリーミキサー、押出機等公知の混練機を用いる方法が挙げられる。また、混合順序にも何ら制限はなく、４成分の一括混練はもちろんのこと、予め任意の２〜３成分を混合した後に残る成分を混合することも可能である。 Examples of the method for mixing the thermoplastic resin composition in the present invention include a method using a known kneader such as a Banbury mixer or an extruder. Also, there is no limitation on the mixing order, and it is possible to mix the remaining components after mixing any two or three components in advance, as well as batch mixing of the four components.
〔実施例〕
以下に実施例を用いて本発明を具体的に説明するが、本発明はこれらによって何ら制限されるものではない。
また、特段の断りが無い限り、％や部は重量を基準とする。
〔Example〕
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by these.
Unless otherwise specified,% and parts are based on weight.
ポリ乳酸樹脂（Ｌ）
ポリ乳酸樹脂（Ｌ）として、三井化学株式会社製ＬＡＣＥＡ Ｈ−４００を用いた。
Polylactic acid resin (L)
LACEA H-400 manufactured by Mitsui Chemicals, Inc. was used as the polylactic acid resin (L).
ゴム状重合体１〜３の作製
ゴム状重合体１：ステンレス製耐圧重合反応機に、減圧下で純水１３０部、ロジン酸カリウム２．０部、オレイン酸カリウム０．５部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物１．０部、水酸化ナトリウム０．０５部、ブタジエン９５部、スチレン３部、アクリロニトリル２.部、ｔ−ドデシルメルカプタン０．２０部を加えて十分攪拌しながら６７℃に昇温した後、過硫酸カリウム０．８部を仕込み６７℃で重合を開始した。重合転化率が６６％を越えた時点で過硫酸カリウム０．２部を仕込み、反応温度を７２℃に上げて反応を継続し、重合転化率が９８％を超えたことを確認して槽内温度を３５℃以下に冷却した。燐酸アグロメ法によって重合体粒子を肥大化させ、ラテックス状のゴム状重合体１を得た。その固形分濃度は３８．７重量％、ｐＨ１０．４、平均粒子径は３９０ｎｍであった。
Preparation of rubber-like polymers 1-3 Rubber-like polymer 1: 130 parts of pure water, 2.0 parts of potassium rosinate, 0.5 parts of potassium oleate, naphthalene sulfonic acid in a pressure-resistant polymerization reactor made of stainless steel under reduced pressure Sodium formalin condensate 1.0 part, sodium hydroxide 0.05 part, butadiene 95 parts, styrene 3 parts, acrylonitrile 2. parts, t-dodecyl mercaptan 0.20 part was added and the temperature was raised to 67 ° C. with sufficient stirring. After warming, 0.8 part of potassium persulfate was charged and polymerization was started at 67 ° C. When the polymerization conversion rate exceeded 66%, 0.2 parts of potassium persulfate was charged, the reaction temperature was raised to 72 ° C., and the reaction was continued, and it was confirmed that the polymerization conversion rate exceeded 98%. The temperature was cooled below 35 ° C. The polymer particles were enlarged by the phosphoric acid agglomeration method to obtain a latex-like rubbery polymer 1. The solid content concentration was 38.7% by weight, pH was 10.4, and the average particle size was 390 nm.
ゴム状重合体２：ステンレス製耐圧重合反応機に、減圧下で純水１４０部、オレイン酸カリウム３．０部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物０．９部、水酸化カリウム０．０６部、ブタジエン９５部、スチレン５部、ｔ−ドデシルメルカプタン０．１７部、ブドウ糖０．０８部、硫酸第一鉄０．００５部を仕込んで撹拌しながら５０℃に昇温した後、加硫酸カリウム０．３部を仕込み５０℃で重合を開始した。重合転化率が６３％を越えた時点でｔ−ブチルハイドロパーオキサイド０．０５部を仕込み、反応温度を７０℃に上げて反応を継続し、重合転化率が９７％を超えたことを確認して槽内温度を４０℃以下に冷却した。燐酸アグロメ法によって重合体粒子を肥大化させ、ラテックス状のゴム状重合体２を得た。その固形分濃度は３６．８重量％、ｐＨ１０．６、平均粒子径は２８０ｎｍであった。 Rubber-like polymer 2: 140 parts of pure water, 3.0 parts of potassium oleate, 0.9 parts of formalin condensate of sodium naphthalene sulfonate, 0.06 part of potassium hydroxide in a pressure-resistant polymerization reactor made of stainless steel under reduced pressure , 95 parts of butadiene, 5 parts of styrene, 0.17 part of t-dodecyl mercaptan, 0.08 part of glucose and 0.005 part of ferrous sulfate, and heated to 50 ° C. with stirring. 3 parts were charged and polymerization was started at 50 ° C. When the polymerization conversion rate exceeded 63%, 0.05 part of t-butyl hydroperoxide was added, the reaction temperature was raised to 70 ° C., and the reaction was continued, and it was confirmed that the polymerization conversion rate exceeded 97%. The tank temperature was cooled to 40 ° C. or lower. The polymer particles were enlarged by the phosphoric acid agglomeration method to obtain a latex-like rubbery polymer 2. The solid content concentration was 36.8% by weight, pH was 10.6, and the average particle size was 280 nm.
ゴム状重合体３：ステンレス製耐圧重合反応機に、減圧下で純水１３０部、アルケニルコハク酸カリウム０．８部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物０．５部、水酸化カリウム０．０２部、ブチルアクリレート９０部、メチルメタクリレート７部、アリルメタクリレート３部、ｔ−ドデシルメルカプタン０．０８部、ブドウ糖０．１０部、硫酸第一鉄０．００５部を仕込んで撹拌しながら５３℃に昇温した後、ｔ−ブチルハイドロパーオキサイド０.０９部を仕込み５３℃で重合を開始した。重合開始から２１０分かけて反応温度を６３℃に上げて反応を継続し、重合転化率６６％を越えた時点で、ブドウ糖０．０２部とクメンハイドロパーオキサイド０．０２部を添加し、７０℃に昇温して反応を継続した。重合転化率が９８％を超えたことを確認して槽内温度を３５℃以下に冷却した。燐酸アグロメ法によって重合体粒子を肥大化させ、ラテックス状のゴム状重合体３を得た。その固形分濃度は３８．０重量％、ｐＨ８．５、平均粒子径は３５０ｍであった。 Rubber-like polymer 3: 130 parts of pure water, 0.8 part of potassium alkenyl succinate, 0.5 part of formalin condensate of sodium naphthalene sulfonate under reduced pressure, 0.02 potassium hydroxide in a pressure resistant polymerization reactor made of stainless steel Part, 90 parts of butyl acrylate, 7 parts of methyl methacrylate, 3 parts of allyl methacrylate, 0.08 part of t-dodecyl mercaptan, 0.10 part of glucose and 0.005 part of ferrous sulfate, and the temperature is raised to 53 ° C. with stirring. After warming, 0.09 part of t-butyl hydroperoxide was charged and polymerization was started at 53 ° C. The reaction temperature was raised to 63 ° C. over 210 minutes from the start of the polymerization, and the reaction was continued. When the polymerization conversion rate exceeded 66%, 0.02 part of glucose and 0.02 part of cumene hydroperoxide were added, and 70% The reaction was continued by raising the temperature to 0 ° C. After confirming that the polymerization conversion rate exceeded 98%, the temperature in the tank was cooled to 35 ° C. or lower. The polymer particles were enlarged by the phosphoric acid agglomeration method to obtain a latex-like rubbery polymer 3. The solid content concentration was 38.0% by weight, pH 8.5, and the average particle size was 350 m.
ゴム含有グラフト共重合体Ｇ１〜Ｇ６の作製
ゴム含有グラフト共重合体Ｇ１：ステンレス製耐圧重合反応機に、減圧下で純水７６．１部、ロジン酸カリウム０．３部、オレイン酸カリウム１．０部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物０．７部、水酸化ナトリウム０．１５部、ゴム状重合体１を固形分で４０部、ブドウ糖０．０８部、硫酸第一鉄０．００４部を仕込んで十分攪拌しながら６７℃に昇温した後、過硫酸カリウム０．３０部を仕込み６７℃で重合を開始した。開始直後からメチルメタクリレート５５部とメチルアクリレート５部、ｔ−ドデシルメルカプタン０．２５部の混合物を３時間にわたって連続添加し、重合転化率が６６％を越えた時点でｔ−ブチルハイドロパーオキサイド０．０４部を仕込み、反応温度を７２℃に上げて反応を２時間以上継続し、重合転化率が９７％を超えたことを確認して槽内温度を４０℃以下に冷却した。得られたラテックス状のゴム含有グラフト共重合体を多量のメタノール中に投入して沈殿させ、１５０メッシュのステンレス製金網に流した後、先ず適量のメタノール、次に多量の純水で洗浄した。その後、減圧下で含水率が1重量％以下になるまで乾燥させ、パウダー状のゴム含有グラフト共重合体Ｇ１を得た。
得られたゴム含有グラフト共重合体Ｇ１を灰化後、酸溶解してＩＣＰ発光分光法および原子吸光法により、アルカリ金属含有量を測定した。結果は０．００３重量％であった。
Preparation of rubber-containing graft copolymers G1 to G6 Rubber-containing graft copolymer G1: In a stainless steel pressure-resistant polymerization reactor, 76.1 parts of pure water, 0.3 part of potassium rosinate, and 1. 0 part, formalin condensate of sodium naphthalenesulfonate 0.7 part, sodium hydroxide 0.15 part, rubber-like polymer 1 40 parts by solid, glucose 0.08 part, ferrous sulfate 0.004 part The mixture was heated to 67 ° C. with sufficient stirring, and 0.30 part of potassium persulfate was charged, and polymerization was started at 67 ° C. Immediately after the start, a mixture of 55 parts of methyl methacrylate, 5 parts of methyl acrylate and 0.25 part of t-dodecyl mercaptan was continuously added over 3 hours, and when the polymerization conversion exceeded 66%, t-butyl hydroperoxide 0. 04 parts were charged, the reaction temperature was raised to 72 ° C., and the reaction was continued for 2 hours or more. After confirming that the polymerization conversion rate exceeded 97%, the temperature in the tank was cooled to 40 ° C. or less. The obtained latex-like rubber-containing graft copolymer was poured into a large amount of methanol, precipitated, poured into a 150-mesh stainless steel wire mesh, and then washed with an appropriate amount of methanol and then with a large amount of pure water. Then, it was dried until the water content became 1% by weight or less under reduced pressure to obtain a powdery rubber-containing graft copolymer G1.
The obtained rubber-containing graft copolymer G1 was incinerated and then dissolved in an acid, and the alkali metal content was measured by ICP emission spectroscopy and atomic absorption. The result was 0.003% by weight.
ゴム含有グラフト共重合体Ｇ２：ステンレス製耐圧重合反応機に、減圧下で純水４５．５部、ロジン酸カリウム１．０部、オレイン酸カリウム０．５部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物０．８部、水酸化カリウム０．０３部、ゴム状重合体２を固形分で５５部、ｔ−ドデシルメルカプタン０．２０部、ブドウ糖０．１１部、硫酸第一鉄０．０３部を仕込んで十分攪拌しながら６５℃に昇温した後、クメンハイドロパーオキサイド０．０７部を仕込み６５℃で重合を開始した。開始直後からメチルメタクリレート２０部、スチレン１５部、アクリロニトリル１０部の単量体混合物を３時間にわたって連続添加し、重合転化率が６３％を越えた時点でｔ−ブチルハイドロパーオキサイド０．０５部を仕込み、反応温度を７２℃に上げて反応を２時間以上継続し、重合転化率が９８％を超えたことを確認して槽内温度を３５℃以下に冷却した。得られたラテックス状のゴム含有グラフト共重合体を多量のメタノール中に投入して沈殿させ、１５０メッシュのステンレス製金網に流した後、先ず適量のメタノール、次に多量の純水で洗浄した。その後、減圧下で含水率が1重量％以下になるまで乾燥させ、パウダー状のゴム含有グラフト共重合体Ｇ２を得た。
得られたゴム含有グラフト共重合体Ｇ２を灰化後、酸溶解してＩＣＰ発光分光法および原子吸光法により、アルカリ金属含有量を測定した。結果は０．００４重量％であった。
Rubber-containing graft copolymer G2: Formalin condensate of 45.5 parts pure water, 1.0 part potassium rosinate, 0.5 parts potassium oleate, sodium naphthalenesulfonate in a pressure-resistant polymerization reactor made of stainless steel under reduced pressure 0.8 part, 0.03 part of potassium hydroxide, 55 parts of solid polymer 2 in solid content, 0.20 part of t-dodecyl mercaptan, 0.11 part of glucose, 0.03 part of ferrous sulfate The mixture was heated to 65 ° C. with sufficient stirring, and then 0.07 part of cumene hydroperoxide was added to initiate polymerization at 65 ° C. Immediately after the start, a monomer mixture of 20 parts of methyl methacrylate, 15 parts of styrene and 10 parts of acrylonitrile was continuously added over 3 hours. When the polymerization conversion exceeded 63%, 0.05 part of t-butyl hydroperoxide was added. The reaction temperature was raised to 72 ° C. and the reaction was continued for 2 hours or longer. After confirming that the polymerization conversion rate exceeded 98%, the temperature in the tank was cooled to 35 ° C. or lower. The obtained latex-like rubber-containing graft copolymer was poured into a large amount of methanol, precipitated, poured into a 150-mesh stainless steel wire mesh, and then washed with an appropriate amount of methanol and then with a large amount of pure water. Then, it was dried until the water content became 1% by weight or less under reduced pressure to obtain a powdery rubber-containing graft copolymer G2.
The obtained rubber-containing graft copolymer G2 was incinerated, then dissolved in an acid, and the alkali metal content was measured by ICP emission spectroscopy and atomic absorption. The result was 0.004% by weight.
ゴム含有グラフト共重合体Ｇ３：ステンレス製耐圧重合反応機に、減圧下で純水７４．７部、オレイン酸カリウム１．２部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物１．０部、水酸化カリウム０．０４部、ゴム状重合体３を固形分で４０部、ブドウ糖０．０９部、硫酸第一鉄０．００４部を仕込んで十分攪拌しながら６８℃に昇温した後、ｔ−ブチルハイドロパーオキサイド０．０７部を仕込み６８℃で重合を開始した。開始直後からメチルメタクリレート５６部、メチルアクリレート３部、スチレン１部、ｔ−ドデシルメルカプタン０．２０部の混合物を４時間にわたって連続添加し、重合転化率が６５％を越えた時点でクメンハイドロパーオキサイド０．０４部を仕込み、反応温度を７３℃に上げて反応を２時間以上継続し、重合転化率が９８％を超えたことを確認して槽内温度を４０℃以下に冷却した。得られたラテックス状のゴム含有グラフト共重合体を多量のメタノール中に投入して沈殿させ、１５０メッシュのステンレス製金網に流した後、先ず適量のメタノール、次に多量の純水で洗浄した。その後、減圧下で含水率が1重量％以下になるまで乾燥させ、パウダー状のゴム含有グラフト共重合体Ｇ３を得た。
得られたゴム含有グラフト共重合体Ｇ３を灰化後、酸溶解してＩＣＰ発光分光法および原子吸光法により、アルカリ金属含有量を測定した。結果は０．００４重量％であった。
Rubber-containing graft copolymer G3: In a pressure-resistant polymerization reactor made of stainless steel, 74.7 parts of pure water, 1.2 parts of potassium oleate, 1.0 part of formalin condensate of sodium naphthalenesulfonate under reduced pressure, potassium hydroxide 0.04 part, 40 parts of rubbery polymer 3 in solid content, 0.09 part of glucose and 0.004 part of ferrous sulfate were charged and heated to 68 ° C. with sufficient stirring. 0.07 part of peroxide was charged and polymerization was started at 68 ° C. A mixture of 56 parts of methyl methacrylate, 3 parts of methyl acrylate, 1 part of styrene and 0.20 part of t-dodecyl mercaptan was added continuously for 4 hours from the start and cumene hydroperoxide was reached when the polymerization conversion exceeded 65%. 0.04 part was charged, the reaction temperature was raised to 73 ° C., and the reaction was continued for 2 hours or more. After confirming that the polymerization conversion rate exceeded 98%, the temperature in the tank was cooled to 40 ° C. or less. The obtained latex-like rubber-containing graft copolymer was poured into a large amount of methanol, precipitated, poured into a 150-mesh stainless steel wire mesh, and then washed with an appropriate amount of methanol and then with a large amount of pure water. Then, it was dried until the water content became 1% by weight or less under reduced pressure to obtain a powdery rubber-containing graft copolymer G3.
The obtained rubber-containing graft copolymer G3 was incinerated, then dissolved in acid, and the alkali metal content was measured by ICP emission spectroscopy and atomic absorption. The result was 0.004% by weight.
ゴム含有グラフト共重合体Ｇ４：容積が１５リットルのプラグフロー塔型反応槽に１０リットルの完全混合槽２基を直列に接続した連続的塊状重合装置を用いた。プラグフロー塔型反応槽が粒子形成工程を、第２反応器である１基目の完全混合槽が粒子径調整工程を、第３反応器が後重合工程を構成する。
プラグフロー塔型反応槽にエチルベンゼン２７重量部、メチルメタクリレート５７．０重量部、メチルアクリレート３．０重量部、ジエン系ゴム状重合体として、日本ゼオン社製Ｎｉｐｏｌ ＮＳ３２０Ｓを１３．０重量部、ｔ−ドデシルメルカプタン０．２２重量部、１、１−ビス（ｔ−ブチルパーオキシ）３、３、５−トリメチルシクロヘキサン０．０５０重量部からなる原料を調整し、この原料を３段の攪拌式重合槽列反応器に毎時１２ｋｇで連続的に供給して単量体の重合を行った。３段目の槽より重合液を予熱器と減圧室より成る分離回収工程に導いた。
回収工程から出た樹脂は押出工程を経て粒状のペレットとしてゴム含有グラフト共重合体Ｇ４を得た。このペレットの組成分析を熱分解クロマトグラフィーで実施したところ、ジエン系ゴム成分２６．０重量％、メチルメタクリレート単量体成分７０．３重量％、メチルアクリレート単量体成分３．７重量％であった。
得られたゴム含有グラフト共重合体Ｇ４を灰化後、酸溶解してＩＣＰ発光分光法および原子吸光法により、アルカリ金属含有量を測定した。結果は０．０００４重量％であった。
Rubber-containing graft copolymer G4: A continuous bulk polymerization apparatus in which two 10-liter complete mixing tanks were connected in series to a plug flow tower type reaction tank having a volume of 15 liters was used. The plug flow tower type reaction vessel constitutes the particle formation step, the first complete mixing vessel as the second reactor constitutes the particle size adjustment step, and the third reactor constitutes the post-polymerization step.
In a plug flow column reactor, 27 parts by weight of ethylbenzene, 57.0 parts by weight of methyl methacrylate, 3.0 parts by weight of methyl acrylate, 13.0 parts by weight of Nipol NS320S manufactured by Nippon Zeon Co., Ltd. as a diene rubbery polymer, t -A raw material consisting of 0.22 parts by weight of dodecyl mercaptan, 0.050 part by weight of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane was prepared, and this raw material was stirred in three stages. The monomer was polymerized by continuously feeding to the tank row reactor at 12 kg / hour. The polymerization solution was led from the third-stage tank to a separation and recovery step comprising a preheater and a decompression chamber.
The resin from the recovery step was subjected to an extrusion step to obtain a rubber-containing graft copolymer G4 as granular pellets. The composition analysis of the pellets was conducted by pyrolysis chromatography. As a result, the diene rubber component was 26.0% by weight, the methyl methacrylate monomer component was 70.3% by weight, and the methyl acrylate monomer component was 3.7% by weight. It was.
The obtained rubber-containing graft copolymer G4 was incinerated, then dissolved in an acid, and the alkali metal content was measured by ICP emission spectroscopy and atomic absorption. The result was 0.0004% by weight.
ゴム含有グラフト共重合体Ｇ５：前述と同様のプラグフロー塔型反応槽にエチルベンゼン２７重量部、メチルメタクリレート５７．０重量部、アクリロニトリル３．０重量部、ジエン系ゴム状重合体として、日本ゼオン社製Ｎｉｐｏｌ ＮＳ３２０Ｓを１３．０重量部、ｔ−ドデシルメルカプタン０．３０重量部、１、１−ビス（ｔ−ブチルパーオキシ）３、３、５−トリメチルシクロヘキサン０．０４０重量部からなる原料を調整し、この原料を３段の攪拌式重合槽列反応器に毎時１２ｋｇで連続的に供給して単量体の重合を行った。３段目の槽より重合液を予熱器と減圧室より成る分離回収工程に導いた。
回収工程から出た樹脂は押出工程を経て粒状のペレットとしてゴム含有グラフト共重合体Ｇ５を得た。このペレットの組成分析を熱分解クロマトグラフィーで実施したところ、ジエン系ゴム成分２６．０重量％、メチルメタクリレート単量体成分７０．５重量％、アクリロニトリル単量体成分３．５重量％であった。
得られたゴム含有グラフト共重合体Ｇ５を灰化後、酸溶解してＩＣＰ発光分光法および原子吸光法により、アルカリ金属含有量を測定した。結果は０．０００６重量％であった。
Rubber-containing graft copolymer G5: 27 parts by weight of ethylbenzene, 57.0 parts by weight of methyl methacrylate, 3.0 parts by weight of acrylonitrile, and diene rubbery polymer in a plug flow tower type reaction vessel similar to the above. Preparation of raw material consisting of Nipol NS320S manufactured by 13.0 parts by weight, t-dodecyl mercaptan 0.30 parts by weight, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 0.040 parts by weight Then, this raw material was continuously supplied to a three-stage stirred polymerization tank train reactor at 12 kg / hour to polymerize the monomer. The polymerization solution was led from the third-stage tank to a separation and recovery step comprising a preheater and a decompression chamber.
The resin from the recovery step was subjected to an extrusion step to obtain a rubber-containing graft copolymer G5 as granular pellets. When the composition analysis of the pellets was performed by pyrolysis chromatography, the diene rubber component was 26.0% by weight, the methyl methacrylate monomer component was 70.5% by weight, and the acrylonitrile monomer component was 3.5% by weight. .
The obtained rubber-containing graft copolymer G5 was incinerated, then dissolved in acid, and the alkali metal content was measured by ICP emission spectroscopy and atomic absorption. The result was 0.0006% by weight.
ゴム含有グラフト共重合体Ｇ６：前述と同様のプラグフロー塔型反応槽にエチルベンゼン２５重量部、メチルメタクリレート３７．８重量部、アクリロニトリル１２．６重量部、スチレン１２．６部、ジエン系ゴム状重合体として、日本ゼオン社製Ｎｉｐｏｌ ＮＳ３２０Ｓを１２．０重量部、ｔ−ドデシルメルカプタン０．３５重量部、１、１−ビス（ｔ−ブチルパーオキシ）３、３、５−トリメチルシクロヘキサン０．０３５重量部からなる原料を調整し、この原料を３段の攪拌式重合槽列反応器に毎時１１ｋｇで連続的に供給して単量体の重合を行った。３段目の槽より重合液を予熱器と減圧室より成る分離回収工程に導いた。
回収工程から出た樹脂は押出工程を経て粒状のペレットとしてゴム含有グラフト共重合体Ｇ６を得た。このペレットの組成分析を熱分解クロマトグラフィーで実施したところ、ジエン系ゴム成分２４．０重量％、メチルメタクリレート単量体成分４５．６重量％、アクリロニトリル単量体成分１５．０重量％、スチレン単量体成分１５．４重量％であった。
得られたゴム含有グラフト共重合体Ｇ６を灰化後、酸溶解してＩＣＰ発光分光法および原子吸光法により、アルカリ金属含有量を測定した。結果は０．０００４重量％であった。
Rubber-containing graft copolymer G6: In the same plug flow column reactor as described above, 25 parts by weight of ethylbenzene, 37.8 parts by weight of methyl methacrylate, 12.6 parts by weight of acrylonitrile, 12.6 parts of styrene, diene rubbery heavy As a combination, 12.0 parts by weight of Nipol NS320S manufactured by Nippon Zeon Co., Ltd., 0.35 parts by weight of t-dodecyl mercaptan, 0.035 weight of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane The raw material consisting of parts was prepared, and this raw material was continuously supplied to a three-stage stirred polymerization tank train reactor at 11 kg / h to polymerize the monomer. The polymerization solution was led from the third-stage tank to a separation and recovery step comprising a preheater and a decompression chamber.
The resin from the recovery step was subjected to an extrusion step to obtain a rubber-containing graft copolymer G6 as granular pellets. The composition of the pellet was analyzed by pyrolysis chromatography. As a result, the diene rubber component was 24.0% by weight, the methyl methacrylate monomer component 45.6% by weight, the acrylonitrile monomer component 15.0% by weight, the styrene monomer The monomer component was 15.4% by weight.
The obtained rubber-containing graft copolymer G6 was incinerated and then dissolved in an acid, and the alkali metal content was measured by ICP emission spectroscopy and atomic absorption. The result was 0.0004% by weight.
ポリカーボネート樹脂（Ｃ）
ポリカーボネート樹脂（Ｃ）として、住友ダウ株式会社製 カリバー２００−３０を用いた。
Polycarbonate resin (C)
As the polycarbonate resin (C), Caliber 200-30 manufactured by Sumitomo Dow Co., Ltd. was used.
α−メチルスチレン−アクリロニトリル共重合体Ａ１〜Ａ２の製造
α−メチルスチレン−アクリロニトリル共重合体Ａ１：容積が１５リットルのプラグフロー塔型反応槽に１０リットルの完全混合槽２基を直列に接続した連続的塊状重合装置を用いた。
プラグフロー塔型反応槽にエチルベンゼン３０重量部、α−メチルスチレン４９．７重量部、アクリロニトリル２０．３重量部、ｔ−ドデシルメルカプタン０．２０重量部、１、１−ビス（ｔ−ブチルパーオキシ）３、３、５−トリメチルシクロヘキサン０．０９０重量部からなる原料を調整し、この原料を３段の攪拌式重合槽列反応器に毎時９ｋｇで連続的に供給して単量体の重合を行った。３段目の槽より重合液を予熱器と減圧室より成る分離回収工程に導いた。
回収工程から出た樹脂は押出工程を経て粒状のペレットとしてα−メチルスチレン−アクリロニトリル共重合体
Ａ１を得た。このペレットの組成分析を熱分解クロマトグラフィーで実施したところ、α−メチルスチレン単量体成分７１重量％、アクリロニトリル単量体成分２９重量％であった。
Production of α-methylstyrene-acrylonitrile copolymers A1 to A2 α-methylstyrene-acrylonitrile copolymer A1: Two 10-liter complete mixing tanks were connected in series to a 15-liter plug flow column reactor. A continuous bulk polymerization apparatus was used.
In a plug flow column reactor, 30 parts by weight of ethylbenzene, 49.7 parts by weight of α-methylstyrene, 20.3 parts by weight of acrylonitrile, 0.20 parts by weight of t-dodecyl mercaptan, 1,1-bis (t-butylperoxy ) A raw material consisting of 0.090 parts by weight of 3,3,5-trimethylcyclohexane was prepared, and this raw material was continuously supplied to a three-stage stirred polymerization tank train reactor at 9 kg / hour to polymerize the monomer. went. The polymerization solution was led from the third-stage tank to a separation and recovery step comprising a preheater and a decompression chamber.
The resin from the recovery step was subjected to an extrusion step to obtain α-methylstyrene-acrylonitrile copolymer A1 as granular pellets. The composition analysis of the pellets was carried out by pyrolysis chromatography. As a result, the α-methylstyrene monomer component was 71% by weight and the acrylonitrile monomer component was 29% by weight.
α−メチルスチレン−アクリロニトリル共重合体Ａ２：ステンレス製耐圧重合反応機に、減圧下で純水１６０部、ロジン酸カリウム２．５部、オレイン酸カリウム０．５部、ナフタレンスルホン酸ナトリウムのホルマリン縮合物０．７部、水酸化ナトリウム０．０８部、α−メチルスチレン７３部、アクリロニトリル２７部、ｔ−ドデシルメルカプタン０．１５部を加えて十分攪拌しながら７０℃に昇温した後、過硫酸カリウム０．７部を仕込み７０℃で重合を開始した。重合転化率が６８％を越えた時点で反応温度を７６℃に上げて反応を継続し、重合転化率が９６％を超えたことを確認して槽内温度を４０℃以下に冷却した。得られたα−メチルスチレン−アクリロニトリル共重合体を多量のメタノール中に投入して沈殿させ、２００メッシュのステンレス製金網に流した後、先ず適量のメタノール、次に多量の純水で洗浄した。その後、減圧下で含水率が1重量％以下になるまで乾燥させ、パウダー状のα−メチルスチレン−アクリロニトリル共重合体Ａ２を得た。 α-methylstyrene-acrylonitrile copolymer A2: formalin condensation of 160 parts of pure water, 2.5 parts of potassium rosinate, 0.5 parts of potassium oleate, sodium naphthalenesulfonate in a pressure-resistant polymerization reactor made of stainless steel under reduced pressure 0.7 parts of sodium hydroxide, 0.08 parts of sodium hydroxide, 73 parts of α-methylstyrene, 27 parts of acrylonitrile, 0.15 part of t-dodecyl mercaptan and heated to 70 ° C. with sufficient stirring, followed by persulfuric acid 0.7 parts of potassium was charged and polymerization was started at 70 ° C. When the polymerization conversion rate exceeded 68%, the reaction temperature was raised to 76 ° C and the reaction was continued. After confirming that the polymerization conversion rate exceeded 96%, the temperature in the tank was cooled to 40 ° C or less. The obtained α-methylstyrene-acrylonitrile copolymer was poured into a large amount of methanol, precipitated, poured into a 200-mesh stainless steel wire mesh, and then washed with an appropriate amount of methanol and then with a large amount of pure water. Then, it was dried until the water content became 1% by weight or less under reduced pressure to obtain a powdery α-methylstyrene-acrylonitrile copolymer A2.
〔実施例１〜６、比較例１〜８〕
上記、ポリ乳酸樹脂（Ｌ）、ゴム含有グラフト共重合体（Ｇ１〜Ｇ６）、ポリカーボネート樹脂（Ｃ）、α−メチルスチレン−アクリロニトリル共重合体（Ａ１〜Ａ２）を表１に示す配合割合で混合し、３０ｍｍニ軸押出機を用いて２４０℃から２６０℃で溶融混合し、ペレット化した後、射出成形機にて各種試験片を作成して物性を評価した。それぞれの評価方法を以下に示し、評価結果を表１にまとめた。
[Examples 1-6, Comparative Examples 1-8]
The above-mentioned polylactic acid resin (L), rubber-containing graft copolymer (G1 to G6), polycarbonate resin (C), and α-methylstyrene-acrylonitrile copolymer (A1 to A2) are mixed in the mixing ratio shown in Table 1. Then, using a 30 mm twin screw extruder, it was melt-mixed at 240 ° C. to 260 ° C. and pelletized, and various test pieces were prepared with an injection molding machine to evaluate physical properties. Each evaluation method is shown below, and the evaluation results are summarized in Table 1.
各物性の評価方法
加工性：ＩＳＯ １１３３に基づき２２０℃、１０Ｋｇの条件でメルトインデックスを測定した。単位はｇ／１０分。得られた測定結果に基づいて下記の様に相対区分した。
◎（優秀）：４０以上
○（良好）：２０以上〜４０未満
△（微劣）：５以上〜２０未満
×（不良）：５未満
Evaluation method of each physical property Workability: Melt index was measured at 220 ° C. and 10 kg based on ISO 1133. The unit is g / 10 minutes. Based on the measurement results obtained, relative classification was performed as follows.
◎ (excellent): 40 or more ○ (good): 20 or more to less than 40 △ (slightly inferior): 5 or more to less than 20 × (defect): less than 5
衝撃強度：ＩＳＯ １７９に準拠し、ノッチ付きのシャルピー衝撃値を測定した。単位はｋJ／ｍ２。
得られた測定結果に基づいて下記の様に相対区分した。
◎（優秀）：１５以上
○（良好）：１０以上〜１５未満
△（微劣）：５以上１０未満
×（不良）：５未満
Impact strength: Based on ISO 179, a Charpy impact value with a notch was measured. Unit is kJ / m 2.
Based on the measurement results obtained, relative classification was performed as follows.
◎ (Excellent): 15 or more ○ (Good): 10 or more and less than 15 △ (Slightly inferior): 5 or more and less than 10 × (Bad): Less than 5
耐熱性：ＩＳＯ ７５に準拠し、荷重１．８ＭＰａの荷重たわみ温度を測定した。単位は℃。
得られた測定結果に基づいて下記の様に相対区分した。
◎（優秀）：８０℃以上
○（良好）：７５℃以上〜８０℃未満
△（微劣）：６５℃以上〜７５℃未満
×（不良）：６５℃未満
Heat resistance: Based on ISO 75, the deflection temperature under load of 1.8 MPa was measured. The unit is ° C.
Based on the measurement results obtained, relative classification was performed as follows.
◎ (Excellent): 80 ° C. or higher ○ (Good): 75 ° C. or higher to lower than 80 ° C.
外観の均一性：２箇所にゲートをもつデュポンインパクト測定用テストピースを肉眼で判定し、
下記の様に相対区分した。
◎（優秀）：まったくウェルドラインが観察されず、表面光沢も良好。
○（良好）：明確なウェルドラインは認められないが、テストピース中央の光沢がやや不均一。
△（微劣）：ウェルドラインが認められ、光沢も不均一。
×（不良）：明確なウェルドラインが認められる。
Appearance uniformity: The test piece for measuring DuPont impact with two gates is judged with the naked eye,
The relative classification was as follows.
◎ (Excellent): No weld line is observed and surface gloss is good.
○ (Good): No clear weld line is observed, but the gloss at the center of the test piece is slightly uneven.
Δ (slightly inferior): Weld line is observed and gloss is not uniform.
X (defect): A clear weld line is recognized.
以上のように、本発明は、衝撃強度、耐熱性、加工性、外観の均一性のバランスに優れた熱可塑性樹脂組成物が得られるものであり、車両分野、家電分野、建材分野、サニタリー分野等に広く用いることができる。
また、石油資源消費の抑制にも貢献できる環境対応型材料である。
As described above, the present invention provides a thermoplastic resin composition having an excellent balance of impact strength, heat resistance, workability, and appearance uniformity, and is used in the vehicle field, home appliance field, building material field, and sanitary field. Can be used widely.
It is also an environmentally friendly material that can contribute to the reduction of petroleum resource consumption.
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| JP2006045486A (en) * | 2004-07-02 | 2006-02-16 | Nippon A & L Kk | Thermoplastic resin composition |
| JP2006137908A (en) * | 2004-11-15 | 2006-06-01 | Umg Abs Ltd | Polylactic acid-based thermoplastic resin composition and molded article of the same |
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| JP2013256591A (en) * | 2012-06-13 | 2013-12-26 | Panasonic Corp | Polylactic acid resin composition, method for producing molded article, and molded article |
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