JP2023505630A - 熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品 - Google Patents
熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品 Download PDFInfo
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- JP2023505630A JP2023505630A JP2022521700A JP2022521700A JP2023505630A JP 2023505630 A JP2023505630 A JP 2023505630A JP 2022521700 A JP2022521700 A JP 2022521700A JP 2022521700 A JP2022521700 A JP 2022521700A JP 2023505630 A JP2023505630 A JP 2023505630A
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- compound
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- copolymer
- vinyl cyanide
- thermoplastic resin
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- -1 vinyl cyanide compound Chemical class 0.000 claims abstract description 97
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
Description
本出願は、2020年10月29日付の韓国特許出願第10-2020-0141893号及びこれに基づいて2021年08月13日付で再出願された韓国特許出願第10-2021-0107006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組み込まれる。
本発明の(A)ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物グラフト共重合体は、一例として、ベース樹脂中に10~40重量%、好ましくは15~40重量%、より好ましくは20~35重量%であってもよく、この範囲内で、機械的強度、流動性及び物性バランスに優れるという効果がある。
本発明の(B)(メタ)アクリル酸アルキルエステル化合物-α-メチルスチレン系化合物-ビニルシアン化合物共重合体は、一例として、ベース樹脂中に18~52重量%、好ましくは20~50重量%、より好ましくは25~45重量%であってもよく、この範囲内で、耐衝撃性、流動性及び耐化学性がいずれも優れるという利点がある。
本発明の(C)芳香族ビニル化合物-ビニルシアン化合物共重合体は、一例として、ベース樹脂中に13~55重量%、好ましくは15~50重量%、より好ましくは20~45重量%含まれてもよく、この範囲内で、機械的強度、流動性及び物性バランスに優れるという効果がある。
本発明の(D)ポリエーテルエステルエラストマー樹脂は、一例として、ベース樹脂100重量部に対して7~17重量部、好ましくは7~15重量部、より好ましくは9~15重量部含まれてもよく、この範囲内で、機械的物性、耐熱性、流動性及び耐化学性に優れるという効果がある。
本発明の(E)変性ポリエステル樹脂は、一例として、ベース樹脂100重量部に対して1.1~10重量部、好ましくは1.5~8重量部、より好ましくは2~7重量部であってもよく、この範囲内で、衝撃強度、引張強度などの機械的物性、耐化学性及び流動性がいずれも優れるという効果がある。
前記(F)アルキレンオキシド共重合体は、一例として、ベース樹脂100重量部に対して0.3~5重量部、好ましくは0.5~4重量部、より好ましくは0.5~2重量部含むことができ、この範囲内で、機械的物性、耐衝撃性及び流動性がさらに改善されるという効果がある。前記範囲未満では、引張強度及び耐化学性が低下する。
x、yまたはzは、x、y及びzの総100モル%に対するそれぞれのモル%であって、x+y+z=100であり、10≦x≦80、10≦y≦50、及び10≦z≦80である。
前記ベース樹脂は、一例として、(A)グラフト共重合体、(B)共重合体、(C)共重合体、(D)樹脂及び(G)塊状重合ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物共重合体を合わせた総重量に対して、前記(G)共重合体を1~20重量%、好ましくは3~15重量%、より好ましくは5~10重量%含むことができ、この範囲内で、流動性及び引張強度などの機械的物性がさらに改善されるという効果がある。
前記熱可塑性樹脂組成物は、一例として、2.0%のひずみ(strain)を有する曲率ジグ(jig)に160×10×4mmの試験片を固定し、アムウェイ社の芳香剤であるアロマナチュラル(製品名)を0.1cc塗布した後、試験片にクラックが発生する時間を測定する耐化学性評価において、24時間後にクラックが発生せず、この場合、物性バランスに優れながら、耐化学性に優れるので、自動車内装材に適用可能であるという効果がある。
本発明の熱可塑性樹脂組成物の製造方法は、(A)ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物グラフト共重合体10~40重量%と、(B)(メタ)アクリル酸アルキルエステル化合物-α-メチルスチレン系化合物-ビニルシアン化合物共重合体18~52重量%と、(C)芳香族ビニル化合物-ビニルシアン化合物共重合体13~55重量%とを含むベース樹脂100重量部に、(D)ポリエーテルエステルエラストマー樹脂7~17重量部及び(E)変性ポリエステル樹脂1.1~10重量部を含んで200~300℃及び200~700rpmの条件下で混練及び押出してペレットに製造するステップを含み、前記(C)芳香族ビニル化合物-ビニルシアン化合物共重合体はビニルシアン化合物10~25重量%を含んでなることを特徴とする。このような場合、流動性及び耐衝撃性、引張強度などの機械的物性に優れながら、耐化学性に優れるという利点がある。
本発明の成形品は本発明の熱可塑性樹脂組成物を含むことができ、この場合、流動性及び耐衝撃性、引張強度などの機械的物性に優れながら、耐化学性に優れるという利点がある。
*(A-1)ABSグラフト共重合体:LG化学社のDP270
*(A-2)ASAグラフト共重合体:LG化学社のSA927
*(B-1)MMA-α-メチルスチレン-アクリロニトリル共重合体:LG化学社の290UH
*(B-2)α-メチルスチレン-アクリロニトリル共重合体:LG化学社の200UH
*(B-3)PMI系耐熱樹脂:DENKA社のMSNI
*(C-1)SAN共重合体:LG化学社の81HF(アクリロニトリルの含量24重量%)
*(C-2)SAN共重合体:LG化学社の97HC(アクリロニトリルの含量30.5重量%)
*(C-3)SAN共重合体:LG化学社の92RF(アクリロニトリルの含量28重量%)
*(D)ポリエーテルエステルエラストマー(TPEE):LG化学社のKEYFLEX BT2140D(溶融指数(230℃、2.16kg):5g/10分、ショアD硬度:40D)
*(E)変性ポリエステル樹脂(PETG):SK Chemical社のJIN100
*(F)PEO/PPO/PEO共重合体:BASF社のPluronic F68
*(G)塊状重合されたABS共重合体:LG化学社のER400
それぞれ、下記表1~表3に記載された成分及び含量を、押出機(SM Twin screw extruder、25φ)にて押出温度250℃、Feed rate 25kg/hr、スクリュー回転数(Screw speed)600rpm下で混練及び押出してペレットを製造した。製造されたペレットを用いて流動指数を測定した。また、製造されたペレットをもって、射出機(ENGEL社、120MT)にて射出温度240℃、金型温度60℃及び射出速度30mm/分の条件下で射出試験片として作製した。
前記実施例1~7及び比較例1~14で製造されたペレット及び射出試験片の特性を下記の方法により測定し、その結果を下記の表1~表3に示した。
Claims (14)
- (A)ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物グラフト共重合体10~40重量%と、
(B)(メタ)アクリル酸アルキルエステル化合物-α-メチルスチレン系化合物-ビニルシアン化合物共重合体18~52重量%と、
(C)芳香族ビニル化合物-ビニルシアン化合物共重合体13~55重量%とを含むベース樹脂100重量部に、
(D)ポリエーテルエステルエラストマー樹脂7~17重量部、及び
(E)変性ポリエステル樹脂1.1~10重量部を含み、
前記(C)芳香族ビニル化合物-ビニルシアン化合物共重合体はビニルシアン化合物10~25重量%を含んでなることを特徴とする、熱可塑性樹脂組成物。 - 前記(A)グラフト共重合体は、共役ジエン化合物を含んでなる平均粒径0.2~0.5μmの共役ジエンゴム45~75重量%、芳香族ビニル化合物15~45重量%、及びビニルシアン化合物1~25重量%を含んでなることを特徴とする、請求項1に記載の熱可塑性樹脂組成物。
- 前記(B)(メタ)アクリル酸アルキルエステル化合物-α-メチルスチレン系化合物-ビニルシアン化合物共重合体は、(メタ)アクリル酸アルキルエステル化合物35~60重量%、α-メチルスチレン系化合物30~50重量%、及びビニルシアン化合物10~20重量%を含んでなることを特徴とする、請求項1または2に記載の熱可塑性樹脂組成物。
- 前記(D)ポリエーテルエステルエラストマー樹脂は、ASTM D1238に準拠して230℃、2.16kg下で測定した溶融指数が0.1~10g/10分であることを特徴とする、請求項1~3のいずれか一項に記載の熱可塑性樹脂組成物。
- 前記(D)ポリエーテルエステルエラストマー樹脂は、芳香族ジカルボン酸またはそのエステル形成誘導体;脂肪族ジオール;及びポリアルキレンオキシド;を溶融重合した後、生成物を固相重合させて収得された樹脂であることを特徴とする、請求項1~4のいずれか一項に記載の熱可塑性樹脂組成物。
- 前記(E)変性ポリエステル樹脂は、1,4-シクロヘキサンジメタノール由来の単位が50重量%以上であることを特徴とする、請求項1~5のいずれか一項に記載の熱可塑性樹脂組成物。
- 前記ベース樹脂は、(A)グラフト共重合体、(B)共重合体、(C)共重合体、及び(G)塊状重合ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物共重合体を合わせた総重量に対して、前記(G)共重合体1~20重量%を含むことを特徴とする、請求項1~6のいずれか一項に記載の熱可塑性樹脂組成物。
- 前記(G)塊状重合ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物共重合体は、共役ジエン化合物を含んでなる共役ジエンゴム5~20重量%、芳香族ビニル化合物55~85重量%及びビニルシアン化合物5~25重量%を含んで塊状重合された塊状共重合体であることを特徴とする、請求項7に記載の熱可塑性樹脂組成物。
- 前記ベース樹脂100重量部に対して(F)アルキレンオキシド共重合体0.3~5重量部を含むことを特徴とする、請求項1~8のいずれか一項に記載の熱可塑性樹脂組成物。
- 2.0%のひずみ(strain)を有する曲率ジグ(jig)に160×10×4mmの試験片を固定し、アムウェイ社の芳香剤であるアロマナチュラル(製品名)を0.1cc塗布した後、試験片にクラックが発生する時間を測定する耐化学性評価において、24時間後にクラックが発生しないことを特徴とする、請求項1~9のいずれか一項に記載の熱可塑性樹脂組成物。
- ISO 179/1eAに準拠して厚さ4mmの試験片にノッチ(notch)を付けて測定したシャルピー衝撃強度が26kJ/m2以上であることを特徴とする、請求項1~10のいずれか一項に記載の熱可塑性樹脂組成物。
- ISO 1133に準拠して220℃、10kg下で測定した溶融流れ指数(MFR)が15g/10分以上であることを特徴とする、請求項1~11のいずれか一項に記載の熱可塑性樹脂組成物。
- (A)ビニルシアン化合物-共役ジエン化合物-芳香族ビニル化合物グラフト共重合体10~40重量%と、(B)(メタ)アクリル酸アルキルエステル化合物-α-メチルスチレン系化合物-ビニルシアン化合物共重合体18~52重量%と、(C)芳香族ビニル化合物-ビニルシアン化合物共重合体13~55重量%とを含むベース樹脂100重量部に、(D)ポリエーテルエステルエラストマー樹脂7~17重量部及び(E)変性ポリエステル樹脂1.1~10重量部を含んで200~300℃及び200~700rpmの条件下で混練及び押出してペレットに製造するステップを含み、
前記(C)芳香族ビニル化合物-ビニルシアン化合物共重合体はビニルシアン化合物10~25重量%を含んでなることを特徴とする、熱可塑性樹脂組成物の製造方法。 - 請求項1~12のいずれか一項に記載の熱可塑性樹脂組成物を含むことを特徴とする、成形品。
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US (1) | US20230357559A1 (ja) |
EP (1) | EP4029915B1 (ja) |
JP (1) | JP7386983B2 (ja) |
CN (1) | CN114710959B (ja) |
TW (1) | TW202216887A (ja) |
WO (1) | WO2022092512A1 (ja) |
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EP0297517A2 (en) * | 1987-06-29 | 1989-01-04 | Idemitsu Petrochemical Co. Ltd. | Polycarbonate composition |
JPH09132684A (ja) * | 1995-11-08 | 1997-05-20 | Toray Ind Inc | 耐薬品性熱可塑性樹脂組成物 |
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KR101689064B1 (ko) * | 2013-12-10 | 2016-12-22 | 주식회사 엘지화학 | 스티렌계 수지 조성물 |
KR101950069B1 (ko) * | 2015-04-30 | 2019-02-19 | 롯데첨단소재(주) | 열가소성 수지 조성물 및 이로부터 제조된 성형품 |
KR102237246B1 (ko) * | 2016-04-21 | 2021-04-07 | 이네오스 스티롤루션 그룹 게엠베하 | 개선된 균열 및 화학적 내성을 갖는 abs 몰딩 조성물 및 그의 사용 |
KR102183901B1 (ko) * | 2016-12-28 | 2020-11-27 | 주식회사 엘지화학 | 스티렌계 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품 |
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KR102367060B1 (ko) * | 2019-01-17 | 2022-02-24 | 주식회사 엘지화학 | 도장성이 우수한 열가소성 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품 |
KR102386835B1 (ko) * | 2019-02-19 | 2022-04-15 | 주식회사 엘지화학 | 열가소성 수지 조성물 및 열가소성 수지 성형품 |
KR20200141893A (ko) | 2019-06-11 | 2020-12-21 | 주식회사 다이야코퍼레이션코리아 | 전자상품권 및 복권당첨금을 이용한 온라인 쇼핑몰에서의 결제시스템 |
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2021
- 2021-08-19 JP JP2022521700A patent/JP7386983B2/ja active Active
- 2021-08-19 EP EP21867906.6A patent/EP4029915B1/en active Active
- 2021-08-19 CN CN202180005640.XA patent/CN114710959B/zh active Active
- 2021-08-19 WO PCT/KR2021/011001 patent/WO2022092512A1/ko unknown
- 2021-08-19 US US17/774,412 patent/US20230357559A1/en active Pending
- 2021-08-26 TW TW110131595A patent/TW202216887A/zh unknown
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JPS62205148A (ja) * | 1986-03-04 | 1987-09-09 | Sumitomo Naugatuck Co Ltd | 熱可塑性樹脂組成物 |
EP0297517A2 (en) * | 1987-06-29 | 1989-01-04 | Idemitsu Petrochemical Co. Ltd. | Polycarbonate composition |
JPH09132684A (ja) * | 1995-11-08 | 1997-05-20 | Toray Ind Inc | 耐薬品性熱可塑性樹脂組成物 |
JPH11152387A (ja) * | 1997-08-30 | 1999-06-08 | Hyundai Motor Co Ltd | 耐薬品性及び耐熱性を有するスチレン系樹脂組成物 |
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US20230357559A1 (en) | 2023-11-09 |
JP7386983B2 (ja) | 2023-11-27 |
TW202216887A (zh) | 2022-05-01 |
CN114710959B (zh) | 2024-05-24 |
EP4029915A4 (en) | 2022-12-28 |
EP4029915B1 (en) | 2024-04-17 |
WO2022092512A1 (ko) | 2022-05-05 |
EP4029915A1 (en) | 2022-07-20 |
CN114710959A (zh) | 2022-07-05 |
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