KR20000071031A - Plastics composition having improved weather resistance - Google Patents
Plastics composition having improved weather resistance Download PDFInfo
- Publication number
- KR20000071031A KR20000071031A KR1019997007298A KR19997007298A KR20000071031A KR 20000071031 A KR20000071031 A KR 20000071031A KR 1019997007298 A KR1019997007298 A KR 1019997007298A KR 19997007298 A KR19997007298 A KR 19997007298A KR 20000071031 A KR20000071031 A KR 20000071031A
- Authority
- KR
- South Korea
- Prior art keywords
- tetramethyl
- bis
- piperidinyl
- compound
- plastic composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 122
- 229920003023 plastic Polymers 0.000 title claims abstract description 103
- 239000004033 plastic Substances 0.000 title claims abstract description 103
- -1 amine compound Chemical class 0.000 claims abstract description 86
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 40
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 40
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 27
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 25
- 239000004611 light stabiliser Substances 0.000 claims abstract description 11
- 229920001155 polypropylene Polymers 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical group C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 25
- 150000002148 esters Chemical class 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 claims description 8
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- NJPUGXZMKBZIQZ-UHFFFAOYSA-N 1,5-dioxaspiro[5.5]undecane-3,3-dicarboxylic acid Chemical compound O1CC(C(=O)O)(C(O)=O)COC11CCCCC1 NJPUGXZMKBZIQZ-UHFFFAOYSA-N 0.000 claims description 6
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- CMXLJKWFEJEFJE-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound C1=CC(OC)=CC=C1C=C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(=O)OC1CC(C)(C)N(C)C(C)(C)C1 CMXLJKWFEJEFJE-UHFFFAOYSA-N 0.000 claims description 6
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000001384 succinic acid Substances 0.000 claims description 5
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 claims description 4
- GUCMKIKYKIHUTM-UHFFFAOYSA-N 3,3,5,5-tetramethyl-1-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]piperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN1C(=O)C(C)(C)NC(C)(C)C1 GUCMKIKYKIHUTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- VPYDVGWWXAYRPP-UHFFFAOYSA-N 1-[2-[[4,6-bis[cyclohexyl-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]amino]-1,3,5-triazin-2-yl]-cyclohexylamino]ethyl]-3,3,5,5-tetramethylpiperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN(C=1N=C(N=C(N=1)N(CCN1C(C(C)(C)NC(C)(C)C1)=O)C1CCCCC1)N(CCN1C(C(C)(C)NC(C)(C)C1)=O)C1CCCCC1)C1CCCCC1 VPYDVGWWXAYRPP-UHFFFAOYSA-N 0.000 claims description 3
- IVVLFHBYPHTMJU-UHFFFAOYSA-N 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11^{8}.2^{6}]henicosan-21-one Chemical compound C1C(C)(C)NC(C)(C)CC21C(=O)NC1(CCCCCCCCCCC1)O2 IVVLFHBYPHTMJU-UHFFFAOYSA-N 0.000 claims description 3
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 claims description 3
- VKQPHJLIVKHAQA-UHFFFAOYSA-N 2-[3-(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]ethanol Chemical compound C1OC(CCO)OCC21COC(CCO)OC2 VKQPHJLIVKHAQA-UHFFFAOYSA-N 0.000 claims description 3
- JVMWIRPVXLBFOI-UHFFFAOYSA-N 2-cycloundecyl-5-(2,2,6,6-tetramethylpiperidin-4-yl)-1,3-oxazole Chemical compound C1C(C)(C)NC(C)(C)CC1C1=CN=C(C2CCCCCCCCCC2)O1 JVMWIRPVXLBFOI-UHFFFAOYSA-N 0.000 claims description 3
- HNTWDNMNGNBFEA-UHFFFAOYSA-N 3,3,5,5-tetramethylpiperazin-2-one Chemical compound CC1(C)CNC(=O)C(C)(C)N1 HNTWDNMNGNBFEA-UHFFFAOYSA-N 0.000 claims description 3
- FBIXXCXCZOZFCO-UHFFFAOYSA-N 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione Chemical compound O=C1C(CCCCCCCCCCCC)CC(=O)N1C1CC(C)(C)NC(C)(C)C1 FBIXXCXCZOZFCO-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- HBWIJRHOEJSLPS-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,5-dioxaspiro[5.5]undecane-3,3-dicarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C1(C(=O)OC2CC(C)(C)N(C)C(C)(C)C2)COC2(CCCCC2)OC1 HBWIJRHOEJSLPS-UHFFFAOYSA-N 0.000 claims description 3
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 claims description 3
- HDFZSCWOTBYTQF-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) 1,5-dioxaspiro[5.5]undecane-3,3-dicarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1(C(=O)OC2CC(C)(C)NC(C)(C)C2)COC2(CCCCC2)OC1 HDFZSCWOTBYTQF-UHFFFAOYSA-N 0.000 claims description 3
- UONLDZHKYCFZRW-UHFFFAOYSA-N n-[6-[formyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-n-(2,2,6,6-tetramethylpiperidin-4-yl)formamide Chemical compound C1C(C)(C)NC(C)(C)CC1N(C=O)CCCCCCN(C=O)C1CC(C)(C)NC(C)(C)C1 UONLDZHKYCFZRW-UHFFFAOYSA-N 0.000 claims description 3
- 229960002920 sorbitol Drugs 0.000 claims description 3
- 235000010356 sorbitol Nutrition 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- OYNOCRWQLLIRON-UHFFFAOYSA-N 1-n,3-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,3-dicarboxamide Chemical compound C1C(C)(C)NC(C)(C)CC1NC(=O)C1=CC=CC(C(=O)NC2CC(C)(C)NC(C)(C)C2)=C1 OYNOCRWQLLIRON-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 17
- 239000012528 membrane Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 101000642226 Apomastus schlingeri U1-cyrtautoxin-As1b Proteins 0.000 description 13
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 13
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- 101710143086 Paralytic peptide 2 Proteins 0.000 description 7
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- 101710100266 Serine/threonine-protein phosphatase 6 catalytic subunit Proteins 0.000 description 6
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- 238000002835 absorbance Methods 0.000 description 5
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- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 5
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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
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- 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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- 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 중합체 및 적어도 하나의 장해-아민 광 안정제(HALS 화합물) 및 적어도 하나의 N-다리목을 갖는 적어도 하나의 다리결합 아민 화합물을 함유하는 플라스틱 조성물에 관한 것으로서,The present invention relates to a plastic composition containing a polymer and at least one obstacle-amine light stabilizer (HALS compound) and at least one bridged amine compound having at least one N-bridge.
상기 다리결합 아민 화합물은 바람직하게 헥사메틸렌테트라민 또는 디아자비시클로[2.2.2]옥탄 또는 상기 화합물의 유도체이며, 중합체는 바람직하게 프로필렌 중합체 또는 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS)이며, 본 발명에 따른 플라스틱 조성물은 내후성을 갖는 것을 특징으로 한다.The bridged amine compound is preferably hexamethylenetetramine or diazabicyclo [2.2.2] octane or a derivative of the compound, the polymer is preferably a propylene polymer or acrylonitrile-butadiene-styrene copolymer (ABS), The plastic composition according to the invention is characterized by having weather resistance.
Description
본 발명은 중합체 및 적어도 하나의 장해-아민 광 안정제를 함유하는 플라스틱 조성물에 관한 것이다.The present invention relates to a plastic composition containing a polymer and at least one obstacle-amine light stabilizer.
하기에서, 장해-아민 광 안정제는 HALS 화합물로 언급될 것이다.In the following, the obstacle-amine light stabilizer will be referred to as a HALS compound.
중합체 및 적어도 하나의 HALS 화합물을 함유하는 플라스틱 조성물은 미국특허 US-A-3,904,581호에 기술되어 있다. 미국특허 US-A-3,904,581호의 특허명세서는 열 및 광에 의해 야기되는 분해에 대해 플라스틱 조성물이 안정화되는 결과로서, 중합체 및, HALS-화합물인 4-아미노피페리딘 화합물을 함유하는 플라스틱 조성물을 기술하고 있다. 일반적으로 열 및 광에 의해 야기되는 분해에 대한, 특히 자외선에 의해 야기되는 분해에 대한 플라스틱 조성물의 안정화는 플라스틱 조성물이 특정의 용도, 예를 들어 실외용도에 적합하게 되는 결과로서 플라스틱 조성물의 내후성을 향상시킨다는 것은 공지되어 있다.Plastic compositions containing a polymer and at least one HALS compound are described in US Pat. No. 3,904,581. The patent specification of US Pat. No. 3,904,581 describes a plastic composition containing a polymer and a 4-aminopiperidine compound, which is a HALS-compound, as a result of stabilizing the plastic composition against degradation caused by heat and light. Doing. In general, the stabilization of a plastic composition against degradation caused by heat and light, in particular against degradation caused by ultraviolet light, is the result of the plastic composition being suitable for a particular use, for example for outdoor use, as a result of the weatherability of the plastic composition. It is known to improve.
중합체 및 적어도 하나의 HALS 화합물을 함유하는 플라스틱 조성물이 이미 양호한 내후성을 가진다 하더라도, 내후성을 갖는 플라스틱 조성물이 필요하다.Although the plastic composition containing the polymer and the at least one HALS compound already has good weather resistance, a plastic composition having weather resistance is needed.
본 발명의 목적은 상기 내후성을 갖는 플라스틱 조성물을 제공하는 것이다.It is an object of the present invention to provide a plastic composition having such weather resistance.
상기 목적은 본 발명에 따른 플라스틱 조성물이 중합체, 적어도 하나의 HALS 화합물 및, 적어도 하나의 N-다리목(bridgehead)을 갖는 적어도 하나의 다리결합(bridge) 아민 화합물을 함유한다는 점에서 본 발명에 따라 이루어진다.This object is according to the invention in that the plastic composition according to the invention contains a polymer, at least one HALS compound and at least one bridge amine compound having at least one N-bridgehead. Is done.
중합체, 적어도 하나의 HALS 화합물 및, 적어도 하나의 N-다리목을 갖는 적어도 하나의 다리결합 아민 화합물을 함유하는 플라스틱 조성물은 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물을 함유하고 있지 않는 공지된 플라스틱 조성물의 내후성보다 매우 향상된 내후성을 가진다는 사실을 알았다. 또한, 중합체, 적어도 하나의 HALS 화합물 및, 적어도 하나의 N-다리목을 갖는 적어도 하나의 다리결합 아민 화합물을 함유하는 플라스틱 조성물은 HALS 화합물 및 다리결합 아민 화합물의 기여합을 기초로 하여 기대된 것보다 더 나은 내후성을 가진다는 것을 알았다. 이는 중합체 및 단지 한 개의 다리결합 아민 화합물을 함유하는 플라스틱 조성물이 열 및 광에 의해 야기되는 분해에 대해 거의 안정화되지 않는다는 것을 알기 때문에 그만큼 더 놀라운 것이다. 따라서, 본 발명에 따른 플라스틱 조성물의 성분중 일부를 선택해서 본 발명의 플라스틱 조성물의 내후성이 공지된 플라스틱 조성물의 내후성의 두배 이상인 내후성을 가질 수 있다는 것을 알았다.Plastic compositions containing a polymer, at least one HALS compound, and at least one bridged amine compound having at least one N-bridge are known to contain no bridged amine compound having at least one N-bridge. It has been found that the plastic composition has weather resistance much improved than the weather resistance of the plastic composition. In addition, plastic compositions containing a polymer, at least one HALS compound, and at least one bridged amine compound having at least one N-bridge are those expected based on the contribution of the HALS compound and the bridged amine compound. It has been found to have better weather resistance. This is even more surprising because we know that plastic compositions containing polymers and only one bridged amine compound are hardly stabilized against degradation caused by heat and light. Accordingly, it has been found that by selecting some of the components of the plastic composition according to the present invention, the weather resistance of the plastic composition of the present invention may have weather resistance that is at least twice the weather resistance of the known plastic composition.
독일특허 DE 2637193호는 광의 영향에 대해 유기 중합체를 보호하는 하기 화학식 1의 구조를 갖는 화합물을 기술하고 있다:DE DE 2637193 describes a compound having the structure of formula (I) which protects the organic polymer against the effects of light:
(상기 화학식 1에서, n=1이면 R은 1 내지 17개의 탄소원자를 갖는 알킬 또는 이소알킬기, 알킬사슬내에 1 내지 4개의 탄소원자를 갖는 페닐알킬기, 페닐기 또는 나프틸기이며, 2개의 염소원자, 히드록실기 또는, 1 내지 4개의 탄소원자를 갖는 많아야 3개의 알콕시기 또는 알킬기로 치환되며, 또는 N 또는 O원자를 갖는 헤테로고리형 5각 또는 6각고리를 나타내며, 반면에 n=2면 R은 2 내지 6개의 탄소원자를 갖는 알킬렌기 또는 페닐렌기를 나타낸다)In Formula 1, when n = 1, R is an alkyl or isoalkyl group having 1 to 17 carbon atoms, a phenylalkyl group having 1 to 4 carbon atoms in the alkyl chain, a phenyl group or a naphthyl group, and two chlorine atoms and a hydroxyl group. Substituted with at most three alkoxy groups or alkyl groups having from 1 to 4 carbon atoms, or a heterocyclic 5- or 6-membered ring having N or O atoms, while n = 2 if R is 2 to Alkylene group or phenylene group having 6 carbon atoms)
독일특허 DE 2637193호는 상기 화학식 1의 화합물이 산화방지제, UV 흡수제, 광 안정제, 아인산염 안정제, 금속 화합물, 에폭시 안정제, 다가 알콜, 정전기 방지제, 방염제 및 색소와 같은 통상의 안정제의 존재하에서 효과적이라는 것을 기술하고 있다. 입체장해 피페리딘 화합물은 UV 흡수제 및/또는 광 안정제의 예로서 언급된다. 상기 화학식 1의 화합물은 HALS 안정제와의 사이에서 상승효과를 갖는 것은 물론이고, 통상의 안정제의 효과를 향상시킨다. 상기 화학식 1의 화합물은 본 발명에 따른 플라스틱 조성물에서 제외된다.German Patent DE 2637193 claims that the compound of formula 1 is effective in the presence of conventional stabilizers such as antioxidants, UV absorbers, light stabilizers, phosphite stabilizers, metal compounds, epoxy stabilizers, polyhydric alcohols, antistatic agents, flame retardants and pigments. It describes. Stereoimmune piperidine compounds are mentioned as examples of UV absorbers and / or light stabilizers. The compound of Formula 1 has a synergistic effect with the HALS stabilizer, as well as improves the effect of the conventional stabilizer. The compound of Formula 1 is excluded from the plastic composition according to the present invention.
본 발명의 범주내에서, 크세논 시험은 내후성을 측정할 때 사용된다. 크세논 시험은 18분 습윤 및 108분 건조의 습윤/건조 사이클에서 55부피%의 상대습도 및 340㎚의 파장에서 0.35W·m-2·㎚-1의 강도를 갖는 62℃의 블랙패널온도에서 여과된 (붕규산 유리) 크세논 램프에서 빛에 노출될 때 분해에 대한 플라스틱 조성물의 내성을 측정한다. 플라스틱 조성물의 분해는 1713㎝-1의 카르보닐 흡광도 및 1860㎝-1의 흡광도에 있어서의 차이와 시간과의 함수로 측정되며, 이를 위해 플라스틱 조성물은 빛, 온도 및 습도의 상기 조합에 적용된다. 내후성은 플라스틱 조성물이 상기 빛, 온도 및 습도의 조합에 적용되는 시간 및 측정된 카르보닐 흡광도사이의 차가 이미 선택된 특정값 이하일때의 시간으로서 나타낸다. 상기 사용된 크세논 시험에서, 상기 값은 막에 대해 0.10 및 플레이트에 대해 0.50이다.Within the scope of the present invention, xenon test is used to measure weather resistance. The xenon test was filtered at a black panel temperature of 62 ° C. with a relative humidity of 55% by volume in a wet / dry cycle of 18 minutes wet and 108 minutes dry and an intensity of 0.35 W · m −2 · nm −1 at a wavelength of 340 nm. The resistance of the plastic composition to degradation is measured when exposed to light in an isolated (borosilicate glass) xenon lamp. Decomposition of the plastic compositions were measured as a function of the difference between the time in the 1713㎝ -1-carbonyl absorbance and the absorbance 1860㎝ -1, plastic compositions for this purpose are applied to the combination of light, temperature and humidity. Weatherability is expressed as the time when the plastic composition is applied to the combination of light, temperature and humidity and when the difference between the measured carbonyl absorbance is below a certain value already selected. In the xenon test used above, the value is 0.10 for the membrane and 0.50 for the plate.
'장해-아민 광 안정제'는 하기 일반식을 갖는 화합물 및 그의 조합물로 이해된다:'Interference-amine light stabilizers' are understood as compounds having the following general formula and combinations thereof:
R1내지 R5는 하기의 독립적인 치환체이다; 적당한 치환체의 예는 수소, 에테르, 에스테르, 아민, 아미드, 알킬, 알케닐, 알키닐, 아랄킬, 시클로알킬 및 아릴기이며, 상기 치환체는 작용기를 함유하는데, 작용기의 예로는 알콜, 케톤, 무수물, 이민, 실록산, 에테르, 카르복실기, 알데히드, 에스테르, 아미드, 이미드, 아민, 니트릴, 에테르, 우레탄 및 그의 조합이 있다. 장해-아민 광 안정제는 또한 중합체의 일부를 형성한다.R 1 to R 5 are the following independent substituents; Examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents contain functional groups, examples of which are alcohols, ketones, anhydrides , Imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and combinations thereof. Hazard-amine light stabilizers also form part of the polymer.
바람직하게, 선택된 HALS 화합물은 치환된 피페리딘 화합물에서 유도된 화합물, 특히 알킬-치환된 피페리딜, 피페리디닐 또는 피페라지논 화합물 및 치환된 알콕시피페리디닐 화합물에서 유도된 특정의 화합물이다. 상기 화합물의 예로는:Preferably, the selected HALS compound is a compound derived from a substituted piperidine compound, in particular a compound derived from an alkyl-substituted piperidyl, piperidinyl or piperazinone compound and a substituted alkoxypiperidinyl compound. . Examples of such compounds are:
- 2,2,6,6-테트라메틸-4-피페리돈;2,2,6,6-tetramethyl-4-piperidone;
- 2,2,6,6-테트라메틸-4-피페리디놀;2,2,6,6-tetramethyl-4-piperidinol;
- 비스-(1,2,2,6,6-펜타메틸피페리딜)-(3',5'-디-tert-부틸-4'-히드록시벤질) 부틸말로네이트;Bis- (1,2,2,6,6-pentamethylpiperidyl)-(3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) butylmalonate;
- 디-(2,2,6,6-테트라메틸-4-피페리딜) 세바케이트(Tinuvin770);Di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin) 770);
- N-(2-히드록시에틸)-2,2,6,6-테트라메틸-4-피페리디놀 및 숙신산의 올리고머(Tinuvin622);Oligomers of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin) 622);
- 시안산과 N,N-디(2,2,6,6-테트라메틸-4-피페리딜) 헥사메틸렌 디아민의 올리고머;Oligomers of cyanic acid with N, N-di (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine;
- 비스-(2,2,6,6-테트라메틸-4-피페리디닐) 숙시네이트;Bis- (2,2,6,6-tetramethyl-4-piperidinyl) succinate;
- 비스-(1-옥틸옥시-2,2,6,6-테트라메틸-4-피페리디닐) 세바케이트 (Tinuvin123);Bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin) 123);
- 비스-(1,2,2,6,6-펜타메틸-4-피페리디닐) 세바케이트(Tinuvin765);Bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin) 765);
- 테트라키스-(2,2,6,6-테트라메틸-4-피페리딜)-1,2,3,4-부탄 테트라카르복실레이트;Tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate;
- N,N'-비스-(2,2,6,6-테트라메틸-4-피페리딜) 헥산-1,6-디아민 (ChimassorbT5);N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine (Chimassorb T5);
- N-부틸-2,2,6,6-테트라메틸-4-피페리딘아민;N-butyl-2,2,6,6-tetramethyl-4-piperidinamine;
- 2,2'-[(2,2,6,6-테트라메틸피페리디닐)이미노]-비스-[에탄올];2,2 '-[(2,2,6,6-tetramethylpiperidinyl) imino] -bis- [ethanol];
- 폴리((6-모르폴린-S-트리아진-2,4-디일) (2,2,6,6-테트라메틸-4-피페리디닐)-이미노헥사메틸렌-(2,2,6,6-테트라메틸-4-피페리디닐)-이미노)(CyasorbUV 3346);Poly ((6-morpholine-S-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) -iminohexamethylene- (2,2,6 , 6-tetramethyl-4-piperidinyl) -imino) (Cyasorb UV 3346);
- 5-(2,2,6,6-테트라메틸-4-피페리디닐)-2-시클로-운데실옥사졸) (HostavinN20);5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cyclo-undecyloxazole) (Hostavin N20);
- 1,1'-(1,2-에탄디일)-비스-(3,3',5,5'-테트라메틸-피페라지논);1,1 '-(1,2-ethanediyl) -bis- (3,3', 5,5'-tetramethyl-piperazinone);
- 8-아세틸-3-도데실-7,7,9,9-테트라메틸-1,3,8-트리아자스피로 (4,5) 데칸-2,4-디온;8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5) decan-2,4-dione;
- 폴리메틸프로필-3-옥시[4(2,2,6,6-테트라메틸)-피페리디닐실록산] (Uvasil299);Polymethylpropyl-3-oxy [4 (2,2,6,6-tetramethyl) -piperidinylsiloxane] (Uvasil 299);
- 1,2,3,4-부탄테트라카르복시산-1,2,3-트리스(1,2,2,6,6-펜타메틸-4-피페리디닐)-4-트리데실 에스테르;1,2,3,4-butanetetracarboxylic acid-1,2,3-tris (1,2,2,6,6-pentamethyl-4-piperidinyl) -4-tridecyl ester;
- α-메틸스티렌-N-(2,2,6,6-테트라메틸-4-피페리디닐)말레이미드 및 N-스테아릴말레이미드의 공중합체;copolymers of α-methylstyrene-N- (2,2,6,6-tetramethyl-4-piperidinyl) maleimide and N-stearylmaleimide;
- 1,2,3,4-부탄테트라카르복시산, β,β,β',β'-테트라메틸-2,4,8,10-테트라옥사스피로[5.5]운데칸-3,9-디에탄올과의 중합체, 1,2,2,6,6-펜타메틸-4-피페리디닐 에스테르(MarkLA63);1,2,3,4-butanetetracarboxylic acid, β, β, β ', β'-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undec-3,9-diethanol Polymers of 1,2,2,6,6-pentamethyl-4-piperidinyl esters (Mark LA63);
- 2,4,8,10-테트라옥사스피로[5.5]운데칸-3,9-디에탄올, β,β,β',β'-테트라메틸-, 1,2,3,4-부탄테트라카르복시산과의 중합체, 2,2,6,6-테트라메틸-4-피페리디닐 에스테르(MarkLA68);2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, β, β, β ', β'-tetramethyl-, 1,2,3,4-butanetetracarboxylic acid Polymers with, 2,2,6,6-tetramethyl-4-piperidinyl esters (Mark LA68);
- D-글루시톨, 1,3:2,4-비스-O-(2,2,6,6-테트라메틸-4-피페리디닐리덴)-(HALS 7);D-glucitol, 1,3: 2,4-bis-O- (2,2,6,6-tetramethyl-4-piperidinylidene)-(HALS 7);
- 7-옥사-3,20-디아자디스피로[5.1.11.2]헤네이코사-21-논의 올리고머, 2,2,4,4-테트라메틸-20-(옥시라닐메틸)(HostavinN30);7-oxa-3,20-diazadispiro [5.1.11.2] heneicosa-21-non oligomer, 2,2,4,4-tetramethyl-20- (oxyranylmethyl) (Hostavin N30);
- 프로판디오산, [(4-메톡시페닐)메틸렌]-, 비스(1,2,2,6,6-펜타메틸-4-피페리디닐) 에스테르 (SanduvorPR 31);Propanedioic acid, [(4-methoxyphenyl) methylene]-, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor PR 31);
- 포름아미드,N,N'-1,6-헥산디일비스[N-(2,2,6,6-테트라메틸-4-피페리디닐)] (Uvinul4050H);Formamide, N, N'-1,6-hexanediylbis [N- (2,2,6,6-tetramethyl-4-piperidinyl)] (Uvinul 4050H);
- 1,3,5-트리아진-2,4,6-트리아민, N,N'''-[1,2-에탄디일비스[[[4,6-비스[부틸(1,2,2,6,6-펜타메틸-4-이페리디닐)아미노]-1,3,5-트리아진-2-일]이미노]-3,1-프로판디일]]-비스[N',N''-디부틸-N',N''-비스(1,2,2,6,6-펜타메틸-4-피페리디닐)(Chimassorb119);1,3,5-triazine-2,4,6-triamine, N, N '''-[1,2-ethanediylbis [[[4,6-bis [butyl (1,2,2) , 6,6-pentamethyl-4-ipridinyl) amino] -1,3,5-triazin-2-yl] imino] -3,1-propanediyl]]-bis [N ', N''-Dibutyl-N', N ''-bis (1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb 119);
- 1,5-디옥사스피로(5,5)운데칸3,3-디카르복시산, 비스(2,2,6,6-테트라메틸-4-페리디닐) 에스테르(CyasorbUV-500);1,5-dioxaspiro (5,5) undecane3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-ferridinyl) ester (Cyasorb UV-500);
- 1,5-디옥사스피로(5,5)운데칸3,3-디카르복시산, 비스(1,2,2,6,6-펜타메틸-4-페리디닐) 에스테르(CyasorbUV-516);1,5-dioxaspiro (5,5) undecane3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-ferridinyl) ester (Cyasorb UV-516);
- N-2,2,6,6-테트라메틸-4-피페리디닐-N-아미노-옥스아미드;N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide;
- 4-아크릴로일옥시-1,2,2,6,6-펜타메틸-4-피페리딘;4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine;
- 1,5,8,12-테트라키스[2',4'-비스(1", 2", 2", 6", 6"-펜타메틸-4"-피페리디닐(부틸)아미노)-1',3',5'-트리아진-6'-일]-1,5,8,12-테트라자도데칸;1,5,8,12-tetrakis [2 ', 4'-bis (1 ", 2", 2 ", 6", 6 "-pentamethyl-4" -piperidinyl (butyl) amino)- 1 ', 3', 5'-triazine-6'-yl] -1,5,8,12-tetrazadodecane;
- HALS PB-41(Clariant Huningue S.A.);HALS PB-41 from Clariant Huningue S.A .;
- NylostabS-EED(Clariant Huningue S.A.);-Nylostab Clariant Huningue SA (S-EED);
- 3-도데실-1-(2,2,6,6-테트라메틸-4-피페리딜)-피롤리딘-2,5-디온 (UvasorbHA88);3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione (Uvasorb HA88);
- 1,1'-(1,2-에탄-디-일)-비스-(3,3',5,5'-테트라메틸-피페라지논) (Good-rite3034);1,1 '-(1,2-ethane-di-yl) -bis- (3,3', 5,5'-tetramethyl-piperazinone) (Good-rite 3034);
- 1,1',1"-(1,3,5-트리아진-2,4,6-트리일트리스((시클로헥실이미노)-2,1-에탄디일)트리스(3,3,5,5-테트라메틸피페라지논)(Good-rite3150);1,1 ', 1 "-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,5 , 5-tetramethylpiperazinone) (Good-rite 3150);
- 1,1',1"-(1,3,5-트리아진-2,4,6-트리일트리스((시클로헥실이미노)-2,1-에탄디일)트리스(3,3,4,5,5-테트라메틸피페라지논)(Good-rite3159)이 있다.1,1 ', 1 "-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,4 , 5,5-tetramethylpiperazinone) (Good-rite 3159).
디-(2,2,6,6-테트라메틸-4-피페리딜)세바케이트(또한 상표명 Tinuvin770으로 공지됨), N-(2-히드록시에틸)-2,2,6,6-테트라메틸-4-피페리디놀 및 숙신산의 올리고머(Tinuvin622); 비스-(1-옥틸옥시-2,2,6,6-테트라메틸-4-피페리디닐) 세바케이트(Tinuvin123); 비스-(1,2,2,6,6-펜타메틸-4-피페리디닐) 세바케이트(Tinuvin765); N,N'-비스-(2,2,6,6-테트라메틸-4-피페리딜) 헥산-1,6-디아민(ChimassorbT5); 폴리((6-모르폴린-S-트리아진-2,4-디일) (2,2,6,6-테트라메틸-4-피페리디닐)-이미노헥사메틸렌-(2,2,6,6-테트라메틸-4-피페리디닐)-이미노)(CyasorbUV 3346); 5-(2,2,6,6-테트라메틸-4-피페리디닐)-2-시클로-운데실옥사졸) (HostavinN20); 폴리메틸프로필-3-옥시[4(2,2,6,6-테트라메틸)-피페리디닐실록산] (Uvasil299); 1,2,3,4-부탄테트라카르복시산, β,β,β',β'-테트라메틸-2,4,8,10-테트라옥사스피로[5.5]운데칸-3,9-디에탄올과의 중합체, 1,2,2,6,6-펜타메틸-4-피페리디닐 에스테르(MarkLA63); 2,4,8,10-테트라옥사스피로[5.5]운데칸-3,9-디에탄올, β,β,β',β'-테트라메틸-, 1,2,3,4-부탄테트라카르복시산과의 중합체, 2,2,6,6-테트라메틸-4-피페리디닐 에스테르(MarkLA68); D-글루시톨, 1,3:2,4-비스-O-(2,2,6,6-테트라메틸-4-피페리디닐리덴)-(HALS7); 7-옥사-3,20-디아자디스피로[5.1.11.2]헤네이코사-21-논, 2,2,4,4-테트라메틸-20-(옥시라닐메틸)(HostavinN30); 프로판디오산, [(4-메톡시페닐)메틸렌]-, 비스(1,2,2,6,6-펜타메틸-4-피페리디닐) 에스테르 (SanduvorPR 31); 포름아미드,N,N'-1,6-헥산디일비스[N-(2,2,6,6-테트라메틸-4-피페리디닐)] (Uvinul4050H); 1,3,5-트리아진-2,4,6-트리아민, N,N'''-[1,2-에탄디일비스[[[4,6-비스[부틸(1,2,2,6,6-펜타메틸-4-이페리디닐)아미노]-1,3,5-트리아진-2-일]이미노]-3,1-프로판디일]]-비스[N',N''-디부틸-N',N''-비스(1,2,2,6,6-펜타메틸-4-피페리디닐)(Chimassorb119); 1,5-디옥사스피로(5,5)운데칸 3,3-디카르복시산, 비스(2,2,6,6-테트라메틸-4-페리디닐) 에스테르(CyasorbUV-500); 1,5-디옥사스피로(5,5)운데칸 3,3-디카르복시산, 비스(1,2,2,6,6-펜타메틸-4-페리디닐) 에스테르(CyasorbUV-516); 2,2,6,6-테트라메틸-4-피페리디놀의 에스테르와 지방산의 혼합물(CyasorbUV 3853); HALS PB-41(Clariant Huningue S.A.); NylostabS-EED(Clariant Huningue S.A.); 3-도데실-1-(2,2,6,6-테트라메틸-4-피페리딜)-피롤리딘-2,5-디온 (UvasorbHA88); 1,1'-(1,2-에탄-디-일)-비스-(3,3',5,5'-테트라메틸-피페라지논) (Good-rite3034); 1,1',1"-(1,3,5-트리아진-2,4,6-트리일트리스((시클로헥실이미노)-2,1-에탄디일)트리스(3,3,5,5-테트라메틸피페라지논)(Good-rite3150); 1,1',1"-(1,3,5-트리아진-2,4,6-트리일트리스((시클로헥실이미노)-2,1-에탄디일)트리스(3,3,4,5,5-테트라메틸피페라지논)(Good-rite3159)을 사용하는 것이 바람직하다.Di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (also trade name Tinuvin 770), N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and oligomers of succinic acid (Tinuvin 622); Bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 123); Bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin) 765); N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine (Chimassorb T5); Poly ((6-morpholine-S-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) -iminohexamethylene- (2,2,6, 6-tetramethyl-4-piperidinyl) -imino) (Cyasorb UV 3346); 5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cyclo-undecyloxazole) (Hostavin N20); Polymethylpropyl-3-oxy [4 (2,2,6,6-tetramethyl) -piperidinylsiloxane] (Uvasil 299); With 1,2,3,4-butanetetracarboxylic acid, β, β, β ', β'-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol Polymer, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark LA63); 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, β, β, β ', β'-tetramethyl-, 1,2,3,4-butanetetracarboxylic acid Polymer of 2,2,6,6-tetramethyl-4-piperidinyl ester (Mark LA68); D-glucitol, 1,3: 2,4-bis-O- (2,2,6,6-tetramethyl-4-piperidinylidene)-(HALS7); 7-oxa-3,20-diazadispiro [5.1.11.2] heneicosa-21-non, 2,2,4,4-tetramethyl-20- (oxyranylmethyl) (Hostavin N30); Propanedioic acid, [(4-methoxyphenyl) methylene]-, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor PR 31); Formamide, N, N'-1,6-hexanediylbis [N- (2,2,6,6-tetramethyl-4-piperidinyl)] (Uvinul 4050H); 1,3,5-triazine-2,4,6-triamine, N, N '''-[1,2-ethanediylbis [[[4,6-bis [butyl (1,2,2, 6,6-pentamethyl-4-ipridinyl) amino] -1,3,5-triazin-2-yl] imino] -3,1-propanediyl]]-bis [N ', N'' -Dibutyl-N ', N''-bis (1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb 119); 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-ferridinyl) ester (Cyasorb UV-500); 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-ferridinyl) ester (Cyasorb UV-516); Mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol with fatty acids UV 3853); HALS PB-41 from Clariant Huningue SA; Nylostab Clariant Huningue SA (S-EED); 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione (Uvasorb HA88); 1,1 '-(1,2-ethane-di-yl) -bis- (3,3', 5,5'-tetramethyl-piperazinone) (Good-rite 3034); 1,1 ', 1 "-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,5, 5-tetramethylpiperazinone) (Good-rite 3150); 1,1 ', 1 "-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,4, 5,5-tetramethylpiperazinone) (Good-rite 3159) is preferred.
본 발명의 범주내에서 사용될 수 있는 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 하기 구조식 1 또는 2의 화합물로부터 유도된 화합물인 것이 바람직하다.It is preferred that the bridged amine compound having at least one N-legged compound that can be used within the scope of the present invention is a compound derived from the compound of formula 1 or 2 below.
구조식 1Structural Formula 1
구조식 2Structural Formula 2
(상기 구조식 1 및 2에서, M1내지 M4는 다리목이며, 각 다리목은 탄소, 질소, 규소 또는 인에서 선택되며, 적어도 하나의 다리목이 항상 질소 원자 및 탄소인 조건부로 규소가 치환되며; N-다리목은 질소원자인 다리목로 정의되며; 여기서 Dl, Dm, Dn, Do, Dp및 Dq는 각각 1 내지 20개 원자의 길이를 갖는 사슬을 나타내며, 사슬이 형성되는 원자의 수는 l, m, n, o, p 및 q와 같으며, 각 원자수 및 원자종류는 독립적으로 선택되며, 사슬은 다른 길이를 가질 수 있고, 다른 종류의 원자로 이루어질 수 있다)(In the above formulas 1 and 2, M 1 to M 4 is a leg, each leg is selected from carbon, nitrogen, silicon or phosphorus, and silicon is conditionally substituted at least one leg is always a nitrogen atom and carbon) N-bridges are defined as bridges which are nitrogen atoms; where D l , D m , D n , D o , D p and D q represent chains with a length of 1 to 20 atoms each; The number of atoms to be formed is equal to l, m, n, o, p, and q, and each atom number and atom type are independently selected, and the chains may have different lengths and may be composed of different kinds of atoms)
상기 사슬은 또한 측기를 포함하며, 측기내 원자수는 사슬의 원자수에 포함되지 않는다. 사슬을 이루는 원자로는 탄소, 질소, 산소, 규소 및 인이 적당하다. 상기 사슬은 1 내지 3개의 탄소원자로 이루어진 것이 바람직하다.The chain also includes side groups and the number of atoms in the side groups is not included in the number of atoms in the chain. Suitable chain atoms are carbon, nitrogen, oxygen, silicon and phosphorus. The chain is preferably composed of 1 to 3 carbon atoms.
바람직하게, 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 HALS 화합물의 양 기준부 약 1:20(m:m) 내지 약 20:1(m:m), 더 바람직하게 약 1:10(m:m) 내지 약 10:1(m:m), 가장 바람직하게 약 1:5(m:m) 내지 약 5:1(m:m)의 비율로 HALS 화합물과 함께 사용된다. 나중 비율의 한계내에서, 내후성은 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물의 양 및 존재하는 HALS 화합물을 기준으로 하여 기대되는 것 이상이다.Preferably, the bridged amine compound having at least one N-bridge is from about 1:20 (m: m) to about 20: 1 (m: m), more preferably about 1:10, based on the amount of HALS compound (m: m) to about 10: 1 (m: m), most preferably from about 1: 5 (m: m) to about 5: 1 (m: m) with a HALS compound. Within the limits of the later ratios, weather resistance is beyond what is expected based on the amount of bridged amine compounds having at least one N-leg and the HALS compounds present.
플라스틱 조성물에 사용될 수 있는 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물의 양은 매우 다양하며, 이는 당 분야에 보통의 기술을 가진 자에 의해 쉽게 측정될 수 있다. 상기 범위는 중합체의 종류, HALS 화합물의 종류, 첨가제 패키지내 다른 첨가제, 이루어진 내후성 또는 플라스틱 조성물의 종류, 그의 특성 및 그의 특정용도에 따라 다르다.The amount of at least one N-bridged crosslinked amine compound that can be used in the plastic composition varies widely and can be readily determined by one of ordinary skill in the art. The range depends on the type of polymer, the type of HALS compound, the other additives in the additive package, the type of weather resistance or plastic composition made, its properties and its particular use.
예를 들어, 다리결합 아민 화합물은 플라스틱 조성물내 중합체의 양 기준부, 바람직하게 약 0.01중량% 내지 약 10.0중량%, 더 바람직하게 0.05중량% 내지 약 5중량%, 가장 바람직하게 약 0.1중량% 내지 약 2.5중량%의 양으로 플라스틱 조성물내에 존재하는 적어도 하나의 N-다리목을 가질 수 있다.For example, the bridged amine compound may be present in an amount based on the amount of the polymer in the plastic composition, preferably from about 0.01% to about 10.0%, more preferably from 0.05% to about 5%, most preferably from about 0.1% to It may have at least one N-bridge present in the plastic composition in an amount of about 2.5% by weight.
바람직하게, 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 크세논 시험에 의해 측정된 내후성이 약 500시간 이상, 더 바람직하게 약 750시간 이상, 및 가장 바람직하게 약 1000시간 이상인 플라스틱 조성물이 얻어지도록 선택된다.Preferably, the bridged amine compound having at least one N-bridge is obtained with a plastic composition having a weather resistance measured by xenon test of at least about 500 hours, more preferably at least about 750 hours, and most preferably at least about 1000 hours. Is chosen to lose.
적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물로는:As a bridged amine compound having at least one N-bridge:
- 7-니트로-1,3,5-트리아자다만탄 및 7-아미노-1,3,5-트리아자다만탄의 유도체,Derivatives of 7-nitro-1,3,5-triazadamantane and 7-amino-1,3,5-triazadamantane,
- 하기 화학식 2 또는 3의 구조를 갖는 7-아미노-1,3,5-트리아자다만탄의 유도체를 선택하는 것이 적당하다:It is suitable to select derivatives of 7-amino-1,3,5-triazadamantane having the structure of formula (2) or (3):
(상기 화학식 2 및 3에서, R 및 R'는 독립적인 치환체이며; 적당한 치환체의 예로는 수소, 에테르, 에스테르, 아민, 아미드, 알킬, 알케닐, 알키닐, 아랄킬, 시클로알킬 및 아릴기가 있으며, 상기 치환체는 차례로 작용기; 예를 들어 알콜, 케톤, 무수물, 이민, 실록산, 에테르, 카르복실기, 알데히드, 에스테르, 아미드, 이미드, 아민, 니트릴, 에테르, 우레탄 및 그의 조합물을 포함한다)(In Formulas 2 and 3, R and R 'are independent substituents; examples of suitable substituents include hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups. , Substituents in turn include functional groups; for example alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and combinations thereof)
게다가 치환체는 여러 Ⅰ 및/또는 Ⅱ 화합물을 다른 것에 연결한다.In addition, substituents link several I and / or II compounds to another.
- 하나 또는 그 이상의 작용기를 함유하는 화합물과 7-아미노-1,3,5-트리아자다만탄과의 반응에서 얻어진 유도체. 상기 작용기의 예로는 알데히드, 산, 에스테르, 아미드, 케톤, 무수물 및 이소시아네이트가 있다.Derivatives obtained by the reaction of a compound containing one or more functional groups with 7-amino-1,3,5-triazadamantane. Examples of such functional groups are aldehydes, acids, esters, amides, ketones, anhydrides and isocyanates.
- 이미드 작용기에 의해 중합체(폴리올레핀이 바람직함)에 결합된 트리아자다만탄 유도체;Triazadamantane derivatives bound to polymers (preferably polyolefins) by imide functionality;
- 말레산 무수물로 기능화된 중합체(폴리올레핀이 바람직함)와 7-아미노-1,3,5-트리아자다만탄과의 반응에 의해 얻어진 중합체-결합 화합물;Polymer-binding compounds obtained by reaction of polymers functionalized with maleic anhydride (preferably polyolefins) with 7-amino-1,3,5-triazadamantane;
- 헥사메틸렌테트라민(HMTA), 디아자비시클로[2.2.2] 옥탄(DABCO) 또는 그의 유도체. HMTA 및 DABCO는 상업적으로 얻어지기 쉬우며, 일반적으로 공지된 방법을 사용하여 제조되기 쉽다. 예를 들어, HMTA는 저렴하고 쉽게 얻을 수 있는 염기성 원료 암모니아 및 포름알데히드로부터 쉽게 제조될 수 있다.Hexamethylenetetramine (HMTA), diazabicyclo [2.2.2] octane (DABCO) or derivatives thereof. HMTA and DABCO are easy to obtain commercially and are generally easy to prepare using known methods. For example, HMTA can be readily prepared from basic raw ammonia and formaldehyde, which are inexpensive and readily available.
적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 바람직하게 염, 더 바람직하게 암모늄염으로 사용된다. 바람직하게, 카르복시산은 염-생성제로서 선택된다. 적당한 카르복시산의 예로는 지방족 카르복시산, 지방족 디카르복시산 및 방향족 카르복시산이 있다. 스테아르산, 세바산, 시크로헥산디카르복시산 및 벤젠트리카르복시산을 선택하는 것이 적당하다. 바람직하게, 염-생성제가 할로겐 또는 황을 함유한다면 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 일반적으로 할로겐-함유 또는 황-함유 화합물은 HALS 안정제의 효과를 감소시킬 수 있다고 알려져 있으므로 염으로 사용되지 않는다.The bridged amine compound having at least one N-leg is preferably used as a salt, more preferably as ammonium salt. Preferably the carboxylic acid is selected as a salt-generating agent. Examples of suitable carboxylic acids are aliphatic carboxylic acids, aliphatic dicarboxylic acids and aromatic carboxylic acids. It is suitable to select stearic acid, sebaic acid, cyclohexanedicarboxylic acid and benzenetricarboxylic acid. Preferably, if the salt-generating agent contains halogen or sulfur, the bridged amine compound having at least one N-bridge is generally known that halogen-containing or sulfur-containing compounds can reduce the effect of HALS stabilizers. Not used as
적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 바람직하게 적어도 50, 더 바람직하게 적어도 100의 분자량을 갖는 적어도 하나의 치환체로 치환되는 것이 바람직하다.The bridged amine compound having at least one N-leg is preferably substituted with at least one substituent having a molecular weight of at least 50, more preferably at least 100.
약 50 이상의 분자량을 갖는 적어도 하나의 치환체로 치환되거나 또는 그의 염 형태로, 또는 약 50 이상의 분자량을 갖는 적어도 하나의 치환체로 치환되고 그의 염 형태로 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물을 사용한 결과, 더 나은 내후성을 갖는 플라스틱 조성물이 얻어진다는 것을 알았다.A bridged amine compound substituted with at least one substituent having a molecular weight of about 50 or greater, or in salt form thereof, or at least one substituent having a molecular weight of about 50 or greater, and having at least one N-bridge in its salt form As a result, it was found that a plastic composition having better weather resistance was obtained.
본 발명의 플라스틱 조성물은 폴리올레핀 및 스티렌 중합체의 그룹에서 선택된 열가소성 중합체를 함유하는 것이 바람직하다. 예를 들어, 프로필렌 중합체, 가령 프로필렌 단일중합체, 에틸렌-프로필렌 랜덤 공중합체, 에틸렌-프로필렌 블록 공중합체 및 그의 혼합물을 선택하는 것이 적당하다. 또한, 본 발명의 범주내의 프로필렌 중합체는 예를 들어 폴리에틸렌 또는 에틸렌-프로필렌-디엔 공중합체; 에틸렌 중합체, 가령 저밀도 폴리에틸렌(LDPE), 고밀도 폴리에틸렌(HDPE), 극 저밀도 폴리에틸렌(VLDPE), 선형-저밀도 폴리에틸렌(LLDPE) 또는 초-고분자량 폴리에틸렌(UHMWPE); 부틸렌 중합체, 가령 폴리(1-부틸렌)을 갖는 상기 프로필렌 중합체의 적어도 50중량%를 함유하는 혼합물이다. 스티렌 중합체로는 예를 들어, 폴리스티렌, 고-내충격성 폴리스티렌(HIPS), 스티렌-아크릴로니트릴 공중합체(SAN), 아크릴로니트릴-부타디엔 스티렌 공중합체(ABS), 스티렌-말레산 무수물 공중합체(SMA) 및 스티렌-말레이미드 공중합체(SMI)를 선택하는 것이 적당하다.The plastic composition of the present invention preferably contains a thermoplastic polymer selected from the group of polyolefins and styrene polymers. For example, it is appropriate to select propylene polymers such as propylene homopolymers, ethylene-propylene random copolymers, ethylene-propylene block copolymers and mixtures thereof. In addition, propylene polymers within the scope of the invention include, for example, polyethylene or ethylene-propylene-diene copolymers; Ethylene polymers such as low density polyethylene (LDPE), high density polyethylene (HDPE), ultra low density polyethylene (VLDPE), linear-low density polyethylene (LLDPE) or ultra-high molecular weight polyethylene (UHMWPE); Butylene polymers, such as mixtures containing at least 50% by weight of said propylene polymer with poly (1-butylene). As the styrene polymer, for example, polystyrene, high-impact polystyrene (HIPS), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene styrene copolymer (ABS), styrene-maleic anhydride copolymer ( SMA) and styrene-maleimide copolymers (SMI) are suitable.
더 바람직하게, 중합체는 프로필렌 중합체 또는 ABS이며, 보다 바람직하게 프로필렌 중합체이다.More preferably, the polymer is a propylene polymer or ABS, more preferably a propylene polymer.
적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 성형 부품, 시트, 막, 섬유, 코팅, 폼, 테잎, 라텍스 또는 분말과 같은 플라스틱 물품을 플라스틱 조성물에서 제조하기 전에 원하는 시간에 당업자에게 공지된 많은 표준방법중 하나에 의해 플라스틱 조성물에 도입될 수 있다.Bridge-bonded amine compounds having at least one N-bridge are known to those skilled in the art at desired times prior to making plastic articles, such as molded parts, sheets, membranes, fibers, coatings, foams, tapes, latexes or powders, in plastic compositions It can be introduced into the plastic composition by one of many standard methods.
제1 방법에 따라, 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 분말 또는 용융물의 형태의 플라스틱 조성물의 다른 성분과 분말, 용액, 유탁액 또는 현탁액의 형태로 혼합된다.According to the first method, the bridged amine compound having at least one N-leg is mixed with other components of the plastic composition in the form of a powder or melt in the form of a powder, solution, emulsion or suspension.
제2 방법에 따라, 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물은 먼저 적어도 하나의 HALS 화합물과 혼합되며, 선택적으로 소위 첨가제 패키지, 예를 들어 분말, 용액, 유탁액 또는 현탁액의 형태로 다른 첨가제와 혼합되며, 상기 패키지는 분말 또는 용융물의 형태로 플라스틱 내에 가해진다.According to the second method, the bridged amine compound having at least one N-leg is first mixed with at least one HALS compound and optionally in the form of a so-called additive package, for example a powder, solution, emulsion or suspension. Mixed with other additives, the package is applied in plastic in the form of a powder or melt.
중합체, 적어도 하나의 HALS 화합물 및 적어도 하나의 N-다리목을 갖는 적어도 하나의 다리결합 아민 화합물을 함유하는 플라스틱 조성물은 다른 첨가제, 예를 들어 산화방지제, 열안정제 및 UV 안정제, 금속 비활성화제, 충진제, 색소, 방염제, 광 표백제 및 플라스틱 조성물에 사용되는 유사 첨가제를 포함한다.Plastic compositions containing a polymer, at least one HALS compound and at least one bridged amine compound having at least one N-legged polymer may be prepared by other additives such as antioxidants, heat stabilizers and UV stabilizers, metal deactivators, fillers. , Pigments, flame retardants, photo bleaches and similar additives used in plastic compositions.
본 발명은 하기의 실시예를 참고로 더 설명될 것이며, 여기에 한정되지 않는다.The invention will be further described with reference to the following examples, which are not intended to be limiting.
실시예Example
본 실시예에서, 하기 방법을 실시했다.In this example, the following method was carried out.
여러 다리결합 아민의 제조Preparation of Multiple Crosslinked Amines
DABCO 스테아레이트:DABCO Stearate:
에탄올내 스테아르산 28.45g(0.1mol) 용액을 실온에서 교반하면서 에탄올내 DABCO 11.2g(0.1mol) 용액에 점적으로 가하였다. 상기 혼합물을 Rotavap에 의해 증발시켰다.A 28.45 g (0.1 mol) solution of stearic acid in ethanol was added dropwise to a 11.2 g (0.1 mol) solution of DABCO in ethanol with stirring at room temperature. The mixture was evaporated by Rotavap.
HMTA 스테아레이트:HMTA Stearate:
에탄올내 스테아르산 28.45g(0.1mol) 용액을 교반하면서 에탄올내 DABCO 14g(0.1mol) 용액에 점적으로 가하였다. 상기 혼합물을 Rotavap에 의해 증발시켰다.A 28.45 g (0.1 mol) solution of stearic acid in ethanol was added dropwise to a 14 g (0.1 mol) solution of DABCO in ethanol with stirring. The mixture was evaporated by Rotavap.
DABCO 세바케이트:DABCO Sebacate:
메탄올내 세바산 20.2g(0.1mol) 용액을 실온에서 교반하면서 메탄올내 DABCO 22.4g(0.2mol) 용액에 점적으로 가하였다. 상기 혼합물을 Rotavap에 의해 증발시켰다.A 20.2 g (0.1 mol) solution of sebaic acid in methanol was added dropwise to a solution of 22.4 g (0.2 mol) of DABCO in methanol with stirring at room temperature. The mixture was evaporated by Rotavap.
DABCO 벤젠 트리카르복실레이트:DABCO Benzene Tricarboxylate:
절대 에탄올내 벤젠 트리카르복실산 21g(0.1mol) 용액을 실온에서 교반하면서 절대 에탄올내 DABCO 33.6g(0.3mol) 용액에 점적으로 가하였다. 상기 용액에서 염이 침전되었다. 상기 혼합물을 Rotavap에 의해 증발시키고, 진공건조 스토브에서 건조시켰다.A 21 g (0.1 mol) solution of benzene tricarboxylic acid in absolute ethanol was added dropwise to a 33.6 g (0.3 mol) solution of DABCO in absolute ethanol with stirring at room temperature. A salt precipitated out of the solution. The mixture was evaporated by Rotavap and dried in a vacuum drying stove.
DABCO 디스테아레이트:DABCO distearate:
에탄올내 스테아르산 56.9g(0.2mol) 용액을 실온에서 교반하면서 에탄올내 DABCO 11.2g(0.1mol) 용액에 점적으로 가하였다. 상기 혼합물을 Rotavap에 의해 증발시키고, 진공건조 스토브에서 건조시켰다.A 56.9 g (0.2 mol) solution of stearic acid in ethanol was added dropwise to a 11.2 g (0.1 mol) solution of DABCO in ethanol with stirring at room temperature. The mixture was evaporated by Rotavap and dried in a vacuum drying stove.
7-니트로-1,3,5-트리아자다만탄:7-nitro-1,3,5-triazadamantane:
니트로메탄 56.8㎖(1.0mol)와 포름산 45㎖(1.2mol)의 혼합물을 일정하게 교반하고, 환류하면서 에탄올(80%) 500㎖내 헥사메틸렌테트라민 140.2g(1.0mol) 용액에 가했다. 상기 혼합물을 4시간동안 환류하고, 하룻밤 방치하였다. 분리된 결정질의 생성물을 물과 에탄올로 몇 분동안 세척했다. 물에서 재결정화후, 생성물(백색 니들(needle)을 진공건조 스토브에서 건조시켰다.(문헌: Czechoslov. Chem. Commun Collection [제40권], 1975, pp.2179-82).A mixture of 56.8 ml (1.0 mol) of nitromethane and 45 ml (1.2 mol) of formic acid was constantly stirred and added to a solution of 140.2 g (1.0 mol) of hexamethylenetetramine in 500 ml of ethanol (80%) while refluxing. The mixture was refluxed for 4 hours and left overnight. The separated crystalline product was washed with water and ethanol for several minutes. After recrystallization in water, the product (white needle was dried on a vacuum drying stove. Czechoslov. Chem. Commun Collection [Vol. 40], 1975, pp. 2179-82).
7-아미노-1,3,5-트리아자다만탄:7-amino-1,3,5-triazadamantane:
7-니트로-1,3,5-트리아자다만탄 15.0g, 메탄올 100㎖ 및 촉매로서의 습윤 라니코발트 1.5g을 교반기 및 배플(baffle)을 구비한 Parr 오토클레이트(부피 160㎖)에 넣었다. 80bar 압력 및 80℃의 수소하에서 최대 속도로 1시간동안 수소화를 실시하였다. 여과를 통해 촉매를 제거한후, Rotavapor에 의해 메탄올을 제거하였다. 결정질의 생성물을 진공건조 스토브에서 건조시켰다.15.0 g of 7-nitro-1,3,5-triazadamantane, 100 ml of methanol and 1.5 g of wet lanicobalt as catalyst were placed in a Parr autoclave (volume 160 ml) with a stirrer and baffle. Hydrogenation was carried out at 80 bar pressure and 80 ° C. for 1 hour at maximum speed. After the catalyst was removed by filtration, methanol was removed by Rotavapor. The crystalline product was dried in a vacuum drying stove.
7-도데실리덴아미노-1,3,5-트리아자다만탄:7-dodecylideneamino-1,3,5-triazadamantane:
7-아미노-1,3,5-트리아자다만탄 8.4g, 도데칸알 10.0g, 메탄올 85㎖, 톨루엔 10㎖ 및 촉매로서의 습윤 라니코발트 2.0g을 교반기 및 배플을 구비한 Parr 오토클레이트(부피 160㎖)에 넣었다. 80℃에서 최대 속도로 질소대기(2bar)하에서 1시간동안 반응을 실시하였다. 여과를 통해 촉매를 제거한후, Rotavapor에 의해 여과물을 증발시킨후 진공건조 스토브에서 건조시켰다.8.4 g of 7-amino-1,3,5-triazadamantane, 10.0 g dodecanal, 85 ml of methanol, 10 ml of toluene and 2.0 g of wet ranicobalt as a catalyst were prepared using a Parr autoclave with a stirrer and a baffle (volume 160 ml). The reaction was carried out at 80 ° C. under a nitrogen atmosphere (2 bar) for 1 hour. After removing the catalyst through filtration, the filtrate was evaporated by Rotavapor and dried on a vacuum drying stove.
PP-MA-7-아미노-1,3,5-트리아자다만탄:PP-MA-7-amino-1,3,5-triazadamantane:
160-165℃에서 일정하게 교반하면서, 용매 75㎖내 7-아미노-1,3,5-트리아자다만탄 0.8g을 비활성 용매 150㎖내 PP-MA(HostaprimeHC5)(약 2.8% 말레산 무수물과 결합된 PP) 10.0g 용액에 점적으로 가하였다. 약 90℃로 냉각시킨후, 상기 생성물을 아세톤 100㎖를 사용하여 침전시켰다. 분리된 생성물을 진공건조 스토브에서 건조시킨후, 210℃에서 압착하여 플레이트를 제조하였다. 그후에 극저온에서 분말로 분쇄하였다.With constant stirring at 160-165 ° C., 0.8 g of 7-amino-1,3,5-triazadamantane in 75 ml of solvent was added to PP-MA (Hostaprime) in 150 ml of inert solvent. Was added dropwise to a 10.0 g solution of HC5) (PP combined with about 2.8% maleic anhydride). After cooling to about 90 ° C., the product was precipitated using 100 ml of acetone. The separated product was dried on a vacuum drying stove and then pressed at 210 ° C. to prepare a plate. It was then ground to powder at cryogenic temperatures.
플라스틱 조성물의 제조Preparation of Plastic Composition
중합체 분말(PP 또는 ABS)을 일정량의 HALS 화합물을 함유하는 용액과 혼합하였다. 상기 혼합물을 28℃의 온도 및 약 20mmHg의 압력에서 24시간동안 오븐(Hereaus Vacutherm)내에서 건조시켰다. 그후, 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물 용액을 플라스틱 조성물에 가했다. 상기 플라스틱 조성물을 또한 상기 기술된 바와 같은 방법으로 건조시켰다. 용액내에 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물 및/또는 HALS 화합물의 양이 0인 플라스틱 조성물(블랭크)은 또한 상기 방법을 사용하여 제조되었다.Polymer powder (PP or ABS) was mixed with a solution containing an amount of the HALS compound. The mixture was dried in an oven (Hereaus Vacutherm) for 24 hours at a temperature of 28 ° C. and a pressure of about 20 mm Hg. Thereafter, a bridged amine compound solution having at least one N-leg was added to the plastic composition. The plastic composition was also dried in the manner as described above. Plastic compositions (blanks) in which the amount of the bridged amine compound and / or the HALS compound having at least one N-leg in the solution are zero were also prepared using the above method.
PP 막 및 플레이트의 제조Preparation of PP Membranes and Plates
Fontijne 프레스(TP200형, 가압하지 않은 상태에서 190℃에서 5분간 예열한후, 100-120kNewton의 압력을 가하고, 그후 상기 압력에서 10분 냉각시킴)를 사용하여 PP 조성물을 압착하여 막을 형성하였다. 두께는 하이덴하인(HeidenHain) 전자계량기를 사용하여 측정하였다. 대략, 120-150㎛ 두께의 막 및 1㎜ 두께의 플레이트가 얻어졌다.The PP composition was pressed to form a film using a Fontijne press (TP200 type, pre-heated at 190 ° C. for 5 minutes without pressurization, followed by a pressure of 100-120 kNewton, then cooled at that pressure for 10 minutes). The thickness was measured using a HeidenHain electron meter. Approximately 120-150 μm thick films and 1 mm thick plates were obtained.
ABS 막 및 플레이트의 제조Preparation of ABS Membrane and Plate
Fontijne 프레스(TP200형, 가압하지 않은 상태에서 210℃에서 5분간 예열한후, 100-120kNewton의 압력을 가하고, 그후 상기 압력에서 10분 냉각시킴)를 사용하여 ABS 조성물을 압착하여 막을 형성하였다. 두께는 하이덴하인(HeidenHain) 전자계량기를 사용하여 측정하였다. 대략, 120-150㎛ 두께의 막 및 1㎜ 두께의 플레이트가 얻어졌다.The film was formed by pressing the ABS composition using a Fontijne press (TP200 type, pre-heated at 210 ° C. for 5 minutes under no pressure, followed by a pressure of 100-120 kNewton, followed by cooling for 10 minutes at that pressure). The thickness was measured using a HeidenHain electron meter. Approximately 120-150 μm thick films and 1 mm thick plates were obtained.
PE 막의 제조Preparation of PE Membrane
160℃에서 혼합에 의해 PE 조성물을 제조하였다. 다음으로, 150㎛의 두께를 갖는 막을 같은 온도에서 블로우하였다.PE compositions were prepared by mixing at 160 ° C. Next, a film having a thickness of 150 mu m was blown at the same temperature.
내후성 측정Weather resistance measurement
플라스틱 조성물의 내후성은 본 명세서에 기술된 방법에 따라 Atlas Material Testing Technology Weather-O 계량기(Ci65형)로 실시한 내후성 실험에서 측정하였다. 분해율은 FT-IR에 의해 측정하였다. 그후, 내후성은 플라스틱 조성물이 빛, 온도 및 습도의 조합에 적용하고, 측정된 카르보닐 흡광도의 차이가 막의 경우 숙성전 및 숙성후 0.10 이하이고, 그리고 플레이트의 경우 0.5 이하인 시간(여러 시간)에 따른 양으로 나타낸다.The weather resistance of the plastic composition was measured in a weather resistance test conducted with an Atlas Material Testing Technology Weather-O meter (type Ci65) according to the method described herein. The degradation rate was measured by FT-IR. The weather resistance is then dependent on the time (multiple hours) that the plastic composition is applied to a combination of light, temperature and humidity, and the difference in measured carbonyl absorbance is 0.10 or less before and after aging for membranes and 0.5 or less for aging. Represented by the amount.
어떤 경우, 숙성의 결과로서 색상변화는 ASTM 스탠다드 1925에 따른 열량계에 의해 특징화되었다.In some cases, color change as a result of ripening was characterized by a calorimeter according to ASTM standard 1925.
실시예에서, 다음 약어 및 상표명이 사용되었다:In the examples, the following abbreviations and trade names were used:
PE: 폴리에틸렌PE: polyethylene
PP: 폴리프로필렌PP: polypropylene
ABS: 아크릴로니트릴-부타디엔-스티렌 공중합체ABS: Acrylonitrile-butadiene-styrene copolymer
Tinuvin770: 디-(2,2,6,6-테트라메틸-4-피페리딜)세바케이트Tinuvin 770: di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate
Tinuvin622: N-(2-히드록시에틸)-2,2,6,6-테트라메틸-4-피페리디놀 및 숙신산의 올리고머Tinuvin 622 oligomers of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and succinic acid
Tinuvin123: 비스-(1-옥틸옥시-2,2,6,6-테트라메틸-4-피페리디닐)세바케이트Tinuvin 123: bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate
Chimassorb944: 시안산 및 N,N-디(2,2,6,6-테트라메틸-4-피페리딜)-헥사메틸렌 디아민의 올리고머Chimassorb 944: oligomer of cyanic acid and N, N-di (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene diamine
Chimassorb119: 1,3,5-트리아진-2,4,6-트리아민, N,N'''-[1,2-에탄-디일비스[[[4,6-비스[부틸(1,2,2,6,6-펜타메틸-4-이페리디닐)아미노]-1,3,5-트리아진-2-일]이미노]-3,1-프로판디일]]-비스[N',N''-디부틸-N',N''-비스(1,2,2,6,6-펜타메틸-4-피페리디닐)Chimassorb 119: 1,3,5-triazine-2,4,6-triamine, N, N '''-[1,2-ethane-diylbis [[[4,6-bis [butyl (1,2 , 2,6,6-pentamethyl-4-ipridinyl) amino] -1,3,5-triazin-2-yl] imino] -3,1-propanediyl]]-bis [N ', N ''-dibutyl-N ', N''-bis (1,2,2,6,6-pentamethyl-4-piperidinyl)
HostavinN30:7-옥사-3,20-디아자디스피로[5.1.11.2]-헤네이코산-21-온, 2,2,4,4-테트라메틸-20-(옥시라닐메틸)Hostavin N30: 7-oxa-3,20-diazadispiro [5.1.11.2] -henicoic acid-21-one, 2,2,4,4-tetramethyl-20- (oxyranylmethyl)
DABCO: 디아자비시클로[2.2.2]옥탄DABCO: diazabicyclo [2.2.2] octane
HMTA: 헥사메틸렌테트라민HMTA: Hexamethylenetetramine
DABCO 스테아레이트: 스테아르산 및 DABCO의 모노염DABCO stearate: monosalts of stearic acid and DABCO
DABCO 디스테아레이트: 두 개의 스테아르산 분자를 함유하는 DABCO염DABCO distearate: DABCO salt containing two stearic acid molecules
DABCO 세바케이트: 두 개의 DABCO 분자를 함유하는 세바산(이산)염DABCO sebacate: sebaic acid (diacid) salt containing two DABCO molecules
DABCO 벤젠트리카르복실레이트: 세 개의 DABCO 분자를 함유하는 벤젠트리카르복실산염DABCO benzenetricarboxylate: Benzenetricarboxylate containing three DABCO molecules
HMTA 스테아레이트: 스테아르산 및 DABCO의 모노염HMTA stearate: monosalts of stearic acid and DABCO
Atade:7-아미노-1,3,5-트리아자다만탄Atade: 7-amino-1,3,5-triazadamantane
도데실리덴-atade: 7-도데실리덴아미노-1,3,5-트리아자다만탄Dodecylidene-atade: 7-dodecylideneamino-1,3,5-triazadamantane
PP-MA-atade: 상기에 따라 합성된, atade로 변형된 MA-결합 폴리프로필렌PP-MA-atade: MA-bonded polypropylene modified atade, synthesized according to the above
실시예 Ⅰ-Ⅱ 및 비교실시예 A-D: 여러 플라스틱 조성물의 내후성Examples I-II and Comparative Examples A-D: Weather Resistance of Various Plastic Compositions
상기 방법을 사용하여 플라스틱 조성물 시리즈를 제조하였다. 상기 방법에서, 플라스틱 조성물의 조성은 다양했다. 디-(2,2,6,6-테트라메틸-4-피페리딜)세바케이트(상표명: Tinuvin770, Ciba-Geigy, Basel)를 HALS 화합물로서 선택하였다. PP(Stamylan, P83m18형, DSM, 네덜란드)는 중합체로서 선택하였다. 상기 방법을 사용하여 플라스틱 조성물로부터 막을 제조하였다. 상기 막을 내후성 시험에 적용하고, 내후성을 상기와 같이 측정하였다. 그 결과는 표 1에 요약되어 있다.The above method was used to prepare a series of plastic compositions. In this method, the composition of the plastic composition varied. Di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: Tinuvin 770, Ciba-Geigy, Basel) was selected as the HALS compound. PP (Stamylan , P83m18 type, DSM, Netherlands) was selected as the polymer. Membranes were prepared from plastic compositions using this method. The membrane was subjected to a weather resistance test and the weather resistance was measured as above. The results are summarized in Table 1.
실시예 Ⅲ-Ⅶ 및 비교실시예 E 및 F: 여러 농도의 HALS 화합물 및 다리결합 아민 화합물을 갖는 플라스틱 조성물의 내후성Examples III-III and Comparative Examples E and F Weather Resistance of Plastic Compositions with HALS Compounds and Bridge amine Compounds at Various Concentrations
실시예 Ⅰ을 반복하고, HALS 안정제의 농도를 선택하고, 적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물을 다양하게 했다. 그 결과는 표 2에 요약되어 있다. 상기에서, 다리결합 아민 화합물의 0.1중량% 내지 0.5중량%의 양을 함유하는 플라스틱 조성물이 향상된 내후성을 나타내고, 이는 더 많은 다리결합 아민 화합물이 사용됨에 따라 증가한다고 결론지을 수 있다. 따라서, 2배 이상의 내후성이 가능했다(실시예 F 대 Ⅶ).Example I was repeated, the concentration of HALS stabilizer was selected, and the bridged amine compound having at least one N-leg was varied. The results are summarized in Table 2. In the above, it can be concluded that plastic compositions containing an amount of 0.1% to 0.5% by weight of the bridged amine compound exhibit improved weather resistance, which increases as more bridged amine compounds are used. Thus, two or more times of weather resistance was possible (Example F vs. heat resistance).
실시예 Ⅸ-ⅩⅡ: 적어도 하나의 N-다리목을 갖는 여러 다리결합 아민 화합물을 함유하는 플라스틱 조성물의 내후성Example VII-XII: Weather Resistance of Plastic Compositions Containing Several Bridge-Bound Amine Compounds Having at least One N-Arm
적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물의 종류가 다양한 HALS(Tinuvin770) 0.2%를 함유하는 플라스틱 조성물을 사용하여 실시예 Ⅰ을 반복하였다. 그 결과는 표 3에 요약되어 있다.HALS (Tinuvin) with various types of bridged amine compounds having at least one N-bridge 770) Example I was repeated using a plastic composition containing 0.2%. The results are summarized in Table 3.
실시예 ⅩⅢ 및 비교실시예 G: PE 막의 내후성Examples XIII and Comparative Example G Weatherability of PE Membranes
가해진 DABCO의 각각 0중량% 및 0.06중량%와 함께 HALS 화합물의 0.05중량%(Tinuvin770) 및 PE(LDPE, 타입 2304 AN00, DSM, 네덜란드)로 조성된 두 개의 플라스틱 조성물을 사용하여 실시예 Ⅰ을 반복하였다. 상기 플라스틱 조성물을 처리하여 두께 150㎛의 막을 블로우성형하였다. 상기 막을 Suntester에서 빛에 노출시켰다. 내후성 처리는 Polym. Deg. & Stab., 39, 225-233 (1993)에 기술된 방법에 따라 붕규산 유리용기내에서 실시하였다. 내후성은 상기 기술된 바와 같이 측정하였으나; 상기 경우, 0.05 유닛의 카르보닐 흡광도에 있어서의 변화는 내후성을 측정할 때 사용되었다. DABCO없는 막의 내후성(비교실시예 G)은 2700시간이었으며, 분해는 2400시간 이상으로 상당히 향상되었으며; DABCO를 함유하는 막의 내후성은 3500시간 이상이었으며, 분해는 0.03유닛에서 일정한 프로필을 나타내었다.0.05% by weight of the HALS compound with 0% and 0.06% by weight of DABCO added respectively (Tinuvin 770) and Example I were repeated using two plastic compositions composed of PE (LDPE, type 2304 AN00, DSM, Netherlands). The plastic composition was treated to blow molded a 150 μm thick film. The membrane was exposed to light in Suntester. Weathering treatments are available in Polym. Deg. & Stab., 39, 225-233 (1993) was carried out in a borosilicate glass container. Weather resistance was measured as described above; In this case, a change in carbonyl absorbance of 0.05 units was used when measuring weather resistance. The weatherability of the membrane without DABCO (Comparative Example G) was 2700 hours and the degradation was significantly improved to over 2400 hours; The weatherability of the membrane containing DABCO was more than 3500 hours and the degradation showed a constant profile at 0.03 units.
실시예 ⅩⅣ 및 비교실시예 H 및 I: ABS막의 내후성Examples XIV and Comparative Examples H and I: Weatherability of ABS Films
ABS(Ronfalin, 타입 356＊＊, DSM, 네덜란드), ABS 및 HALS 화합물의 0.5중량%(Tinuvin770), 및 ABS, HALS 화합물의 0.5중량% 및 DABCO 스테아레이트의 0.5중량%로 각각 조성된 세 개의 플라스틱 조성물을 사용하여 실시예 Ⅰ을 반복하였다. 분해는 열량계를 사용하여 색상변화로 측정하고, 내후성은 플라스틱 조성물이 상기 내후성 시험에 적용되고, 측정된 색상변화가 5유닛 이하인 시간의 양(시간 수)에 있어서 ASTM 스탠다드 1925에 따라 측정하였다. 그 결과는 표 4에 요약되어 있다.ABS (Ronfalin , Type 356 ＊＊ , DSM, Netherlands), 0.5% by weight of ABS and HALS compounds (Tinuvin 770), and Example I was repeated using three plastic compositions, each consisting of 0.5% by weight of ABS, HALS compounds and 0.5% by weight of DABCO stearate. Degradation was measured by color change using a calorimeter, and weatherability was measured according to ASTM Standard 1925 in the amount of time (number of hours) that the plastic composition was subjected to the weathering test and the measured color change was 5 units or less. The results are summarized in Table 4.
실시예 ⅩⅤ-ⅩⅦ 및 비교실시예 J: ABS 막의 내후성Example VII-V and Comparative Example J: Weatherability of ABS Film
상기 방법을 사용하여 플라스틱 조성물 시리즈를 제조하였다. 상기 방법에서, 플라스틱 조성물의 조성은 다양했다. 디-(2,2,6,6-테트라메틸-4-피페리딜) 세바케이트(상표명: Tinuvin770, Ciba-Geigy, Basel)는 HALS 화합물로서 선택되었다. ABS(Ronfalin, 타입 356**, DSM, 네덜란드)는 중합체로서 선택되었다. 플레이트는 상기 방법을 사용하여 플라스틱 조성물에서 제조되었다. 분해는 열량계를 사용하여 색상변화로서 측정하고, 내후성은 플라스틱 조성물이 상기 내후성 시험에 적용되고, 측정된 색상변화가 5유닛 이하인 시간의 양(시간 수)에 있어서 ASTM 스탠다드 1925에 따라 측정하였다. 그 결과는 표 5에 요약되어 있다.The above method was used to prepare a series of plastic compositions. In this method, the composition of the plastic composition varied. Di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: Tinuvin 770, Ciba-Geigy, Basel) was selected as the HALS compound. ABS (Ronfalin , Type 356 ** , DSM, The Netherlands) was chosen as the polymer. Plates were made in plastic compositions using the above method. Degradation was measured as color change using a calorimeter, and weatherability was measured according to ASTM Standard 1925 in the amount of time (number of hours) that the plastic composition was subjected to the weathering test and the measured color change was 5 units or less. The results are summarized in Table 5.
실시예 ⅩⅧ-ⅩⅩⅢ 및 비교실시예 K-O: 적어도 하나의 N-다리목을 갖는 여러 다리결합 아민 화합물을 함유하는 플라스틱 조성물의 내후성Examples VIII-IIIIII and Comparative Example K-O: Weather Resistance of Plastic Compositions Containing Several Bridge-Bound Amine Compounds Having at least One N-Arm
적어도 하나의 N-다리목을 갖는 다리결합 아민 화합물의 종류가 다양한, 실시예 Ⅲ-Ⅷ을 반복하였다. 그 결과는 표 6에 요약되어 있다.Example III-VII was repeated, with various types of bridged amine compounds having at least one N-bridge. The results are summarized in Table 6.
실시예 ⅩⅩⅣ-ⅩⅩⅨ: 적어도 하나의 N-다리목을 갖는 여러 다리결합 아민 화합물을 함유하는 플라스틱 조성물의 내후성Example XIV-VII Weather Resistance of Plastic Compositions Containing Several Bridge-Bound Amine Compounds Having at least One N-Arm
7-아미노-1,3,5-트리아자다만탄의 농도가 다양한, 실시예 Ⅲ-Ⅷ을 반복하였다. 그 결과는 표 7에 요약되어 있다.Example III-VII was repeated, varying the concentration of 7-amino-1,3,5-triazadamantane. The results are summarized in Table 7.
실시예 ⅩⅩⅩ-LⅩⅩⅩV 및 비교실시예 R-AJ: 여러 플라스틱 조성물의 내후성Example VII-LV and Comparative Example R-AJ: Weather Resistance of Various Plastic Compositions
상기 방법을 사용하여 플라스틱 조성물 시리즈를 제조하였다. 상기 방법에서, 플라스틱 조성물의 조성은 다양했다. 디-(2,2,6,6-테트라메틸-4-피페리딜)세바케이트(Tinuvin770), N-(2-히드록시에틸)-2,2,6,6-테트라메틸-4-피페리디놀과 숙신산의 올리고머(Tinuvin622), 비스-(1-옥틸옥시-2,2,6,6-테트라메틸-4-피페리디닐)세바케이트(Tinuvin123), 시안산과 N,N-디(2,2,6,6-테트라메틸-4-피페리딜)헥사메틸렌 디아민의 올리고머(Chimassorb944), 1,3,5-트리아진-2,4,6-트리아민, N,N'''-[1,2-에탄-디일비스[[4,6-비스[부틸(1,2,2,6,6-펜타메틸-4-이페리디닐)아미노]-1,3,5-트리아진-2-일]이미노]-3,1-프로판디일]]-비스[N',N''-디부틸-N',N''-비스(1,2,2,6,6-펜타메틸-4-피페리디닐)(Chimassorb119) 및 7-옥사-3,20-디아자디스피로[5.1.11.2]-헤네이코산-21-온의 올리고머 ,2,2,4,4-테트라메틸-20-(옥시라닐메틸)(HostavinN30)은 HALS 화합물로서 선택하였다. HMTA 스테아레이트, 7-도데실리덴아미노-1,3,5-트리아자다만탄 및 PP-MA-7-아미노-1,3,5-트리아자다만탄은 다리결합 아민으로서 선택하였다. PP(Stamylan, 타입 P83m18, batch Ⅵ DSM, 네덜란드)는 중합체로서 선택하였다. 상기 방법을 사용하여 플라스틱 조성물에서 막을 제조하였다. 상기 막을 내후성 시험하여, 내후성은 상기와 같이 측정하였다. 그 결과는 표 8-20에 요약되어 있다.The above method was used to prepare a series of plastic compositions. In this method, the composition of the plastic composition varied. Di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770), oligomer of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol with succinic acid (Tinuvin 622), bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin) 123), an oligomer of cyanic acid and N, N-di (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine (Chimassorb 944), 1,3,5-triazine-2,4,6-triamine, N, N '''-[1,2-ethane-diylbis [[4,6-bis [butyl (1,2 , 2,6,6-pentamethyl-4-ipridinyl) amino] -1,3,5-triazin-2-yl] imino] -3,1-propanediyl]]-bis [N ', N ''-dibutyl-N ', N''-bis (1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb 119) and oligomer of 7-oxa-3,20-diazadispiro [5.1.11.2] -henicoic acid-21-one, 2,2,4,4-tetramethyl-20- (oxyranylmethyl) (Hostavin N30) was chosen as the HALS compound. HMTA stearate, 7-dodecylideneamino-1,3,5-triazadamantane and PP-MA-7-amino-1,3,5-triazadamantane were selected as bridged amines. PP (Stamylan , Type P83m18, batch VI DSM, Netherlands) was chosen as the polymer. The method was used to prepare membranes in plastic compositions. The membrane was tested for weather resistance, and weather resistance was measured as above. The results are summarized in Table 8-20.
비교실시예 AK-AR: 여러 플라스틱 조성물의 내후성Comparative Example AK-AR: Weather Resistance of Various Plastic Compositions
상기 방법을 사용하여 플라스틱 조성물 시리즈를 제조하였다. 상기 방법에서, 플라스틱 조성물의 조성은 여러 비-HALS 안정제를 사용하여 다양했다. 2-히드록시-4-n-옥톡시-벤조페논(Chimmasorb81), 2-(2'-히드록시-3',5'-디-tert-부틸-페닐)-5-클로로-벤조트리아졸(Tinuvin327) 및 옥타데실-3-(3,5-디-tert-부틸-4-히드록시-페닐)-프로피오네이트(Irganox1076)는 비-HALS 안정제로서 선택하였다. DABCO 스테아레이트 및 HMTA 스테아레이트는 N-다리목을 갖는 다리결합 아민으로서 선택하였다.The above method was used to prepare a series of plastic compositions. In this method, the composition of the plastic composition was varied using several non-HALS stabilizers. 2-hydroxy-4-n-octoxy-benzophenone (Chimmasorb 81), 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chloro-benzotriazole (Tinuvin 327) and octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-phenyl) -propionate (Irganox 1076) was chosen as the non-HALS stabilizer. DABCO stearate and HMTA stearate were selected as bridged amines with N-legs.
PP(Stamylan, 타입 P83m18, DSM, 네덜란드)는 중합체로서 선택하였다. 상기 방법을 사용하여 플라스틱 조성물에서 막을 제조하였다. 막을 내후성 시험하여, 내후성은 상기와 같이 측정하였다. 그 결과는 표 21에 요약되어 있다.PP (Stamylan , Type P83m18, DSM, Netherlands) was chosen as the polymer. The method was used to prepare membranes in plastic compositions. The membrane was tested for weather resistance and weather resistance was measured as above. The results are summarized in Table 21.
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| EP1571177A1 (en) * | 2004-03-03 | 2005-09-07 | DSM IP Assets B.V. | Elastomer with improved weather resistance |
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| DE2702205A1 (en) * | 1977-01-20 | 1978-07-27 | Hoechst Ag | N-SUBSTITUTED TRIAZAADAMANTANYL URNENTS AS STABILIZERS FOR THERMOPLASTICS |
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