KR100711421B1 - 물과 장기간 접촉하는 열가소성 중합체용 상승적 안정화제조성물 - Google Patents
물과 장기간 접촉하는 열가소성 중합체용 상승적 안정화제조성물 Download PDFInfo
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- KR100711421B1 KR100711421B1 KR1020027008723A KR20027008723A KR100711421B1 KR 100711421 B1 KR100711421 B1 KR 100711421B1 KR 1020027008723 A KR1020027008723 A KR 1020027008723A KR 20027008723 A KR20027008723 A KR 20027008723A KR 100711421 B1 KR100711421 B1 KR 100711421B1
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- Prior art keywords
- bis
- butyl
- hydroxy
- methyl
- component
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- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
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- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 장애 아민 안정화제(HAS), 페놀계 항산화제, 및 필요에 따라 자외선 흡수제를 포함하는, 열가소성 중합체, 특히 물과 장기간 접촉하는 폴리올레핀 파이프 및 기타 폴리올레핀 성형 물질용 상승적 안정화제 조성물에 관한 것이다. 본 발명의 혼합물은 산화 유도 시간(OIT)과 같은 표준 시험 방법으로 측정할 때 우수한 장기간 성능을 보인다.
Description
본 발명은 장애(hindered) 아민 안정화제(HAS), 페놀계 항산화제, 및 필요에 따라 자외선 흡수제를 포함하는, 열가소성 중합체, 특히 물과 장기간 접촉하는 폴리올레핀 파이프 및 기타 폴리올레핀 성형 물질용 상승적 안정화제 조성물에 관한 것이다.
열가소성 중합체, 특히 흔히 부분적으로 가교된 폴리올레핀 파이프, 토목섬유(geotextile), 및 기타 물과 장기간 접촉하는 성형 물질의 유용성 및 수명은 중합체의 기계적 특성, 밀도, 몰질량 및 질량 분포와 같은 수많은 매개변수에 의해 영향을 받는다. 최종적 사용처 및 사용중 특이적 조건(온도, 응력 및 환경 영향)에 따라, 수십년까지의 수명이 보장되어야 한다. 기대 수명에 대한 새로운 추세는 50년 이상이다. 수상 운송에 사용되는 경우에는 적절한 안정화제의 첨가 및 안정화제 조건에 의해 달성될 수 있는 특정의 요건이 충족되어야 한다. 고온수 저장에 의한 상승된 온도에서의 가속 시험 조건하에서 그 기여도를 결정할 수 있다. 중요한 기술적 지표로서 산화 유도 시간(OIT) 및 기계적 안정성을 이용하여 폴리올레핀 파이프 또는 기타 폴리올레핀계 성형 물질의 안정화를 평가한다. OIT 측정은, OIT-데이터의 보외법이 통상의 오븐 노화 결과에 비하여 지나치게 낙관적이어서 오랫동안 논란이 되고 있다는 사실에도 불구하고 여전히 기술적으로 중요한 지표로서 확립되어 널리 사용되고 있다. 중합체 기질에의 영향, 예를 들면 결정성, 자유 부피, 형태학 및 확산 계수와 반응 동력학의 변화는 분해 메카니즘에서 변화를 일으킨다. 그럼에도 불구하고, 특히 PE-MD- 및 PE-HD-섹터에서 210℃에서 30분 이상의 OIT-제한이 요구된다. 소정의 기술적 요건을 충족시켜야 하는 또 다른 기술적 지표는 황색 지수(YI)로서 측정되는 색상이다. 물과의 접촉에 사용되는 수지의 품질을 판정하는 추가의 기술적 지표는 함유된 수지의 생산자 및 완성 제품의 제조자의 표준 시험 프로그램의 일부인 고온수 저장(95℃)후 잔류 안정화제 함량이다.
하기 공개 문헌들에 전술한 문제들에 관하여 기술되어 있다:
1) Higuchi, Y.; Nishimura, H.; Tamamura, H.; Harada, T. Osaka Gas Co., Ltd., Japan. Proc. Int. Gas Res. Conf. (1998), (Vol. 3), 67-75; 및
2) Advanced extraction resistant long-term thermal stabilizers for polyolefin pipes. Schmutz, Th.; Kramer, E.; Zweifel, H.; Dorner, G. Ciba Specialty Chemicals, Inc., Basel, Switz. J. Elastomers Plast. (1998), 30(1), 55-67.
열가소성 중합체의 급속한 산화성 분해를 방지하는 결정적인 지표중 하나는 장기간 안정화제의 사용이다. 그 효능은 파이프 수지에서 상용성, 용해도, 이동도 및 첨가제의 이동(migration)에 따라 좌우된다.
폴리올레핀 파이프 및 기타 폴리올레핀 성형 물질과 같은 열가소성 물질의 우수한 장기간 열 안정성은 입체 장애 페놀 또는 피페리딘계 입체 장애 아민 안정화제(HAS)를 사용하여 달성될 수 있다(문헌[F. Gugumus, Polym. Degrad. Stab. 44, 299, (1994)] 참조). 또한 상기 두가지 유형의 안정화제의 조합도 사용되므로 이들은 근본적으로 최신의 기술 수준이다. 페놀계 항산화제의 아인산염과의 조합이 문헌[H. Zweifel in "Stabilization of Polymeric Materials", Springer, Berlin, Heidelberg, New York, 1998, p. 71-75]에 기술되어 있다. 독일 특허 공개 제 196 37 181 호에는 페놀계 항산화제, 입체 장애 아민 및 유기 아인산염 또는 포스포나이트(phosphonite)의 안정화 혼합물이 개시되어 있다.
앞에서 이미 지적한 바와 같이, 시스템의 장기간 안정성과 관련하여 추출 매질(extracting media)과 장기간 접촉하는 중합체 기재에 사용되는 안정화제 시스템을 개선시킬 소정의 기술적 필요성이 상존하고 있다(이동, 가수분해에 대한 안정성 등의 문제).
본 발명자들은 특정의 페놀계 안정화제와 소정의 장애 아민 안정화제의 적절한 조합물을 사용함으로써 고온수 저장후 물 추출 조건하에서 사용되는 폴리올레핀 파이프 및 일반적으로 폴리올레핀계 성형물에서 우수한 장기간 열 안정성을 달성할 수 있음을 발견하였다.
또한 특정의 페놀 성분과 통상의 입체 장애 페놀 및 소정의 입체 장애 아민의 다중 조합물도 우수한 효과를 나타낸다. 본 발명의 안정화제 조합물은 놀랍게도 최신의 기술 수준을 능가하는 가능성을 제공한다.
본 발명의 목적은
(a) 에피클로르히드린과 2,2,4,4-테트라메틸-7-옥사-3,20-디아자-20-(2,3-에폭시-프로필)-디스피로-[5.1.11.2]-헤네이코산-21-온의 중합체(LS1)를 필수적으로 포함하는 1종 이상의 입체 장애 아민; 및
(b) 1종 이상의 페놀계 항산화제를 포함하고,
상기 성분 (a)의 총중량비 대 상기 성분 (b)의 총중량비가 10:1 내지 1:5인, 열가소성 중합체용 안정화제 조성물을 제공하는 것이다.
상기 입체 장애 아민은 폴리-{[6-[1,1,3,3-테트라메틸부틸)-이미노]-1,3,5-트리아진-2,4-디일][2-(2,2,6,6-테트라메틸피페리딜)-아미노]-헥사메틸렌-[4-(2,2,6,6-테트라메틸피페리딜)-이미노]}(LS2) 또는 폴리-(N-하이드록시에틸-2,2,6,6-테트라메틸-4-하이드록시-피페리딜-숙시네이수)(LS3)을 추가적으로 포함할 수 있다.
상기 입체 장애 아민은 폴리-{[6-[1,1,3,3-테트라메틸부틸)-이미노]-1,3,5-트리아진-2,4-디일][2-(2,2,6,6-테트라메틸피페리딜)-아미노]-헥사메틸렌-[4-(2,2,6,6-테트라메틸피페리딜)-이미노]}(LS2) 또는 폴리-(N-하이드록시에틸-2,2,6,6-테트라메틸-4-하이드록시-피페리딜-숙시네이수)(LS3)을 추가적으로 포함할 수 있다.
상기 안정화제 조성물에서 바람직하게는 성분 (b)가 하기 화합물 (AO1) 내지 (AO8)로 구성된 군에서 선택된다:
비스-[3,3-비스-(4'-하이드록시-3'-t-부틸페닐)-부탄산]-글리콜에스테르(AO1);
테트라키스메틸렌(3,5-디-t-부틸-4-하이드록시페닐)-하이드로신나메이트(AO2);
옥타데실-3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트(AO3);
4,4',4"-[(2,4,6-트리메틸-1,3,5-벤젠트리일)트리스(메틸렌)]-트리스[2,6-비스(1,1-디메틸에틸)페놀](AO4);
1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 1,3,5-트리스[[4-(1,1-디메틸에틸)-3-하이드록시-2,6-디메틸페닐]메틸](AO5);
페놀, 4,4,',4"-(1-메틸-1-프로파닐-3-일리덴)트리스[2-(1,1-디메틸에틸)-5-메틸(AO6);
페놀, 2,6-비스[[3-(1,1-디메틸에틸)-2-하이드록시-5-메틸페닐]옥타하이드로-4,7-메타노-1H-인데닐]-4-메틸(AO7); 및
벤젠프로판산, 3-(1,1-디메틸에틸)-4-하이드록시-5-메틸-2,4,8,10-테트라옥사스피로[5.5]운데칸-3,9-디일비스(2,2-디메틸-2,1-에탄디일)에스테르(AO8).
또한, 성분 (b)가 화합물 (AO1), (AO2), (AO3) 및 이들의 혼합물로 구성된 군에서 선택된 안정화제 조성물이 바람직하고, 성분 (b)가 중량비 5:1 내지 1:5, 더욱 바람직하게는 2:1 내지 1:2의 화합물 (AO1)과 (AO2)의 혼합물인 안정화제 조성물이 특히 바람직하다.
또한, 추가의 성분 (c)로서 메탄온, [2-하이드록시-4-(옥틸옥시)페닐]페닐(UV1); 페놀, 2-(5-클로로-2H-벤조트리아졸-2-일)-6-(1,1-디메틸에틸)-4-메틸(UV2); 및 2-하이드록시벤조페논, 2-(2-하이드록시페닐)-벤조트리아졸, 2-(2-하이드록시페닐)-1,3,5-벤조트리아진, 옥사닐리드, 신나메이트 및 살리실레이트로 구성된 군에서 선택된 자외선 흡수제를 포함하고,
이 때, 성분 (a):성분 (b):성분 (c)의 중량비가 5:1:1 내지 1:5:5인 안정화제 조성물에 의해 매우 우수한 안정화 특성을 달성할 수 있다.
화합물 (LS1) 내지 (LS3), (AO1) 내지 (AO8) 및 (UV1) 내지 (UV2)는 하기 화학식을 갖는 공지의 시판 물질이다:
본 발명의 추가의 목적은 물과 같은 추출 매질과 장기간 접촉하는 열가소성 중합체, 특히 폴리올레핀의 안정화용 안정화제 조성물을, 중합체를 기준으로 0.001 내지 2.000중량%, 바람직하게는 0.020 내지 0.20중량%의 농도로 사용하는 방법을 제공하는 것이다.
본 발명의 다른 목적은 물과 같은 추출 매질과 장기간 접촉하는 열가소성 중합체, 특히 폴리올레핀에, 중합체를 기준으로 0.001 내지 2.000중량%, 바람직하게는 0.020 내지 0.20중량%의 안정화제 조성물을 혼입시킴으로써 상기 열가소성 중합체를 안정화시키는 방법을 제공하는 것이다.
본 발명에 따라 안정화되는 적합한 열가소성 중합체의 예로는 하기 중합체들이 포함된다:
(1) 모노올레핀 및 디올레핀의 중합체, 예를 들면 폴리프로필렌, 폴리이소부틸렌, 폴리부트-1-엔, 폴리-4-메틸펜트-1-엔, 폴리이소프렌 또는 폴리부타디엔; 사이클로올레핀의 중합체, 예를 들면 사이클로펜텐 또는 노보르넨; 및 선택적으로 가교될 수 있는 폴리에틸렌, 예를 들면 고밀도 폴리에틸렌(HDPE), 고밀도 및 고몰질량의 폴리에틸렌(HDPE-HMW), 고밀도 및 초고몰질량의 폴리에틸렌(HDPE-UHMW), 중밀도 폴리에틸렌(MDPE), 저밀도 폴리에틸렌(LDPE), 선형 저밀도 폴리에틸렌(LLDPE) 및 분지형 저밀도 폴리에틸렌(BLDPE).
폴리올레핀, 즉 전 단락에 예시된 바와 같은 모노올레핀의 중합체, 특히 폴리에틸렌 및 폴리프로필렌은 다양한 방법에 의해, 특히 하기의 방법에 의해서 제조될 수 있다:
(a) 통상적으로 고압 및 승온하에서의 유리-라디칼 중합, 또는
(b) 통상적으로 주기율표의 제 IVb, Vb, VIb 또는 VIII 족의 하나 이상의 금속을 함유하는 촉매를 사용한 촉매성 중합. 이들 금속은 통상적으로 π- 또는 σ-배위된 산화물, 할로겐화물, 알코올레이트, 에스테르, 에테르, 아민, 알킬, 알케닐 및/또는 아릴과 같은 하나 이상의 리간드를 갖는다. 이들 금속 착체는 유리된 형태이거나 활성화된 염화마그네슘, 염화 티탄(III), 알루미나 또는 산화 규소와 같은 기질 상에 고정될 수 있다. 이들 촉매는 중합 매질에 가용성 또는 불용성일 수 있다. 촉매가 중합시 자체적으로 활성적이거나, 또는, 추가의 활성화제로, 예를 들면 금속 알킬, 금속 수화물, 금속 알킬 할로겐화물, 금속 알킬 산화물 또는 금속 알킬록산, 주기율표의 제 Ia, IIa 및/또는 IIIa 족의 금속 원소를 사용할 수 있다. 활성화제는, 예를 들면 추가의 에스테르, 에테르, 아민 또는 실릴 에테르 기로 개질될 수 있다. 이들 촉매 시스템은 소위 필립스(Phillips), 스탠다드 오일 인디애나(Standard Oil Indiana), 지글러(-나타)(Ziegler(-Natta)), TNZ(듀퐁(Dupont)), 메탈로센 또는 단일 부위 촉매(SSC; single site catalysts)로 지칭된다.
(2) 상기 (1)에서 언급된 중합체의 혼합물, 예를 들면 폴리프로필렌과 폴리이소부틸렌의 혼합물, 폴리에틸렌과 폴리이소부틸렌의 혼합물, 폴리프로필렌과 폴리에틸렌의 혼합물(예를 들면, PP/HDPE/LDPE) 및 기타 유형의 폴리에틸렌(예를 들면, LDPE/HDPE)의 상호간의 혼합물.
(3) 모노올레핀과 디올레핀의 상호간의 또는 다른 비닐 단량체와의 공중합체, 예를 들면 에틸렌-프로필렌 공중합체, 선형 저밀도 폴리에틸렌(LLDPE) 및 이와 저밀도 폴리에틸렌(LDPE)의 혼합물, 프로필렌-부트-1-엔 공중합체, 프로필렌-이소부틸렌 공중합체, 에틸렌-부트-1-엔 공중합체, 에틸렌-헥센 공중합체, 에틸렌-메틸펜텐 공중합체, 에틸렌-헵텐 공중합체, 에틸렌-옥텐 공중합체, 프로필렌-부타디엔 공중합체, 이소부틸렌-이소프렌 공중합체, 에틸렌-알킬 아크릴레이트 공중합체, 에틸렌-알킬 메트아크릴레이트 공중합체, 에틸렌-비닐 아세테이트 공중합체 및 이들의 일산화탄소와의 공중합체; 에틸렌-아크릴산 공중합체 및 이의 염(이오노머); 에틸렌과 프로필렌 및 헥사디엔, 디사이클로펜타디엔 또는 에틸리덴-노보르넨과 같은 디엔과의 3원공중합체; 및 이러한 공중합체 상호간의 및 상기 (1)에 기술된 중합체간의 혼합물, 예를 들면 폴리프로필렌-에틸렌-프로필렌 공중합체, LDPE-에틸렌-비닐 아세테이트 공중합체, LDPE-에틸렌-아크릴산 공중합체, LLDPE-에 틸렌-비닐 아세테이트 공중합체, LLDPE-에틸렌-아크릴산 공중합체 및 교대 및 랜덤 폴리알킬렌-일산화탄소 공중합체 및 이들의 다른 중합체와의 혼합물, 예를 들면 폴리아미드.
(4) 탄화수소 수지의 수소화 개질물(예를 들면, 점착성 수지) 및 폴리알킬렌과 전분의 혼합물을 포함하는 탄화수소 수지(예를 들면, C5-C9).
(5) 폴리스티렌,
폴리(p-메틸스티렌) 및 폴리(α-메틸스티렌).
(6) 스티렌 또는 α-메틸스티렌과 디엔 또는 아크릴 유도체의 공중합체, 예를 들면 스티렌-부타디엔, 스티렌-아크릴로니트릴, 스티렌-알킬 메트아크릴레이트, 스티렌-부타디엔-알킬 아크릴레이트, 스티렌-부타디엔-알킬 메트아크릴레이트, 스티렌-말레산 무수물 및 스티렌-아크릴로니트릴-메트아크릴레이트; 고충격 강도의 스티렌 공중합체와 다른 중합체의 혼합물, 예를 들면 폴리아크릴레이트, 디엔 중합체 또는 에틸렌-프로필렌-디엔 3원공중합체; 및 스티렌-부타디엔-스티렌, 스티렌-이소프렌-스티렌, 스티렌-에틸렌/부틸렌-스티렌 또는 스티렌-에틸렌/프로필렌-스티렌과 같은 스티렌의 블록 공중합체.
(7) 스티렌 또는 α-메틸스티렌의 그라프트 공중합체, 예를 들면 폴리부타디엔 상의 스티렌, 폴리부타디엔-스티렌 또는 폴리부타디엔-아크릴로니트릴 공중합체 상의 스티렌, 및 폴리부타디엔 상의 스티렌 및 아크릴로니트릴(또는 메트아크릴로니트릴); 폴리부타디엔 상의 스티렌, 아크릴로니트릴 및 메틸 메트아크릴레이트; 폴리부타디엔 상의 스티렌 및 말레산 무수물; 폴리부타디엔 상의 스티렌, 아크릴로니트 릴 및 말레산 무수물 또는 말레이미드; 폴리부타디엔 상의 스티렌 및 말레이미드; 폴리부타디엔 상의 스티렌 및 알킬 아크릴레이트 또는 알킬 메트아크릴레이트, 에틸렌-프로필렌-디엔 3원공중합체상의 스티렌 및 아크릴로니트릴, 폴리알킬 아크릴레이트 또는 폴리알킬 메트아크릴레이트 상의 스티렌 및 아크릴로니트릴, 아크릴레이트-부타디엔 공중합체 상의 스티렌 및 아크릴로니트릴; 및 이들과 상기 (6)에 언급된 공중합체와의 혼합물, 예를 들면, ABS, MBS, ASA 또는 AES 중합체로 공지된 공중합체 혼합물.
(8) 할로겐-함유 중합체, 예를 들면 폴리클로로프렌, 염소화 고무, 이소부틸렌-이소프렌의 염소화 및 브롬화 공중합체(할로부틸 고무), 염소화 또는 황염소화 폴리에틸렌, 에틸렌 및 염소화된 에틸렌의 공중합체, 에피클로하이드린 동종 및 공중합체, 특히 할로겐-함유 비닐 화합물의 중합체, 예를 들면 염화 폴리비닐, 염화 폴리비닐리덴, 불화 폴리비닐, 불화 폴리비닐리덴, 및 염화 비닐-염화 비닐리덴, 염화 비닐-비닐 아세테이트 또는 염화 비닐리덴-비닐 아세테이트와 같은 이들의 공중합체.
(9) α,β-불포화산 및 그의 유도체로부터 유도된 중합체, 예를 들면 폴리아크릴레이트 및 폴리메트아크릴레이트, 폴리아크릴로니트릴, 폴리아크릴아미드 및 부틸 아크릴레이트로 충격-개질된 폴리메틸 메트아크릴레이트.
(10) 상기 (9)에 언급된 단량체 상호간의 또는 다른 불포화된 단량체와의 공중합체, 예를 들면 아크릴로니트릴-부타디엔 공중합체, 아크릴로니트릴-알킬 아크릴레이트 공중합체, 아크릴로니트릴-알콕시알킬 아크릴레이트 공중합체, 아크릴로니트 릴-비닐 할로겐화물 공중합체 또는 아크릴로니트릴-알킬 메트아크릴레이트-부타디엔 3원공중합체.
(11) 불포화된 알코올 및 아민, 이들의 아실 유도체 또는 아세탈로부터 유도된 중합체, 예를 들면 폴리비닐 알코올, 폴리비닐 아세테이트, 폴리비닐 스테아레이트, 폴리비닐 벤조에이트, 폴리비닐 말리에이트, 폴리비닐 부티랄, 폴리알릴 프탈레이트 또는 폴리알릴 멜라민; 및 이들과 상기 (1)에 언급된 올레핀과의 공중합체.
(12) 사이클릭 에테르의 동종중합체 및 공중합체, 예를 들면 폴리알킬렌 글리콜, 폴리에틸렌 산화물, 폴리프로필렌 산화물 또는 이들과 비스글리시딜 에테르와의 공중합체.
(13) 폴리옥시메틸렌 및 공단량체, 예를 들면 에틸렌 산화물을 함유하는 폴리옥시메틸렌과 같은 폴리아세탈; 및 열가소성 폴리우레탄, 아크릴레이트 또는 MBS로 개질된 폴리아세탈.
(14) 폴리페닐렌 산화물 및 황화물, 및 이들과 스티렌 중합체 또는 폴리아미드와의 혼합물.
(15) 한편으로 하이드록실-종결된 폴리에테르, 폴리에스테르 및 폴리부타디엔, 다른 한편으로 지방족 또는 방향족 폴리이소시아네이트로부터 유도된 폴리우레탄 및 이의 전구체.
(16) 디아민 및 디카복실산 및/또는 아미노카복실산 또는 상응하는 락탐으로부터 유도된 폴리아미드 및 공중합 폴리아미드, 예를 들면 폴리아미드 4, 6, 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, 11 및 12, 및 m-크실렌, 디아민 및 지방산으로부터 개시된 방향족 폴리아미드; 개질제로서 엘라스토머를 함유하거나 함유하지 않는, 헥사메틸렌디아민 및 이소프탈린 및/또는 테레프탈산으로부터 제조된 폴리아미드, 예를 들면 폴리-2,4,4-트리메틸헥사메틸렌 테레프탈아미드 또는 폴리-m-페닐렌 이소프탈아미드. 전술한 폴리아미드의 폴리올레핀, 올레핀 공중합체, 이오노머 또는 화학적으로 결합되거나 그라프트된 엘라스토머와의 또는 폴리에테르, 예를 들면 폴리에틸렌 글리콜, 폴리프로필렌 글리콜 또는 폴리테트라메틸렌 글리콜과의 블록 공중합체. EPDM 또는 ABS로 개질된 폴리아미드 또는 공중합 폴리아미드 및 가공중 축합된 폴리아미드(RIM 폴리아미드계).
(17) 폴리우레아, 폴리이미드, 폴리아미드-이미드, 폴리에테르 이미드, 폴리에스테르 아미드, 폴리히단토인 및 폴리벤즈이미다졸.
(18) 디카복실산 및 디알코올 및/또는 하이드록시카복실산 또는 상응하는 락톤으로부터 유도된 폴리에스테르, 예를 들면 폴리에틸렌 테레프탈레이트, 폴리부틸렌 테레프탈레이트, 폴리-1,4-디메틸올사이클로헥산 테레프탈레이트, 폴리하이드록시벤조에이트; 하이드록실-종결된 폴리에테르로부터 유도된 블록 폴리에테르 에스테르; 및 폴리카보네이트 또는 MBS로 개질된 폴리에스테르.
(19) 폴리카보네이트 및 폴리에스테르 카보네이트.
(20) 폴리설폰, 폴리에테르 설폰 및 폴리에테르 케톤.
(21) 한편으로는 알데히드 및 다른 한편으로 페놀, 우레아 또는 멜라민으로부터 유도된 가교된 중합체, 예를 들면 페놀/포름알데히드 수지, 우레아/포름알데히드 수지 및 멜라민/포름알데히드 수지.
(22) 건조 및 비건조 알키드 수지.
(23) 포화 또는 불포화 디카복실산의 다가 알코올 및 가교결합제로서 비닐 화합물과의 공중합 폴리에스테르로부터 유도된 불포화 폴리에스테르 수지 및 낮은 인화성을 갖는 이들의 할로겐-함유 개질물.
(24) 치환 아크릴레이트, 예를 들면 에폭시 아크릴레이트, 우레탄 아크릴레이트 또는 폴리에스테르 아크릴레이트로부터 유도된 가교성 아크릴 수지.
(25) 멜라민 수지, 우레아 수지, 이소시아네이트, 이소시아누레이트, 폴리이소시아네이트 또는 에폭시 수지와 가교된 알키드 수지, 폴리에스테르 수지 및 아크릴 수지.
(26) 지방족, 지환족, 헤테로환족 또는 방향족 글리시딜 화합물로부터 유도된 가교 에폭시 수지, 예를 들면 촉진제의 존재하에 또는 부재하에 무수물 또는 아민과 같은 통상적인 경화제로 가교된 비스페놀 A 디글리시딜 에테르 또는 비스페놀 F 디글리시딜 에테르의 생성물.
(27) 중합체와 유사한 방식으로 화학적 개질된 셀룰로즈, 천연 고무, 젤라틴 및 이의 유도체와 같은 천연 중합체, 예를 들면 셀룰로즈 아세테이트, 셀룰로즈 프로피오네이트 및 셀룰로즈 부티레이트; 메틸 셀룰로즈와 같은 셀룰로즈 에테르; 및 로진 및 이의 유도체.
(28) 전술한 중합체의 혼합물(폴리블렌드), 예를 들면 PP/EPDM, 폴리아미드/EPDM 또는 ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/아크릴레이트, POM/열가소성 PUR, PC/열가소성 PUR, POM/아크릴레이 트, POM/MBS, PPO/MBS, PPO/HIPS, PPO/PA 6.6 및 공중합체, PA/HDPE, PA/PP, PA/PPO, PBT/ABS 또는 PBT/PET/PC.
(29) 순수한 단량체 화합물 또는 이의 혼합물을 구성하는 천연 및 합성 유기 물질, 예를 들면 광유, 동물성 또는 식물성 지방, 오일 및 왁스 또는 합성 에스테르(예를 들면, 프탈레이트, 아디페이트, 포스페이트 또는 트리멜리테이트)에 기초한 오일, 왁스 및 지방; 및, 합성 에스테르와, 예를 들면 회전 마감제로 사용된 임의의 바람직한 중량비의 광유와의 블렌드 및 이의 수성 유화액.
(30) 천연 또는 합성 고무의 수성 유화액, 예를 들면 천연 고무 라텍스 및 카복실화 스티렌-부타디엔 공중합체의 라텍스.
본 발명의 안정화제 조성물 또는 안정화되는 열가소성 중합체는 필요시 추가의 첨가제, 예를 들면 항산화제, 광 안정화제, 금속 불활성화제, 정전기 방지제, 난연제, 윤활제, 증핵제, 산 소거제(염기성 조안정화제), 안료 및 충전제를 또한 포함할 수 있다. 조합되어 추가로 사용될 수 있는 적합한 첨가제의 예로는 하기의 화합물들이 포함된다:
1. 항산화제
1.1. 알킬화 모노페놀, 예를 들면 2,6-디-t-부틸-4-메틸페놀, 2-부틸-4,6-디메틸페놀, 2,6-디-t-부틸-4-에틸페놀, 2,6-디-t-부틸-4-n-부틸페놀, 2,6-디-t-부틸-4-이소부틸페놀, 2,6-디사이클로펜틸-4-메틸페놀, 2-(α-메틸사이클로헥실)-4,6-디메틸페놀, 2,6-디옥타데실-4-메틸페놀, 2,4,6-트리사이클로헥실페놀, 2,6-디-t-부틸-4-메톡시메틸페놀; 선형 또는 측쇄-분지형 노닐페놀, 예를 들면 2,6-디-노닐-4-메 틸페놀, 2,4-디메틸-6-(1-메틸운데스-1'-일)페놀, 2,4-디메틸-6-(1'-메틸헵타데스-1'-일)페놀, 2,4-디메틸-6-(1'-메틸트리데크-1'-일)페놀; 및 이들의 혼합물.
1.2. 알킬티오메틸페놀, 예를 들면 2,4-디옥틸티오메틸-6-t-부틸페놀, 2,4-디옥틸티오메틸-6-메틸페놀, 2,4-디옥틸티오메틸-6-에틸페놀 및 2,6-디도데실티오메틸-4-노닐페놀.
1.3. 하이드로퀴논 및 알킬화 하이드로퀴논, 예를 들면 2,6-디-t-부틸-4-메톡시페놀, 2,5-디-t-부틸하이드로퀴논, 2,5-디-t-아밀하이드로퀴논, 2,6-디페닐-4-옥타데실옥시페놀, 2,6-디-t-부틸하이드로퀴논, 2,5-디-t-부틸-4-하이드록시아니솔, 3,5-디-t-부틸-4-하이드록시아니솔, 3,5-디-t-부틸-4-하이드록시페닐 스테아레이트 및 비스(3,5-디-t-부틸-4-하이드록시페닐)아디페이트.
1.4. 하이드록실화 티오디페닐 에테르, 예를 들면 2,2'-티오비스(6-t-부틸-4-메틸페놀), 2,2'-티오비스(4-옥틸페놀), 4,4'-티오비스(6-t-부틸-3-메틸페놀), 4,4'-티오비스(6-t-부틸-2-메틸페놀), 4,4'-티오비스(3,6-디-sec-아밀페놀) 및 4,4'-비스(2,6-디메틸-4-하이드록시페닐)디설피드.
1.5. 알킬리덴비스페놀, 예를 들면 2,2'-메틸렌비스(6-t-부틸-4-메틸페놀), 2,2'-메틸렌비스(6-t-부틸-4-에틸페놀), 2,2'-메틸렌비스[4-메틸-6-(α-메틸사이클로헥실)페놀], 2,2'-메틸렌비스(4-메틸-6-사이클로헥실페놀), 2,2'-메틸렌비스(6-노닐-4-메틸페놀), 2,2'-메틸렌비스(4,6-디-t-부틸페놀), 2,2'-에틸리덴비스 (4,6-디-t-부틸페놀), 2,2'-에틸리덴비스(6-t-부틸-4-이소부틸페놀), 2,2'-메틸렌비스[6-(α-메틸벤질)-4-노닐페놀], 2,2'-메틸렌비스[6-(α,α-디메틸벤질)-4-노닐페놀], 4,4'-메틸렌비스(2,6-디-t-부틸페놀), 4,4'-메틸렌비스(6-t-부틸-2-메틸페놀), 1,1-비스(5-t-부틸-4-하이드록시-2-메틸페닐)부탄, 2,6-비스(3-t-부틸-5-메틸-2-하이드록시벤질)-4-메틸페놀, 1,1,3-트리스(5-t-부틸-4-하이드록시-2-메틸페닐)부탄, 1,1-비스(5-t-부틸-4-하이드록시-2-메틸페닐)-3-n-도데실머캅토부탄, 비스(3-t-부틸-4-하이드록시-5-메틸페닐)-디사이클로펜타디엔, 비스[2-(3'-t-부틸-2'-하이드록시-5'-메틸벤질)-6-t-부틸-4-메틸페닐]테레프탈레이트, 1,1-비스(3,5-디메틸-2-하이드록시페닐)부탄, 2,2-비스(3,5-디-t-부틸-4-하이드록시페닐)프로판, 2,2-비스(5-t-부틸-4-하이드록시-2-메틸페닐)-4-n-도데실머캅토부탄, 1,1,5,5-테트라-(5-t-부틸-4-하이드록시-2-메틸페닐)펜탄 및 에틸렌 글리콜 비스[3,3-비스(3'-t-부틸-4'-하이드록시페닐)부티레이트].
1.6. O-, N- 및 S-벤질 화합물, 예를 들면 3,5,3', 5'-테트라-t-부틸-4,4'-디하이드록시디벤질 에테르, 옥타데실 4-하이드록시-3,5-디메틸벤질머캅토아세테이트, 트리스(3,5-디-t-부틸-4-하이드록시벤질)아민, 비스(4-t-부틸-3-하이드록시-2,6-디메틸벤질)디티오테레프탈레이트, 비스(3,5-디-t-부틸-4-하이드록시벤질)설피드, 이소옥틸 3,5-디-t-부틸-4-하이드록시벤질머캅토아세테이트, 및 트리데실 4-하이드록시-3,5-디-t-부틸벤질머캅토아세테이트.
1.7. 하이드록시벤질화 말로네이트, 예를 들면 디옥타데실 2,2-비스(3,5-디-t-부틸-2-하이드록시벤질)말로네이트, 디옥타데실 2-(3-t-부틸-4-하이드록시-5-메틸벤질)말로네이트, 디도데실 머캅토에틸-2,2-비스(3,5-디-t-부틸-4-하이드록시벤질)말로네이트 및 디-[4-(1,1,3,3-테트라메틸부틸)페닐]2,2-비스(3,5-디-t-부틸-4-하이 드록시벤질)말로네이트.
1.8. 방향족 하이드록시벤질 화합물, 예를 들면 1,3,5-트리스(3,5-디-t-부틸-4-하이드록시벤질)-2,4,6-트리메틸벤젠, 1,4-비스(3,5-디-t-부틸-4-하이드록시벤질)-2,3,5,6-테트라메틸벤젠 및 2,4,6-트리스(3,5-디-t-부틸-4-하이드록시벤질)페놀.
1.9. 트리아진 화합물, 예를 들면 2,4-비스옥틸머캅토-6-(3,5-디-t-부틸-4-하이드록시아닐리노)-1,3,5-트리아진, 2-옥틸머캅토-4,6-비스(3,5-디-t-부틸-4-하이드록시아닐리노)-1,3,5-트리아진, 2-옥틸머캅토-4,6-비스(3,5-디-t-부틸-4-하이드록시페녹시)-1,3,5-트리아진, 2,4,6-트리스(3,5-디-t-부틸-4-하이디록시페녹시)-1,2,3-트리아진, 1,3,5-트리스(3,5-디-t-부틸-4-하이드록시벤질)이소시아누레이트, 1,3,5-트리스(4-t-부틸-3-하이드록시-2,6-디메틸벤질)이소시아누레이트, 2,4,6-트리스(3,5-디-t-부틸-4-하이드록시페닐에틸)-1,3,5-트리아진, 1,3,5-트리스(3,5-디-t-부틸-4-하이드록시페닐프로피오닐)헥사하이드로-1,3,5-트리아진 및 1,3,5-트리스(3,5-디사이클로헥실-4-하이드록시벤질)이소시아누레이트.
1.10. 벤질포스포네이트, 예를 들면 디메틸 2,5-디-t-부틸-4-하이드록시벤질포스포네이트, 디에틸 3,5-디-t-부틸-4-하이드록시벤질포스포네이트, 디옥타데실 3,5-디-t-부틸-4-하이드록시벤질포스포네이트, 디옥타데실 5-t-부틸-4-하이드록시-3-메틸벤질포스포네이트, 및 3,5-디-t-부틸-4-하이드록시벤질포스폰산의 모노에틸 에스테르의 Ca 염.
1.11. 아실아미노페놀, 예를 들면 4-하이드록시라우르아닐리드, 4-하이드록시스테아르아닐리드 및 옥틸 N-(3,5-디-t-부틸-4-하이드록시페닐)카바메이트.
1.12. β-(3,5-디-t-부틸-4-하이드록시페닐)프로피온산과 일가 또는 다가 알코올, 예를 들면 메탄올, 에탄올, n-옥탄올, 이소옥탄올, 옥타데카놀, 1,6-헥산디올, 1,9-노난디올, 에틸렌 글리콜, 1,2-프로판디올, 네오펜틸 글리콜, 티오디에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 펜타에리트리톨, 트리스(하이드록시에틸) 이소시아누레이트, N,N'-비스(하이드록시에틸)옥살아미드, 3-티아운데카놀, 3-티아펜타데카놀, 트리메틸헥산디올, 트리메틸올프로판 또는 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과의 에스테르.
1.13. β-(5-t-부틸-4-하이드록시-3-메틸페닐)프로피온산과 일가 또는 다가 알코올, 예를 들면 메탄올, 에탄올, n-옥탄올, 이소옥탄올, 옥타데카놀, 1,6-헥산디올, 1,9-노난디올, 에틸렌 글리콜, 1,2-프로판디올, 네오펜틸 글리콜, 티오디에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 펜타에리트리톨, 트리스(하이드록시에틸) 이소시아누레이트, N,N'-비스(하이드록시에틸)옥살아미드, 3-티아운데카놀, 3-티아펜타데카놀, 트리메틸헥산디올, 트리메틸올프로판 또는 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과의 에스테르.
1.14. β-(3,5-디사이클로헥실-4-하이드록시페닐)프로피온산과 일가 또는 다가 알코올, 예를 들면 메탄올, 에탄올, n-옥탄올, 이소옥탄올, 옥타데카놀, 1,6-헥산디올, 1,9-노난디올, 에틸렌 글리콜, 1,2-프로판디올, 네오펜틸 글리콜, 티오디에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 펜타에리트리톨, 트리스(하이드록시에틸) 이소시아누레이트, N,N'-비스(하이드록시에틸)옥살아미드, 3-티아운데카놀, 3-티아펜타데카놀, 트리메틸헥산디올, 트리메틸올프로판 또는 4-하이드록시메 틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과의 에스테르.
1.15. 3,5-디-t-부틸-4-하이드록시페닐아세트산과 일가 또는 다가 알코올, 예를 들면 메탄올, 에탄올, n-옥탄올, 이소옥탄올, 옥타데카놀, 1,6-헥산디올, 1,9-노난디올, 에틸렌 글리콜, 1,2-프로판디올, 네오펜틸 글리콜, 티오디에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 펜타에리트리톨, 트리스(하이드록시에틸) 이소시아누레이트, N,N'-비스(하이드록시에틸)옥살아미드, 3-티아운데카놀, 3-티아펜타데카놀, 트리메틸헥산디올, 트리메틸올프로판 또는 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과의 에스테르.
1.16. 3,3-비스(3'-t-부틸-4'-하이드록시페닐)부티르산과 일가 또는 다가 알코올, 예를 들면 메탄올, 에탄올, n-옥탄올, 이소옥탄올, 옥타데카놀, 1,6-헥산디올, 1,9-노난디올, 에틸렌 글리콜, 1,2-프로판디올, 네오펜틸 글리콜, 티오디에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 펜타에리트리톨, 트리스(하이드록시에틸) 이소시아누레이트, N,N'-비스(하이드록시에틸)옥살아미드, 3-티아운데카놀, 3-티아펜타데카놀, 트리메틸헥산디올, 트리메틸올프로판 또는 4-하이드록시메틸-1-포스파-2,6,7-트리옥사비사이클로[2.2.2]옥탄과의 에스테르.
1.17. β-(3,5-디-t-부틸-4-하이드록시페닐)프로피온산의 아미드, 예를 들면 N,N'-비스(3,5-디-t-부틸-4-하이드록시페닐프로피오닐)헥사메틸렌디아민, N,N'-비스(3,5-디-t-부틸-4-하이드록시페닐프로피오닐)트리메틸렌디아민 및 N,N'-비스(3,5-디-t-부틸-4-하이드록시페닐프로피오닐)하이드라진.
1.18. α-토코페롤, β-토코페롤, γ-토코페롤, δ-토코페롤 및 이들의 혼합물과 같은 토코페롤(비타민 E).
1.19. 아스코르브산(비타민 C).
1.20. 아민 항산화제, 예를 들면 N,N'-디이소프로필-p-페닐렌디아민, N,N'-디-sec-부틸-p-페닐렌디아민, N,N'-비스(1,4-디메틸펜틸)-p-페닐렌디아민, N,N'-비스(1-에틸-3-메틸펜틸)-p-페닐렌디아민, N,N'-비스(1-메틸헵틸)-p-페닐렌디아민, N,N'-디사이클로헥실-p-페닐렌디아민, N,N'-디페닐-p-페닐렌디아민, N,N'-디(나프틸-2-)-p-페닐렌디아민, N-이소프로필-N'-페닐-p-페닐렌디아민, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민, N-(1-메틸헵틸)-N'-페닐-p-페닐렌디아민, N-사이클로헥실-N'-페닐-p-페닐렌디아민, 4-(톨루엔설폰아미도)디페닐아민, N,N'-디메틸-N,N'-디-sec-부틸-p-페닐렌디아민, 디페닐아민, N-알릴디페닐아민, 4-이소프로폭시디페닐아민, N-페닐-1-나프틸아민, N-(4-t-옥틸페닐)-1-나프틸아민, N-페닐-2-나프틸아민, 옥틸화 디페닐아민, 예를 들면 p,p'-디-t-옥틸디페닐아민, 4-n-부틸아미노페놀, 4-부티릴아미노페놀, 4-노나노일아미노페놀, 4-도데카노일아미노페놀, 4-옥타데카노일아미노페놀, 디(4-메톡시페닐)아민, 2,6-디-t-부틸-4-디메틸아미노메틸페놀, 2,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐메탄, N,N,N',N'-테트라메틸-4,4'-디아미노디페닐메탄, 1,2-디-[(2-메틸페닐)아미노]에탄, 1,2-디(페닐아미노)프로판, (o-톨릴)비구아니드, 디[4-(1',3'-디메틸부틸)-페닐]아민, t-옥틸화 N-페닐-1-나프틸아민, 모노- 및 디알킬화 t-부틸/t-옥틸디페닐아민의 혼합물, 모노- 및 디알킬화 노닐디페닐아민의 혼합물, 모노- 및 디알킬화 도데실디페닐아민의 혼합물, 모노- 및 디알킬화 이소프로필/이소헥실-디페닐아민의 혼합물, 모노- 및 디알킬화 t-부틸디페닐아민의 혼합물, 2,3-디하이드로-3,3-디메틸-4H-1,4-벤조티아진, 페노티아진, 모노- 및 디알킬화된 t-부틸/t-옥틸페노티아진의 혼합물, 모노- 및 디알킬화된 t-옥틸페노티아진의 혼합물, N-알릴페노티아진, N,N,N',N'-테트라페닐-1,4-디아미노부트-2-엔, N,N-비스(2,2,6,6-테트라메틸피페리딘-4-일)헥사메틸렌디아민, 비스(2,2,6,6-테트라메틸피페리딘-4-일)세바케이트, 2,2,6,6-테트라메틸피페리딘-4-온 및 2,2,6,6-테트라메틸피페리딘-4-올.
2. 자외선 흡수제 및 광 안정화제
2.1. 2-(2'-하이드록시페닐)벤조트리아졸, 예를 들면 2-(2'-하이드록시-5'-메틸페닐)벤조트리아졸, 2-(3',5'-디-t-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(5'-t-부틸-2'-하이드록시페닐)벤조트리아졸, 2-[2'-하이드록시-5'-(1,1,3,3-테트라메틸부틸)페닐]벤조트리아졸, 2-(3',5'-디-t-부틸-2'-하이드록시페닐)-5-클로로벤조트리아졸, 2-(3'-t-부틸-2'-하이드록시-5'-메틸페닐)-5-클로로벤조트리아졸, 2-(3'-sec-부틸-5'-t-부틸-2'-하이드록시페닐)벤조트리아졸, 2-(2'-하이드록시-4'-옥톡시페닐)벤조트리아졸, 2-(3',5'-디-t-아밀-2'-하이드록시페닐)벤조트리아졸, 2-(3',5'-비스(α,α-디메틸벤질)-2'-하이드록시페닐)벤조트리아졸; 2-(3'-t-부틸-2'-하이드록시-5'-(2-옥틸옥시카보닐에틸)페닐)-5-클로로벤조트리아졸, 2-(3'-t-부틸-5'-[2-(2-에틸헥실옥시)카보닐에틸]-2'-하이드록시페닐)-5-클로로벤조트리아졸, 2-(3'-t-부틸-2'-하이드록시-5'-(2-메톡시카보닐에틸)페닐)-5-클로로벤조트리아졸, 2-(3'-t-부틸-2'-하이드록시-5'-(2-메톡시카보닐에틸)페닐)벤조트리아졸, 2-(3'-t-부틸-2'-하이드록시-5'-(2-옥틸옥시카보닐에틸)페닐)벤조트리아졸, 2-(3'-t-부틸- 5'-[2-(2-에틸헥실옥시)카보닐에틸]-2'-하이드록시페닐)벤조트리아졸, 2-(3'-도데실-2'-하이드록시-5'-메틸페닐)벤조트리아졸 및 2-(3'-t-부틸-2'-하이드록시-5'-(2-이소옥틸옥시카보닐에틸)페닐벤조트리아졸의 혼합물; 2,2'-메틸렌비스[4-(1,1,3,3-테트라메틸부틸)-6-벤조트리아졸-2-일페놀]; 2-[3'-t-부틸-5'-(2-메톡시카보닐에틸)-2'-하이드록시페닐]벤조트리아졸을 폴리에틸렌 글리콜 300으로 에스테르교환 반응시킨 생성물; 및 [R-CH2CH2-COO(CH2)3]2(여기서, R은 3'-t-부틸-4'-하이드록시-5'-2H-벤조트리아졸-2-일페닐이다).
2.2. 2-하이드록시벤조페논, 예를 들면 4-하이드록시, 4-메톡시, 4-옥톡시, 4-데실옥시, 4-도데실옥시, 4-벤질옥시, 4,2',4'-트리하이드록시 및 2'-하이드록시-4,4'-디메톡시 유도체.
2.3. 치환 또는 비치환 벤조산의 에스테르, 예를 들면 4-t-부틸-페닐 살리실레이트, 페닐 살리실레이트, 옥틸페닐 살리실레이트, 디벤조일레소시놀, 비스(4-t-부틸벤조일)레소시놀, 벤조일레소시놀, 2,4-디-t-부틸페닐 3,5-디-t-부틸-4-하이드록시벤조에이트, 헥사데실 3,5-디-t-부틸-4-하이드록시벤조에이트, 옥타데실 3,5-디-t-부틸-4-하이드록시벤조에이트 및 2-메틸-4,6-디-t-부틸페닐 3,5-디-t-부틸-4-하이드록시벤조에이트.
2.4. 아크릴레이트, 예를 들면 에틸 α-시아노-β,β-디페닐아크릴레이트 또는 이소옥틸 α-시아노-β,β-디페닐아크릴레이트, 메틸 α-카보메톡시신나메이트, 메틸 α-시아노-β-메틸-p-메톡시신나메이트 또는 부틸 α-시아노-β-메틸-p-메톡시신나 메이트, 메틸 α-카보메톡시-p-메톡시신나메이트 및 N-(β-카보메톡시-β-시아노비닐)-2-메틸인돌린.
2.5. 니켈 화합물, 예를 들면 n-부틸아민, 트리에탄올아민 또는 N-사이클로헥실디에탄올아민과 같은 추가적인 리간드를 포함하거나 포함하지 않은, 1:1 또는 1:2 착체와 같은 2,2'-티오비스[4-(1,1,3,3-테트라메틸부틸)페놀]의 니켈 착체; 니켈 디부틸디티오카바메이트; 4-하이드록시-3,5-디-t-부틸벤질포스폰산의 메틸 또는 에틸 에스테르와 같은 모노알킬 에스테르의 니켈 염; 케토심, 예를 들면 2-하이드록시-4-메틸페닐 운데실 케토심의 니켈 착체; 및 추가의 리간드를 포함하거나 포함하지 않는 1-페닐-4-라우로일-5-하이드록시피라졸의 니켈 착체.
2.6. 입체 장애 아민, 예를 들면 비스(2,2,6,6-테트라메틸피페리딘-4-일)세바케이트, 비스(2,2,6,6-테트라메틸피페리딘-4-일)글루타레이트, 비스(2,2,6,6-테트라메틸피페리딘-4-일)숙시네이트, 비스(1,2,2,6,6-펜타메틸피페리딘-4-일)세바케이트, 비스(1,2,2,6,6-펜타메틸피페리딘-4-일)글루타레이트, 2,2,6,6-테트라메틸피페리딜 베헤네이트, 1,2,2,6,6-펜타메틸피페리딜 베헤네이트, 1-하이드록시에틸-2,2,6,6-테트라메틸-4-하이드록시피페리딘 및 석신산의 축합물, N,N'-비스-(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민 및 4-t-옥틸아미노-2,6-디클로로-1,3,5-s-트리아진의 축합물, 트리스(2,2,6,6-테트라메틸-4-피페리딜)니트릴로트리아세테이트, 테트라키스(2,2,6,6-테트라메틸-4-피페리딜)-1,2,3,4-부탄테트라오에이트, 1,1'-(1,2-에탄디일)-비스(3,3,5,5-테트라메틸피페라지논), 4-벤조일-2,2,6,6-테트라메틸피페리딘, 4-스테아릴옥시-2,2,6,6-테트라메틸피페리딘, 4-스테아로일옥시-2,2,6,6-테트라메틸피페리딘, 4-스테아릴옥시-1,2,2,6,6-펜타메틸피페리딘, 4-스테아로일옥시-1,2,2,6,6-펜타메틸피페리딘, 비스(1,2,2,6,6-펜타메틸피페리딜)2-n-부틸-2-(2-하이드록시-3,5-디-t-부틸벤질)말로네이트, 비스(1,2,2,6,6-펜타메틸피페리딜)2-n-부틸-2-(4-하이드록시-3,5-디-t-부틸벤질)말로네이트, 3-n-옥틸-7,7,9,9-테트라메틸-1,3,8-트리아자스피로[4.5]데칸-2,4-디온, 비스(1-옥틸옥시-2,2,6,6-테트라메틸피페리딜)세바케이트, 비스(1-옥틸옥시-2,2,6,6-테트라메틸피페리딜)숙시네이트, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민 및 4-모르폴리노-2,6-디클로로-1,3,5-트리아진의 축합물, N,N'-비스(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌디아민 및 4-사이클로헥실아미노-2,6-디클로로-1,3,5-트리아진의 축합물, 2-클로로-4,6-디-(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-1,3,5-트리아진 및 1,2-비스(3-아미노프로필아미노)-에탄의 축합물, 2-클로로-4,6-디-(4-메톡시프로필아미노-2,2,6,6-테트라메틸피페리딜)-1,3,5-트리아진 및 1,2-비스(3-아미노프로필아미노)에탄의 축합물, 2-클로로-4,6-디-(4-메톡시프로필아미노-1,2,2,6,6-펜타메틸피페리딜)-1,3,5-트리아진 및 1,2-비스(3-아미노프로필아미노)에탄의 축합물, 2-클로로-4,6-디-(4-n-부틸아미노-1,2,2,6,6-펜타메틸피페리딜)-1,3,5-트리아진 및 1,2-비스(3-아미노프로필아미노)에탄의 축합물, 2-클로로-4,6-디-(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-1,3,5-트리아진과, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 헥사메틸렌디아민 및 1,2-비스(3-아미노프로필아미노)에탄과 같은, 아민상의 하나 내지 모든 활성 수소 원자가 치환된, 단일- 또는 다-작용성 아민과의 반응 생성물, 2-클로로-4,6-디-(4-n-부틸아미노-1,2,2,6,6-펜타메틸피페리딜)-1,3,5-트리아진과, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 헥사메틸렌디아민 및 1,2-비스(3-아미노프로필아미노)에탄과 같은, 아민상의 하나 내지 모든 활성 수소 원자가 치환된, 단일- 또는 다-작용성 아민과의 반응 생성물, 2-클로로-4,6-디-(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-1,3,5-트리아진 및 4-t-옥틸아미노-2,6-디클로로-1,3,5-s-트리아진과, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 헥사메틸렌디아민 및 1,2-비스(3-아미노프로필아미노)에탄과 같은, 아민상의 하나 내지 모든 활성 수소 원자가 치환된, 단일- 또는 다-작용성 아민과의 반응 생성물, 2-클로로-4,6-디-(4-n-부틸아미노-1,2,2,6,6-펜타메틸피페리딜)-1,3,5-트리아진 및 4-t-옥틸아미노-2,6-디클로로-1,3,5-s-트리아진과, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 헥사메틸렌디아민 및 1,2-비스(3-아미노프로필아미노)에탄과 같은, 아민상의 하나 내지 모든 활성 수소 원자가 치환된, 단일- 또는 다-작용성 아민과의 반응 생성물, 2-클로로-4,6-디-(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-1,3,5-트리아진 및 4-(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-2,6-디클로로-1,3,5-s-트리아진과, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 헥사메틸렌디아민 및 1,2-비스(3-아미노프로필아미노)에탄과 같은, 아민상의 하나 내지 모든 활성 수소 원자가 치환된, 단일- 또는 다-작용성 아민과의 반응 생성물, 2-클로로-4,6-디-(4-n-부틸아미노-1,2,2,6,6-펜타메틸피페리딜)-1,3,5-트리아진 및 4-(4-n-부틸아미노-2,2,6,6-테트라메틸피페리딜)-2,6-디클로로-1,3,5-s-트리아진과, 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 헥사메틸렌디아민 및 1,2-비스(3-아미노프로필아미노)에탄과 같은, 아민상의 하나 내지 모든 활성 수소 원자가 치환된, 단일- 또는 다-작용성 아민과의 반응 생성물; 1,2-비스(3-아미노프로필아미노)에탄 및 2,4,6-트리클로로-1,3,5-트리아진의 축합물, 4-부틸아미노-2,2,6,6-테트라메틸피페리딘, N-(2,2,6,6-테트라메틸-4-피페리딜)-n-도데실석신이미드, N-(1,2,2,6,6-펜타메틸-4-피페리딜)-n-도데실석신이미드, 8-아세틸-3-도데실-7,7,9,9-테트라메틸-1,3,8-트리아자스피로[4.5]데칸-2,4-디온, 올리고머화 2,2,4,4-테트라메틸-20-(옥시라닐메틸)-7-옥사-3,20-디아자-디스피로[5.1.11.2]헤네이코산-21-온, 올리고머화 1,2,2,4,4-펜타메틸-20-(옥시라닐메틸)-7-옥사-3,20-디아자디스피로[5.1.11.2]헤네이코산-21-온, 올리고머화 1-아세틸-2,2,4,4-테트라메틸-20-(옥시라닐메틸)-7-옥사-3,20-디아자디스피로[5.1.11.2]헤네이코산-21-온, 3-도데실-1-(2,2,6,6-테트라메틸-4-피페리딜)피롤리딘-2,5-디온, 3-도데실-1-(1,2,2,6,6-펜타메틸-4-피페리딜)피롤리딘-2,5-디온, 2,2,4,4-테트라메틸-7-옥사-3,20-디아자디스피로[5.1.11.2]헤네이코산-21-온, 2,2,4,4-테트라메틸-7-옥사-21-옥소-3,20-디아자디스피로[5.1.11.2]헤네이코산-3-프로판산 도데실 에스테르, 2,2,4,4-테트라메틸-7-옥사-21-옥소-3,20-디아자디스피로[5.1.11.2]헤네이코산-3-프로판산 테트라데실 에스테르, 2,2,3,4,4-펜타메틸-7-옥사-3,20-디아자디스피로[5.1.11.2]헤테이코산-21-온, 2,2,3,4,4,-펜타메틸-7-옥사-21-옥소-3,20-디아자디스피로[5.1.11.2]헤네이코산-3-프로판산 도데실 에스테르, 2,2,3,4,4-펜타메틸-7-옥사-21-옥소-3,20-디아자디스피로[5.1.11.2]-헤네이코산-3-프로판산 테트라데실 에스테르, 3-아세틸-2,2,4,4-테트라메틸-7-옥사-3,20-디아자디스피로[5.1.11.2]헤네이코산-21-온, 3-아세틸-2,2,4,4-테트라메틸-7-옥사-21-옥소-3,20-디아자디스피로[5.1.11.2]헤네이코산-3-프로판산 도데실 에스테르, 3-아세틸-2,2,4,4-테트라메틸-7-옥사-21-옥소-3,20-디아자디스피로[5.1.11.2]헤네이코산-3-프로판산 테트라데실 에스테르, 1,1',3,3',5,5'-헥사하이드로-2,2',4,4',6,6'-헥사아자-2,2',6,6'-비스메타노-7,8-디옥소-4,4'-비스(1,2,2,6,6-펜타메틸-4-피페리딜)비페닐, 폴리-N,N'-비스-(2,2,6,6-테트라메틸-4-피페리딜)-1,8-디아자데실렌, 2,2,6,6-테트라메틸-4-알릴옥시피페리딘 및 폴리메틸하이드리도실록산의 부가물(몰질량 4000 이하), 1,2,2,6,6-펜타메틸-4-아릴옥시피페리딘 및 폴리메틸하이드리도실록산의 부가물(몰질량 4000 이하), N,N'-디포르밀-N,N'-비스(2,2,6,6-테트라메틸-4-피페리디닐)헥사메틸렌디아민, N,N'-디포밀-N,N'-비스(1,2,2,6,6-펜타메틸-4-피페리디닐)헥사메틸렌디아민, 5,11-비스(2,2,6,6-테트라메틸-4-피페리디닐)-3,5,7,9,11,13-헥사아자테트라사이클로[7.4.0.02,7.13,13]테트라데칸-8,14-디온, 5,11-비스(1,2,2,6,6-펜타메틸-4-피페리디닐)-3,5,7,9,11,13-헥사아자테트라사이클로[7.4.0.02,7.13,13]테트라데칸-8,14-디온, [(4-메톡시페닐)메틸렌]프로판디온산 비스(2,2,6,6-테트라메틸-4-피페리디닐)에스테르, [(4-메톡시페닐)메틸렌]프로판디온산 비스(1,2,2,6,6-펜타메틸-4-피페리디닐)에스테르, 2,4,6-트리스(N-사이클로헥실-N-[2-(3,3,4,5,5-펜타메틸피페라지논-1-일)에틸]아미노)-1,3,5-트리아진, 메틸스티렌을 포함하는 스티렌과 4-아미노-2,2,6,6-테트라메틸피페리딘 및 옥타데실아민과 반응시킨 말레산 무수물의 공중합체, α-메틸스티렌을 포함하는 스티렌과 4-아미노-1,2,2,6,6-펜타메틸피페리딘 및 옥타데실아민과 반응시킨 말레산 무수물의 공중합체, 디올 성분으로 2,2'-[(2,2,6,6-테트라메틸-4-피페리디닐)이미노]비스[에탄올]을 포함하는 폴리카보네이트, 디올 성분으로 2,2'-(1,2,2,6,6-펜타메틸-4-피페리디닐)이미노]비스[에탄올]을 포함하는 폴리카보네이트, 말레산 무수물과 4-아미노-2,2,6,6-테트라메틸피페리딘과 반응시킨 C30 이하의 α-올레핀의 공중합체, 말레산 무수물 및 1-아세틸-4-아미노-2,2,6,6-테트라메틸피페리딘과 반응시킨 C30 이하의 α-올레핀의 공중합체, 말레산 무수물 및 4-아미노-1,2,2,6,6-펜타메틸피페리딘과 반응시킨 C30 이하의 α-올레핀의 공중합체, 및 피페리딘 상에 유리된 NH 기와 전술한 화합물의 N-알킬- 및 N-아릴 옥시 유도체, 특히 C1 내지 C18인 α-메틸벤질옥시 및 알킬옥시 유도체.
2.7. 옥살아미드, 예를 들면 4,4'-디옥틸옥시옥사닐리드, 2,2'-디에톡시아닐리드, 2,2'-디옥틸옥시-5,5'-디-t-부틸옥사닐리드, 2,2'-디도데실옥시-5,5'-디-t-부틸옥사닐리드, 2-에톡시-2'-에틸옥사닐리드, N,N'-비스(3-디메틸아미노프로필)옥살아미드, 2-에톡시-5-t-부틸-2'-에틸옥사닐리드 및 이들의 2-에톡시-2'-에틸-5,4'-디-t-부틸옥사닐리드드와의 혼합물, o- 및 p-메톡시-이치환된 옥사닐리드와의 혼합물 및 o- 및 p-에톡시-이치환된 옥사닐리드와의 혼합물.
2.8. 2-(2-하이드록시페닐)-1,3,5-트리아진, 예를 들면 2,4,6-트리스(2-하이드록 시-4-옥틸옥시페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-옥틸옥시페닐)-4',6-비스 (2',4-디메틸페닐)-1,3,5-트리아진, 2-(2,4-디하이드록시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2,4-디하이드록시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2,4-비스(2-하이드록시-4-프로필옥시페닐)-6-(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-옥틸옥시페닐)-4,6-비스(4-메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-도데실옥시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-[2-하이드록시-4-(2-하이드록시-3-부틸옥시프로필옥시)페닐]-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-[2-하이드록시-4-(2-하이드록시-3-옥틸옥시프로필옥시)페닐]-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-트리데실옥시페닐)-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-[4-도데실옥시/트리데실옥시-2-하이드록시프로폭시)-2-하이드록시페닐]-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-[2-하이드록시-4-(2-하이드록시-3-도데실옥시프로폭시)페닐]-4,6-비스(2,4-디메틸페닐)-1,3,5-트리아진, 2-(2-하이드록시-4-헥실옥시)페닐-4,6-디페닐-1,3,5-트리아진, 2-(2-하이드록시-4-메톡시페닐)-4,6-디페닐-1,3,5-트리아진, 2,4,6-트리스[2-하이드록시-4-(3-부톡시-2-하이드록시프로폭시)페닐]-1,3,5-트리아진 및 2-(2-하이드록시페닐)-4-(4-메톡시페닐)-6-페닐-1,3,5-트리아진.
3. 금속 불활성화제, 예를 들면 N,N'-디페닐옥살아미드, N-살리실랄-N'-살리실로일하이드라진, N,N'-비스(살리실로일)하이드라진, N,N'-비스(3,5-디-t-부틸-4-하이드록시페닐프로피오닐)하이드라진, 3-살리실로일아미노-1,2,4-트리아졸, 비스(벤질 리덴)옥살릴 디하이드라지드, 옥사닐리드, 이소프탈로일 디하이드라지드, 세바코일 비스페닐하이드라지드, N,N'-디아세틸아디포일 디하이드라지드, N,N'-비스(살리실로일)옥살릴 디하이드라지드 및 N,N'-비스(살리실로일)티오프로피오닐 디하이드라지드.
4. 포스파이트 및 포스포나이트, 예를 들면 트리페닐 포스파이트, 디페닐 알킬 포스파이트, 페닐 디알킬 포스파이트, 트리스(노닐페닐)포스파이트, 트리라우릴 포스파이트, 트리옥타데실 포스파이트, 디스테아릴 펜타에리트리톨 디포스파이트, 트리스(2,4-디-t-부틸페닐)포스파이트, 디이소데실 펜타에리트리톨 디포스파이트, 비스(2,4-디-t-부틸페닐)펜타에리트리톨 디포스파이트, 비스(2,6-디-t-부틸-4-메틸페닐)펜타에리트리톨 디포스파이트, 비스이소데실옥시 펜타에리트리톨 디포스파이트, 비스(2,4-디-t-부틸-6-메틸페닐)펜타에리트리톨 디포스파이트, 비스(2,4,6-트리-t-부틸페닐)펜타에리트리톨 디포스파이트, 트리스테아릴 소르비톨 트리포스파이트, 테트라키스(2,4-디-t-부틸페닐)4,4'-비페닐렌디포스포나이트, 6-이소옥틸옥시-2,4,8,10-테트라-t-부틸-12H-디벤조[d,g]-1,3,2-디옥사포스포신, 6-플루오로-2,4,8,10-테트라-t-부틸-12-메틸-디벤조[d,g]-1,3,2-디옥사포스포신, 비스(2,4-디-t-부틸-6-메틸페닐)메틸 포스파이트, 비스(2,4-디-t-부틸-6-메틸페닐)에틸 포스파이트, 트리스(2-t-부틸-4-티오(2'-메틸-4'-하이드록시-5'-t-부틸)페닐-5-메틸)페닐 포스파이트, 2,2',2"-니트릴로[트리에틸 트리스(3,3',5,5'-테트라-t-부틸-1,1'-비페닐-2,2'-디일)포스파이트] 및 비스[2-메틸-4,6-비스(1,1-디메틸에틸)페놀]인산 에틸 에스테르.
5. 하이드록실아민, 예를 들면 N,N-디벤질하이드록실아민, N,N-디에틸하이드록실아민, N,N-디옥틸하이드록실아민, N,N-디라우릴하이드록실아민, N,N-디테트라데실하이드록실아민, N,N-디헥사데실하이드록실아민, N,N-디옥타데실하이드록실아민, N-헥사데실-N-옥타데실하이드록실아민, N-헵타데실-N-옥타데실하이드록실아민, 및 수소화 탈로우 지방산 아민으로부터 제조된 N,N-디알킬하이드록실아민.
6. 니트론, 예를 들면 N-벤질 알파-페닐 니트론, N-에틸 알파-메틸 니트론, N-옥틸 알파-헵틸 니트론, N-라우릴 알파-운데실 니트론, N-테트라데실 알파-트리데실 니트론, N-헥사데실 알파-펜타데실 니트론, N-옥타데실 알파-헵타데실 니트론, N-헥사데실 알파-헵타데실 니트론, N-옥타데실 알파-펜타데실 니트론, N-헵타데실 알파-헵타데실 니트론, N-옥타데실 알파-헥사데실 니트론, 및 수소화 탈로우 지방산 아민으로부터 제조된 N,N-디알킬하이드록실아민으로부터 유도된 니트론.
7. 제올라이트 및 DHT(등록상표) 4A와 같은 하이드로탈사이트. 이 종류의 하이드로탈사이트는 하기 일반식으로 나타낼 수 있다:
[(M2+)1-x(M3+)x(OH)2(An-)x/n
yH2O]
상기 식에서,
(M2+)는 Mg, Ca, Sr, Ba, Zn, Pb, Sn 또는 Ni이고;
(M3+)는 Al, B 또는 Bi이고;
An은 원자가 n의 음이온이고;
n은 1 내지 4의 정수이고;
x는 0 내지 0.5의 값이고;
y는 0 내지 2의 값이고;
A는 OH-, Cl-, Br-, I-, ClO4
-, CH3
COO-, C6H5COO-, CO3
2-, SO4
2-, (OOC-COO)2-, (CHOHCOO)2
2-, (CHOH)4CH2OHCOO-, C2H
4(COO)2
2-, (CH2COO)2
2-, CH3CHOHCOO
-, SiO3
2-, SiO4
4-, Fe(CN)6
3-, Fe(CN)6
4-, BO3
3-, PO3
3- 또는 HPO4
2-이다.
(M2+)가 (Ca2+), (Mg2+) 또는 (Mg2+) 및 (Zn2+)의 혼합물이고, (An-)가 CO3
2-, BO3
3- 또는 PO3
3-이고, x가 0 내지 0.5의 값이고, y가 0 내지 2의 값인 하이드로탈사이트를 사용하는 것이 바람직하다. 또한 하기 일반식으로 나타낼 수 있는 하이드로탈사이트를 사용할 수 있다:
[(M2+)x(Al3+)2(OH)2x+6nz(An-)2
yH2O]
상기 식에서,
(M2+)는 Mg2+ 또는 Zn2+이나, 바람직하게는 Mg2+이고;
(An-)는 특히 CO3 2-, (OOC-COO)2-, OH- 및 S2-로 구성된 군에서 선택된 음이온이고, 이 때 n은 이온의 원자가를 나타내고;
y는 양의 수, 보다 바람직하게는 0 내지 5, 특히 0.5 내지 5인 수이고;
x 및 z는 양의 값을 가지며, 이 때 x는 바람직하게는 2 내지 6이고, z는 2 미만이다. 하기 분자식의 하이드로탈사이트가 특히 바람직하다:
Al2O3 x 6MgO x CO2 x 12H2O,
Mg4.5Al2(OH)13 x CO3 x 3.5H2O,
4MgO x Al2O3 x CO2 x 9H2O,
4MgO x Al2O3 x CO2 x 6H2O,
ZnO x 3MgO x Al2O3 x CO2 x 8-9H2O,
ZnO x 3MgO x Al2O3 x CO2 x 5-6H2O, 및
Mg4.5Al2(OH)13 x CO3.
하이드로탈사이트는 전체 중합체 배합물을 기준으로, 바람직하게는 0.01 내지 5중량%, 특히 0.2 내지 3중량%의 농도로 중합체에 사용된다.
8. 티오시너지스트, 예를 들면 디라우릴 티오디프로피오네이트 및 디스테아릴 티오디프로피오네이트.
9. 과산화물 소거제, 예를 들면 β-티오디프로피온산의 에스테르, 예를 들면 라우릴, 스테아릴, 미리스틸 또는 트리데실 에스테르, 머캅토벤즈이미다졸, 2-머캅토벤즈이미다졸의 아연 염, 아연 알킬디티오카바메이트, 아연 디부틸디티오카바메이트, 디옥타데실 모노설피드, 디옥타데실 디설피드, 펜타에리트리톨 테트라키스(β-도데 실머캅토)프로피오네이트.
10. 폴리아미드 안정화제, 예를 들면 요오드화물 및/또는 인 화합물과 조합된 구리 염, 및 이원자가 망간의 염.
11. 염기성 조안정화제, 예를 들면 멜라민, 폴리비닐피롤리돈, 디시안디아미드, 트리알릴 시아누레이트, 우레아 유도체, 하이드라진 유도체, 아민, 폴리아민, 폴리우레탄, 고지방산의 알칼리 금속 및 알칼리 토금속 염, 예를 들면 Ca 스테아레이트, Zn 스테아레이트, Mg 베헤네이트, Mg 스테아레이트, Na 리시놀레이트, K 팔미테이트, 안티몬 피로카테콜레이트 또는 주석 피로카테콜레이트, 알칼리 금속 및 알칼리 토금속 염 및 락트산의 아연 염 또는 알루미늄 염.
12. 증핵제, 예를 들면 무기 물질, 예를 들면 활석, 금속 산화물, 예를 들면 산화 티탄 또는 산화 마그네슘, 바람직하게는 알칼리 토금속의 인산염, 탄산염 또는 황산염; 유기 화합물, 예를 들면 모노- 또는 폴리카복실산 및 그의 염, 예를 들면 4-t-부틸벤조산, 아디프산, 디페닐아세트산, 나트륨 숙시네이트 또는 나트륨 벤조에이트, 방향족 알데히드의 아세탈 및 소르비톨과 같은 다작용성 알코올, 예를 들면 1,3-2,4-디(벤질리덴)-D-소르비톨, 1,3-2,4-디(4-톨릴리덴)-D-소르비톨 및 1,3-2,4-디(4-에틸벤질리덴)-D-소르비톨; 및 중합성 화합물, 예를 들면 이온성 공중합체(이오노머).
13. 충전제 및 강화제, 예를 들면 탄산 칼슘, 실리케이트, 유리 섬유, 석면, 활석, 카올린, 운모, 황산 바륨, 금속 산화물 및 금속 수산화물, 카본 블랙, 흑연, 목재 가루, 기타 천연 생성물의 가루 또는 섬유, 및 합성 섬유.
14. 기타 첨가제, 예를 들면, 가소제, 윤활제, 유화제, 안료, 유동성 첨가제, 촉매, 평활 보조제, 광학 표백제, 화염방지제, 정전기 방지제 및 취입제.
15. 예를 들면, 미국 특허 제 4,325,863 호, 제 4,338,244 호, 제 5,175,312, 제 5,216,052 호 및 제 5,252,643 호, 독일 특허 공개 제 43 16 611 호, 제 43 16 622 호 및 제 43 16 876 호, 및 유럽 특허 공개 제 0 589 839 호 및 제 0 591 102 호에 기술된 벤조푸라논 및 인돌린, 또는 3-[4-(2-아세톡시에톡시)페닐]-5,7-디-t-부틸벤조푸란-2-온, 5,7-디-t-부틸-3-[4-(2-스테아로일옥시에톡시)페닐]-벤조푸란-2-온, 3,3'-비스[5,7-디-t-부틸-3-[4-(2-하이드록시에톡시]페닐)-벤조푸란-2-온, 5,7-디-t-부틸-3-(4-에톡시페닐)-벤조푸란-2-온, 3-(4-아세톡시-3,5-디메틸페닐)-5,7-디-t-부틸벤조푸란-2-온 및 3-(3,5-디에틸-4-피발로일옥시페닐)-5,7-디-t-부틸벤조푸란-2-온.
이들 혼합물은 고온수 저장후 또는 그와 관련하여 물 추출 조건하에서 사용되는 폴리올레핀 제품에 사용되는 경우에 산화 유도 시간(OIT)과 같은 표준 시험 방법에 의해 측정시 우수한 장기간 성능을 나타낸다. 폴리올레핀 수지는 또한 강관 또는 해저케이블과 같은 금속 제품에 피복층 또는 적층물로서 적용될 수 있다.
특히 고온수 처리 중 또는 후 물 추출 조건에 노출되는 폴리올레핀 제품을 안정화시키는 데 사용되는 전술한 안정화제 시스템은 중합체 수지로부터의 이동에 의한 초기 소비를 방지할 수 있다. 이러한 작용은 언급한 제품의 장기간 안정성을 명백하게 개선시킨다.
물 추출 조건에 노출되는 폴리올레핀 제품을 안정화시키는 최신의 기술 수준 을 고려할 때 특정 안정화제의 그러한 명백한 개선 및 기여는 예상되지 못했던 것이다.
하기 실시예는 본 발명을 예시한다.
시료의 제조 및 시험
하기 실시예에서 "부" 및 "%"는 각각 "중량부" 및 "중량%"를 의미한다.
폴리에틸렌-HD와 안정화제와의 분말 혼합물의 제조
플라스크에 폴리에틸렌-HD(PE-HD CRP 100형, 무착색, 이정점(bimodal) 분자량 분포, 제조자: 독일 프랑크푸르트 소재의 엘레낙 게엠베하(Elenac GmbH)) 100부를 Ca-스테아레이트 0.1부, 트리스(2,4-디-t-부틸페닐)포스파이트 0.1부 및 페놀계 성분(AO1, AO2 또는 이들 페놀의 1:1 혼합물) 0.1부로 구성된 기제 안정화제 조성물과 혼합하였다. LS1, LS2 또는 LS3에 기초한 광 안정화제 또는 광 안정화제 혼합물, 또는 UV1 또는 UV2와 같은 자외선 흡수제 0.2부 또는 0.3부를 추가로 첨가하였다.
청색 착색된 시험편을 이용하여, 청색 안료(Pigment Blue) 4.1% 및 TiO2(금홍석-형) 2.8%를 포함하는 소위 레마핀-블루(Remafin-Blue(등록상표))로 불리는 마스터배치 2부를 추가로 첨가하였다.
첨가제를 중합체의 존재하에 아세톤에 용해시킨 후 용매를 진공증발시켰다.
210 내지 240℃/125rpm에서 단일 스크류 압출기(브라벤더(Brabender)형, 스크류 직경 16mm, L/D=20)를 사용하여 균질화를 수행하였다. 안료 마스터배치를 첨가하고 동일 조건에서 3배 압출을 실시하였다.
증기가열/수냉 수압 압형기를 사용하여 온도 185℃, 접촉 압력 5분동안 30바 및 최종 압력 3분동안 200바의 조건에서 생산된 압착 플라크(300x300mm, 두께 1mm)로부터 목적물을 천공하여 시험편을 제조하였다.
시험 과정
시료를 90℃의 고온수에 2개월동안 저장하였다.
DIN ISO 4892-2에 따라 제노테스트 베타(Xenotest Beta)법을 적용하여 인공 풍화를 일으켰다(무광(black) 표준 온도: 65℃, 에너지 밀도: 60W/m2(λ=300 내지 400nm), 강우 주기: 18/102, 여과장치: 제노크롬(Xenochrome) 300).
산소 기류(60ml/분)하에서 가열 속도 20K/분을 사용하여 200℃에서 산화 유도 시간(OIT) 측정을 수행하였다. 청색 착색된 송수관에 대한 OIT 결과를 하기 표 1a 내지 1c에 나타낸다:
자외선/열 안정화제 | OIT/분 수처리 전/후 |
비교예(HAS 사용 안함) | 32 5 |
LS1 0.2부 | 41 17 |
LS2 0.1부; LS3 0.1부 | 48 4 |
LS1 0.3부 | 53 22 |
UV1 0.3부 | 28 3 |
LS1 0.15부; LS2 0.15부 | 56 4 |
LS2 0.2부; UV1 0.1부 | 52 3 |
LS3 0.1부; LS2 0.1부; UV1 0.1부 | 42 3 |
자외선/열 안정화제 | OIT/분 수처리 전/후 |
LS1 0.2부 | 37 17 |
LS3 0.1부; LS2 0.1부 | 41 10 |
LS1 0.3부 | 43 14 |
LS1 0.2부; UV2 0.1부 | 45 18 |
LS1 0.2부; UV1 0.1부 | 48 16 |
UV1 0.3부 | 32 4 |
LS2 0.2부; UV1 0.1부 | 36 8 |
LS3 0.1부; LS2 0.1부; UV1 0.1부 | 50 9 |
자외선/열 안정화제 | OIT/분 수처리 전/후 |
비교예(HAS 사용 안함) | 58 18 |
LS1 0.2부 | 69 41 |
LS3 0.15부; LS2 0.15부 | 78 17 |
LS1 0.3부 | 78 47 |
LS1 0.2부; UV2 0.1부 | 68 39 |
LS1 0.2부; UV1 0.1부 | 56 38 |
UV1 0.3부 | 40 4 |
LS2 0.2부; UV1 0.1부 | 80 10 |
상기 실험 결과는 선행기술에 비하여 놀랄만큼 우수한 본 발명의 안정화제 조성물의 안정화 특성을 명백히 보여준다.
Claims (10)
- (a) 에피클로르히드린과 2,2,4,4-테트라메틸-7-옥사-3,20-디아자-20-(2,3-에폭시-프로필)-디스피로-[5.1.11.2]-헤네이코산-21-온의 중합체(LS1)를 필수적으로 포함하고, 폴리-{[6-[1,1,3,3-테트라메틸부틸)-이미노]-1,3,5-트리아진-2,4-디일][2-(2,2,6,6-테트라메틸피페리딜)-아미노]-헥사메틸렌-[4-(2,2,6,6-테트라메틸피페리딜)-이미노]}(LS2) 또는 폴리-(N-하이드록시에틸-2,2,6,6-테트라메틸-4-하이드록시-피페리딜-숙시네이트)(LS3)를 추가로 포함할 수 있는 1종 이상의 입체 장애 아민; 및(b) 하기 화합물 (A01) 내지 (A08)로 구성된 군에서 선택된 1종 이상의 페놀계 항산화제:비스-[3,3-비스-(4'-하이드록시-3'-t-부틸페닐)-부탄산]-글리콜에스테르(AO1);테트라키스메틸렌(3,5-디-t-부틸-4-하이드록시페닐)-하이드로신나메이트(AO2);옥타데실-3-(3,5-디-t-부틸-4-하이드록시페닐)-프로피오네이트(AO3);4,4',4"-[(2,4,6-트리메틸-1,3,5-벤젠트리일)트리스(메틸렌)]-트리스[2,6-비스(1,1-디메틸에틸)페놀](AO4);1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 1,3,5-트리스[[4-(1,1-디메틸에틸)-3-하이드록시-2,6-디메틸페닐]메틸](AO5);페놀, 4,4,',4"-(1-메틸-1-프로파닐-3-일리덴)트리스[2-(1,1-디메틸에틸)-5-메틸(AO6);페놀, 2,6-비스[[3-(1,1-디메틸에틸)-2-하이드록시-5-메틸페닐]옥타하이드로-4,7-메타노-1H-인데닐]-4-메틸(AO7); 및벤젠프로판산, 3-(1,1-디메틸에틸)-4-하이드록시-5-메틸-2,4,8,10-테트라옥사스피로[5.5]운데칸-3,9-디일비스(2,2-디메틸-2,1-에탄디일)에스테르(AO8)를 포함하고,상기 성분 (a)의 총중량비 대 상기 성분 (b)의 총중량비가 10:1 내지 1:5인,열가소성 중합체용 안정화제 조성물.
- 삭제
- 제 1 항에 있어서,성분 (b)가 화합물 (AO1), (AO2), (AO3) 및 이들의 혼합물로 구성된 군에서 선택된 안정화제 조성물.
- 제 3 항에 있어서,성분 (b)가 중량비 2:1 내지 1:2의 화합물 (AO1)과 (AO2)의 혼합물인 안정화제 조성물.
- 제 1 항에 있어서,메탄온, [2-하이드록시-4-(옥틸옥시)페닐]페닐(UV1); 페놀, 2-(5-클로로-2H-벤조트리아졸-2-일)-6-(1,1-디메틸에틸)-4-메틸(UV2); 및 2-하이드록시벤조페논, 2-(2-하이드록시페닐)-벤조트리아졸, 2-(2-하이드록시페닐)-1,3,5-벤조트리아진, 옥사닐리드, 신나메이트 및 살리실레이트로 구성된 군에서 선택된 자외선 흡수제를 추가의 성분 (c)로서 포함하고,이 때, 성분 (a):성분 (b):성분 (c)의 중량비가 5:1:1 내지 1:5:5인 안정화제 조성물.
- 열가소성 중합체를 기준으로 안정화제 조성물 0.001 내지 2.000중량%를 열가소성 중합체에 혼입시키는, 제 1 항 내지 제 5 항중 어느 한 항에 따른 안정화제 조성물의 사용 방법.
- 제 6 항에 있어서,안정화제 조성물의 양이 열가소성 중합체를 기준으로 0.020 내지 0.20중량%인 사용 방법.
- 제 6 항에 있어서,열가소성 중합체가 폴리에틸렌인 사용 방법.
- 가공 이전 또는 가공 도중 열가소성 수지에 제 1 항 내지 제 5 항중 어느 한 항에 따른 안정화제 조성물을 안정화량으로 혼입시킴을 포함하는, 물과 장기간 접촉하는 열가소성 중합체를 안정화시키는 방법.
- 제 9 항에 있어서,안정화제 조성물이 열가소성 중합체를 기준으로 0.020 내지 0.20중량%의 양으로 첨가되는 방법.
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2000
- 2000-02-25 GB GBGB0004436.2A patent/GB0004436D0/en not_active Ceased
-
2001
- 2001-02-21 KR KR1020027008723A patent/KR100711421B1/ko not_active IP Right Cessation
- 2001-02-21 US US10/204,397 patent/US6787591B2/en not_active Expired - Lifetime
- 2001-02-21 AT AT01908030T patent/ATE280197T1/de not_active IP Right Cessation
- 2001-02-21 EP EP01908030A patent/EP1268644B1/en not_active Expired - Lifetime
- 2001-02-21 WO PCT/IB2001/000245 patent/WO2001062840A1/en active IP Right Grant
- 2001-02-21 DE DE60106583T patent/DE60106583T2/de not_active Expired - Lifetime
- 2001-02-21 AU AU2001235889A patent/AU2001235889A1/en not_active Abandoned
- 2001-02-21 ES ES01908030T patent/ES2227138T3/es not_active Expired - Lifetime
- 2001-02-21 JP JP2001562619A patent/JP5427335B2/ja not_active Expired - Lifetime
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US5169925A (en) | 1989-06-16 | 1992-12-08 | Hoechst Aktiengesellschaft | Polymeric polyalkyl-1-oxa-diazaspirodecanes |
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Also Published As
Publication number | Publication date |
---|---|
DE60106583T2 (de) | 2005-03-24 |
EP1268644B1 (en) | 2004-10-20 |
JP2003524050A (ja) | 2003-08-12 |
GB0004436D0 (en) | 2000-04-12 |
EP1268644A1 (en) | 2003-01-02 |
ES2227138T3 (es) | 2005-04-01 |
AU2001235889A1 (en) | 2001-09-03 |
DE60106583D1 (de) | 2004-11-25 |
WO2001062840A1 (en) | 2001-08-30 |
ATE280197T1 (de) | 2004-11-15 |
KR20020079770A (ko) | 2002-10-19 |
JP5427335B2 (ja) | 2014-02-26 |
US20030073768A1 (en) | 2003-04-17 |
US6787591B2 (en) | 2004-09-07 |
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