JP7391197B2 - 熱可塑性樹脂組成物及びその成形品 - Google Patents
熱可塑性樹脂組成物及びその成形品 Download PDFInfo
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- JP7391197B2 JP7391197B2 JP2022518306A JP2022518306A JP7391197B2 JP 7391197 B2 JP7391197 B2 JP 7391197B2 JP 2022518306 A JP2022518306 A JP 2022518306A JP 2022518306 A JP2022518306 A JP 2022518306A JP 7391197 B2 JP7391197 B2 JP 7391197B2
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- aromatic vinyl
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- 229920000578 graft copolymer Polymers 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- -1 aromatic vinyl compound Chemical class 0.000 claims description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 32
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- 239000005060 rubber Substances 0.000 claims description 28
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- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
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- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
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- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DMFXLIFZVRXRRR-UHFFFAOYSA-N octyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O DMFXLIFZVRXRRR-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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Description
本出願は、2020年09月22日付の韓国特許出願第10-2020-0122542号及びこれに基づいて2021年05月18日付で再出願された韓国特許出願第10-2021-0064033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。
前記(A-1)グラフト共重合体のアクリレートゴムは、一例として平均粒径が50~150nm、好ましくは50~130nm、より好ましくは100~130nmであってもよく、この範囲内で、最終製造される熱可塑性樹脂組成物に優れた衝撃強度及び外観品質を付与することができる。
前記(A-2)グラフト共重合体のアクリレートゴムは、一例として平均粒径が300~600nm、好ましくは350~600nm、より好ましくは350~550nmであってもよく、この範囲内で、引張強度、伸び率及び衝撃強度などの機械的強度に優れるという効果がある。
本発明のB-1)高分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体は、好ましくは、重量平均分子量が160,000~200,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体であってもよく、より好ましくは、重量平均分子量が160,000~190,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体、さらに好ましくは、重量平均分子量が160,000~180,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体、より一層好ましくは、重量平均分子量が160,000~170,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体であり、この範囲内で、衝撃強度などの機械的強度に優れながらも、耐熱度に優れるという利点がある。
本発明のB-2)低分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体は、好ましくは、重量平均分子量が80,000g/mol以上~160,000g/mol未満である芳香族ビニル化合物-ビニルシアン化合物共重合体であってもよく、より好ましくは、重量平均分子量が80,000~110,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2a)、重量平均分子量が110,000g/mol超~110,000g/mol以下である芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2b)、及び重量平均分子量が110,000g/mol超~160,000g/mol未満である芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2c)からなる群から選択された1種以上であり、さらに好ましくは、重量平均分子量が80,000~110,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2a)、または重量平均分子量が110,000g/mol超~160,000g/mol未満である芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2c)であり、この範囲内で、200℃未満の低温で加工性に優れるので、PVC樹脂との共押出時にもフローマークやピーリングなどの表面不良が発生せず、エネルギー消費が少なくなるので経済性に優れるという利点がある。
本発明のポリアミド樹脂は、好ましくは、(A)アクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体と(B)非グラフト共重合体を合わせた総100重量部を基準として0.1~10重量部、より好ましくは1~10重量部、さらに好ましくは3~9重量部、最も好ましくは4~7重量部であり、この範囲内で、機械的物性及び低温加工性などが同等以上に維持されながらも、艶消し特性に優れるという利点がある。
本発明の無機顔料は、(A)アクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体と(B)非グラフト共重合体を合わせた総100重量部を基準として、好ましくは0.1~5重量部、より好ましくは0.1~2重量部、さらに好ましくは0.1~1重量部、より一層好ましくは0.3~0.8重量部含まれてもよく、この範囲内で、耐候性及び隠ぺい力に優れるという効果がある。
本発明の熱可塑性樹脂組成物は、好ましくは、滑剤、酸化防止剤及び紫外線安定剤を含むことができる。
本発明の熱可塑性樹脂組成物は、好ましくは、バレル温度190℃及びダイ温度200℃の条件下で押出RPMを20から60まで変化させるとき、シート成形用シングルスクリュー押出機(ダイの形態:T-Die)にかかる熱可塑性樹脂組成物の圧力傾きが130以下、より好ましくは100~130、さらに好ましくは110~130であってもよく、この範囲内で、せん断(shear)による粘度の変化が小さいため加工安定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を特徴とし、この場合、従来のASA樹脂と比較して、200℃未満の低温で加工性に優れるので、PVC樹脂との共押出時にもフローマークやピーリングなどの表面不良が発生せず、エネルギー消費量が少なく、ASA樹脂の少ない投入量でもPVC樹脂を効果的に覆うことができるので経済性に優れ、また、耐熱度も優れるという利点がある。
下記実施例1~6及び比較例1~5で用いられた物質は、次の通りである。
A-2)グラフト共重合体:アクリレートゴムの平均粒径が500nmであるブチルアクリレート-スチレン-アクリロニトリル共重合体(ブチルアクリレート50重量%、スチレン35重量%及びアクリロニトリル15重量%)
B-1)バルク重合方式のSAN樹脂(95HCP、LG化学社製、重量平均分子量91,000g/mol)
B-2)バルク重合方式のSAN樹脂(92HR、LG化学社製、重量平均分子量130,000g/mol)
B-3)バルク重合方式のSAN樹脂(90HR、LG化学社製、重量平均分子量150,000g/mol)
B-4)バルク重合方式のSAN樹脂(97HC、LG化学社製、重量平均分子量170,000g/mol)
B-5)バルク重合方式の耐熱SAN樹脂(200UH、LG化学社製、重量平均分子量90,000g/mol)
D)ナイロン66
それぞれ、下記表1に記載された成分及び含量に、滑剤としてEBS(SUNKOO社製)0.5重量部、酸化防止剤としてオクタデシル3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート(octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate)0.4重量部及びトリス(2,4-ジ-tert-ブチルフェニル)ホスファイト(Tris(2,4-di-tert-butylphenyl)phosphite))0.4重量部、紫外線安定剤としてベンゾトリアゾール系紫外線安定剤であるTinuvin329(BASF社製)0.6重量部及びHALS系紫外線安定剤であるTinuvin770(BASF社製)0.6重量部を均一に混合した後、これを二軸押出機にて280℃下で混練及び押出してペレットを製造した。また、製造されたペレットをもってバレル部の温度50、190、190、190℃及びダイ部の温度200、200、200℃でシングルスクリューTダイ押出機を用いて0.15Tのシートを製造し、光沢(gloss)及び表面粗さ値を測定した。さらに、前記製造されたペレットを成形温度220℃で射出して物性測定用試験片を作製し、これを用いて引張強度及び衝撃強度を測定した。
前記実施例1~6及び比較例1~5で製造されたペレット、シート及び試験片の特性を下記の方法で測定し、その結果を下記の表1に示した。
Claims (11)
- (A)平均粒径が50~150nmであるアクリレートゴムを含むアクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体(A-1)及び平均粒径が300~600nmであるアクリレートゴムを含むアクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体(A-2)を含む、グラフト共重合体10~70重量%と、
(B)アクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体(A)及び非グラフト共重合体(B)の総重量に対して、重量平均分子量が160,000~200,000g/molである高分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体20~55重量%(B-1)及び重量平均分子量が80,000g/mol以上~160,000g/mol未満である低分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体5~35重量%(B-2)を含む、非グラフト共重合体30~90重量%とからなる、ベース樹脂100重量部を含み、
バレル温度190℃及びダイ温度200℃の条件下で押出RPMを20から60まで変化させるとき、シート成形用シングルスクリュー押出機(Collin社製、E20T製品)にかかる熱可塑性樹脂組成物の圧力を測定したとき、RPMに対する圧力変化の対数トレンドラインから得られる圧力傾きが130以下であることを特徴とする、熱可塑性樹脂組成物であって、
(A)アクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体と(B)非グラフト共重合体を合わせた総100重量部を基準として、熱可塑性樹脂組成物は、ポリアミド樹脂0.1~10重量部を含み、
前記(A-1)グラフト共重合体と前記(A-2)グラフト共重合体の重量比は1:1.2~1:2.5であり、
前記(A-1)グラフト共重合体は、アクリレート系ゴム40~60重量%、芳香族ビニル化合物20~40重量%及びビニルシアン化合物10~20重量%を含んでなり、
前記(A-2)グラフト共重合体は、アクリレート系ゴム40~60重量%、芳香族ビニル化合物25~45重量%及びビニルシアン化合物10~20重量%を含んでなり、
前記(B-1)高分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体及び前記(B-2)低分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体は、それぞれ、芳香族ビニル化合物65~80重量%及びビニルシアン化合物20~35重量%を含んでなり、
前記(B-1)高分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体及び前記(B-2)低分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体に、それぞれ含まれる芳香族ビニル化合物は、スチレンであり、
前記低分子量の芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2)は、重量平均分子量が80,000~110,000g/molである芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2a)、又は重量平均分子量が110,000g/mol超~160,000g/mol未満である芳香族ビニル化合物-ビニルシアン化合物共重合体(B-2c)である、熱可塑性樹脂組成物。 - バレル温度190℃、ダイ温度200℃及び押出RPM50の条件下でシングルスクリューTダイ押出機のTダイ(Collin社製、E20T製品)を介して1分30秒間吐出される熱可塑性樹脂組成物の吐出量で計算される吐出速度が18g/分以上であ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。
- (A)アクリレート-芳香族ビニル化合物-ビニルシアン化合物グラフト共重合体と(B)非グラフト共重合体を合わせた総100重量部を基準として、無機顔料0.1~5重量部を含むことを特徴とする、請求項1又は2に記載の熱可塑性樹脂組成物。
- ガラス転移温度125℃以上の熱可塑性樹脂を含まないことを特徴とする、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。
- デッキング(decking)材料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。
- ASTM D648に準拠して18.6kgfの荷重下で測定した耐熱度が80℃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。
- 190℃の条件及びせん断範囲(Shear range)100/sでの毛細管粘度が2,500~3,200Pa・sであることを特徴とする、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。
- 温度条件190℃、ストレイン(Strain)条件0.1%及び周波数(Frequency)条件10rad/sでの貯蔵弾性率(ジオメトリーは25mmのパラレルプレート(Parallel Plate))が70,000~150,000MPaであることを特徴とする、請求項1~7のいずれか一項に記載の熱可塑性樹脂組成物。
- 熱可塑性樹脂組成物のペレットを、バレル部の温度制御区域の温度が順に50、190、190、190℃及びダイ部の温度制御区域の温度が順に200、200、200℃でシングルスクリューTダイ押出機(Collin社製、E20T製品)を用いて作製した0.15Tのシートの非対称度Rsk(200℃)が0~0.5であり、熱可塑性樹脂組成物のペレットを、バレル部の温度制御区域の温度が順に50、200、210、210℃及びダイ部の温度制御区域の温度が順に220、220、230℃でシングルスクリューTダイ押出機(Collin社製、E20T製品)を用いて作製した0.15Tのシートの非対称度Rsk(220℃)が0.65~1.35であることを特徴とする、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。
- 熱可塑性樹脂組成物のペレットを、バレル部の温度制御区域の温度が順に50、190、190、190℃及びダイ部の温度制御区域の温度が順に200、200、200℃でシングルスクリューTダイ押出機(Collin社製、E20T製品)を用いて作製した0.15Tのシートの60°で測定したフィルムグロス(film gloss)の値が15以下である艶消し熱可塑性樹脂組成物であることを特徴とする、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。
- 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を含むことを特徴とする、成形品。
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