JP6616019B2 - Asa系グラフト共重合体の製造方法、それを含む熱可塑性樹脂組成物の製造方法及び成形品の製造方法 - Google Patents
Asa系グラフト共重合体の製造方法、それを含む熱可塑性樹脂組成物の製造方法及び成形品の製造方法 Download PDFInfo
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- 125000005843 halogen group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- 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
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- 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
- C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2096/00—Use of specified macromolecular materials not provided for in a single one of main groups B29K2001/00 - B29K2095/00, as moulding material
- B29K2096/02—Graft polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0085—Copolymers
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Description
本出願は、2017年03月20日付の韓国特許出願第10−2017−0034357号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
本記載のシード製造ステップは、一例として、グラフト共重合体の製造時に使用される単量体の合計100重量部を基準として、芳香族ビニル単量体、ビニルシアン単量体及びアルキルアクリレート単量体から選択された1種以上の単量体4〜30重量部及び乳化剤0.005〜0.5重量部を含んで重合させてシードを製造することができる。
本記載のコア製造ステップは、前記シードの存在下でアルキルアクリレート単量体を投入し、重合させて、シードを囲むコアを形成するステップである。
本記載において、シェル製造ステップは、前記コアの存在下で芳香族ビニル単量体、ビニルシアン単量体及び乳化剤を含んでグラフト重合させて、前記コアを囲むシェルを形成するステップであり、このとき、乳化剤は、炭素数20〜60個の多官能カルボン酸又はその塩を含むことを特徴とすることができる。
本記載のASA系グラフト共重合体の製造方法は、開始剤の活性を促進して反応効率を向上させるために、開始剤を酸化−還元系触媒と併用して使用することが可能である。
実施例1
1.高分子シード製造ステップ
窒素置換された反応器にブチルアクリレート6重量部、ドデシル硫酸ナトリウム0.05重量部、エチレングリコールジメタクリレート0.04重量部、アリルメタクリレート0.02重量部、水酸化カリウム0.1重量部及び蒸留水45重量部を一括投入し、70℃まで昇温させた後、過硫酸カリウム0.04重量部を入れて反応を開始させた。その後、重合を2時間行った。
前記高分子シードに、ブチルアクリレート44重量部、ドデシル硫酸ナトリウム0.5重量部、エチレングリコールジメタクリレート0.2重量部、アリルメタクリレート0.2重量部、蒸留水30重量部及び過硫酸カリウム0.05重量部を混合した混合物を、70℃で3時間連続投入し、投入終了後、1時間さらに重合を行った。
前記高分子コアの存在下で、蒸留水23重量部、スチレン38重量部、アクリロニトリル12重量部を含む単量体混合物と;炭素数36個のモノサイクリック二官能性カルボン酸80重量%、炭素数54個のバイサイクリック二官能性カルボン酸15重量%及び炭素数18個以下の非環状二官能性5重量%を含む混合乳化剤FS200(LG生活健康)0.8重量部、3級ドデシルメルカプタン(TDDM)0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液と;ピロリン酸ナトリウム0.09重量部、デキストロース0.12重量部、及び硫化第一鉄0.002重量部を含む混合液とを、それぞれ75℃で3時間連続投入しながら重合反応を行った。重合転化率を高めるために、前記乳化液と混合液の投入が完了した後、75℃で1時間さらに反応させ、60℃まで冷却させて重合反応を終了して、グラフト共重合体ラテックスを製造した。
前記で製造されたアクリレート−スチレン−アクリロニトリルグラフト共重合体ラテックスに塩化カルシウム水溶液0.8重量部を適用して、70℃で常圧凝集を行った後、93℃で熟成し、脱水及び洗浄して、90℃の熱風で30分間乾燥した後、アクリレート−スチレン−アクリロニトリル共重合体粉末を製造した。
前記グラフト共重合体粉末44重量部、硬質のマトリックススチレン−アクリロニトリル共重合体90HR(アクリロニトリル27重量%及びスチレン73重量%を含む、LG化学社製)56重量部、滑剤1.5重量部、酸化防止剤1.0重量部、紫外線安定剤1.0重量部を添加して混合した。この混合物を、220℃のシリンダー温度で36Φ押出混練機を使用してペレットの形態で製造し、このペレット形態の樹脂を射出成形(射出成形温度200〜230℃、射出圧力40〜60bar)して、物性測定のための試片を製造した。
実施例1の高分子グラフトシェル製造ステップにおいて、混合乳化剤FS200(LG生活健康)0.8重量部、3級ドデシルメルカプタン(TDDM)0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液の代わりに、FS200(LG生活健康)0.4重量部、ロジン酸ナトリウム0.7重量部、TDDM0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液を使用した以外は、実施例1と同様の方法で行った。
実施例1の高分子シード製造ステップにおいて、ドデシル硫酸ナトリウムを0.05重量部の代わりに0.03重量部投入し、ブチルアクリレート6重量部の代わりにスチレン6重量部を使用した以外は、実施例1と同様の方法で高分子シードを製造し、これを使用して実施例1と同様の方法でアクリル系熱可塑性樹脂組成物を製造した。
実施例1の高分子シード製造ステップにおいて、ドデシル硫酸ナトリウムを0.05重量部の代わりに0.03重量部投入し、ブチルアクリレート6重量部の代わりにブチルアクリレート4重量部及びスチレン2重量部を使用した以外は、実施例1と同様の方法で高分子シードを製造し、これを使用して実施例1と同様の方法でアクリル系熱可塑性樹脂組成物を製造した。
実施例1の高分子グラフトシェル製造ステップにおいて、混合乳化剤FS200(LG生活健康)0.8重量部、3級ドデシルメルカプタン(TDDM)0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液の代わりに、炭素数18〜20個の二官能性カルボン酸カリウム塩29重量%を含む乳化剤AS200(LG生活健康)0.5重量部、ロジン酸ナトリウム0.6重量部、TDDM0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液を使用した以外は、前記実施例1と同様の方法で行った。
前記実施例1の高分子グラフトシェル製造ステップにおいて、混合乳化剤FS200(LG生活健康)0.8重量部、3級ドデシルメルカプタン(TDDM)0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液の代わりに、ロジン酸カリウム1.8重量部、TDDM0.02重量部及びクメンヒドロペルオキシド0.05重量部を含む乳化液を使用した以外は、実施例1と同様の方法で行った。
実施例1の高分子シード製造ステップにおいて、ドデシル硫酸ナトリウムを0.05重量部の代わりに0.3重量部とした以外は、実施例1と同様の方法で行った。
前記実施例及び比較例で製造されたASA系グラフト共重合体及びそれを含む樹脂組成物の物性を、下記の方法で測定し、その結果を下記の表1に示す。
Claims (15)
- a)芳香族ビニル単量体、ビニルシアン単量体及びアルキルアクリレート単量体から選択された1つ以上の単量体及び乳化剤を含んで重合させてシードを製造するシード製造ステップと、
b)前記シードの存在下でアルキルアクリレート単量体を投入し、重合させて、前記シードを囲むコアを製造するコア製造ステップと、
c)前記コアの存在下で芳香族ビニル単量体、ビニルシアン単量体及び乳化剤を投入し、グラフト重合させて、前記コアを囲むシェルを製造するシェル製造ステップと、を含み、
前記シェル製造ステップの乳化剤は、炭素数20〜60の多官能カルボン酸又はその塩を含み、
前記シェルは、平均サイズが250〜750nm(コアの平均サイズよりも大きい)であり、
前記シードは、平均サイズが90〜400nmである
ことを特徴とする、ASA系グラフト共重合体の製造方法。 - 前記多官能カルボン酸は、構造内にカルボキシル基を2つ又は3つ含む、請求項1に記載のASA系グラフト共重合体の製造方法。
- 前記シェル製造ステップにおいて使用される乳化剤の総重量に対して、炭素数20〜60の多官能カルボン酸又はその塩は、30〜100重量%含まれる、請求項1または2に記載のASA系グラフト共重合体の製造方法。
- 前記シェル製造ステップの乳化剤は、炭素数20〜60の多官能カルボン酸又はその塩と、炭素数10〜20のモノカルボン酸塩とを含む、請求項1〜3のいずれか一項に記載のASA系グラフト共重合体の製造方法。
- 前記シェル製造ステップの乳化剤は、炭素数20〜60の多官能カルボン酸又はその塩と、前記炭素数10〜20のモノカルボン酸塩とを1:0.1〜1:10の重量比で含む、請求項4に記載のASA系グラフト共重合体の製造方法。
- 前記シード製造ステップにおいて、シードを製造するために、共重合体の製造に使用される単量体の合計100重量部に対して、芳香族ビニル単量体、ビニルシアン単量体及びアルキルアクリレート単量体から選択された1種以上を含む単量体4〜30重量部及び乳化剤0.005〜0.5重量部が用いられる、請求項1〜5のいずれか一項に記載のASA系グラフト共重合体の製造方法。
- 前記コア製造ステップにおいて、前記シードの存在下でコアを製造するために、アルキルアクリレート単量体30〜60重量部及び架橋剤0.01〜1重量部が用いられる、請求項1〜6のいずれか一項に記載のASA系グラフト共重合体の製造方法。
- 前記架橋剤は、アクリル系架橋剤を含む、請求項7に記載のASA系グラフト共重合体の製造方法。
- 前記コアは、平均サイズが180〜600nmであり、シードの平均サイズよりも大きい、請求項7または8に記載のASA系グラフト共重合体の製造方法。
- 前記シェル製造ステップにおいて、前記コアの存在下で、芳香族ビニル単量体及びビニルシアン単量体30〜60重量部及び乳化剤0.1〜3重量部をグラフト重合させてシェルを製造する、請求項1〜9のいずれか一項に記載のASA系グラフト共重合体の製造方法。
- 請求項1乃至10のいずれか1項に記載の製造方法により製造されたASA系グラフト共重合体20〜60重量%と、ビニルシアン単量体−芳香族ビニル単量体共重合体40〜80重量%とを混練するステップを含む、熱可塑性樹脂組成物の製造方法。
- 前記混練時に、難燃剤、滑剤、抗菌剤、離型剤、核剤、可塑剤、熱安定剤、酸化防止剤、光安定剤、顔料、染料及び相溶化剤からなる群から選択された1つ以上の添加剤をさらに含む、請求項11に記載の熱可塑性樹脂組成物の製造方法。
- 請求項11または12に記載の方法によって製造された熱可塑性樹脂組成物を射出成形するステップを含む、成形品の製造方法。
- 前記成形品は、260℃で10分間滞留させた後、射出成形し、分光色差計を用いて測定した滞留前と滞留後の色度変化値(ΔE)が0超〜4以下である、請求項13に記載の成形品の製造方法。
- 前記射出成形時のガス発生量が1,000ppm以下である、請求項13または14に記載の成形品の製造方法。
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