TWI586742B - 含有鹵原子之樹脂組成物、其製造方法及包含其之成形品 - Google Patents
含有鹵原子之樹脂組成物、其製造方法及包含其之成形品 Download PDFInfo
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- TWI586742B TWI586742B TW100134981A TW100134981A TWI586742B TW I586742 B TWI586742 B TW I586742B TW 100134981 A TW100134981 A TW 100134981A TW 100134981 A TW100134981 A TW 100134981A TW I586742 B TWI586742 B TW I586742B
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- Prior art keywords
- halogen atom
- mass
- parts
- polyol
- polymerization
- Prior art date
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- 125000005843 halogen group Chemical group 0.000 title claims description 85
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 88
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 88
- 229920005862 polyol Polymers 0.000 claims description 56
- 150000003077 polyols Chemical class 0.000 claims description 56
- 238000006116 polymerization reaction Methods 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 26
- 238000007127 saponification reaction Methods 0.000 claims description 26
- 150000003752 zinc compounds Chemical class 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
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- 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 16
- 239000000600 sorbitol Substances 0.000 claims description 16
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 229940105990 diglycerin Drugs 0.000 claims description 7
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000223 polyglycerol Polymers 0.000 claims description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 37
- 229920000915 polyvinyl chloride Polymers 0.000 description 36
- -1 polyethylene Polymers 0.000 description 33
- 238000000034 method Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
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- 238000011156 evaluation Methods 0.000 description 19
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- 230000000052 comparative effect Effects 0.000 description 18
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- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
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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 9
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
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- 239000000853 adhesive Substances 0.000 description 8
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
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- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- SPBMMWPWMPIQPR-UHFFFAOYSA-L calcium;zinc;octadecanoate Chemical compound [Ca+2].[Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SPBMMWPWMPIQPR-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
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- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明關於在食品用途、醫療用途或日用品等的一般用途等之領域適用的含有鹵素原子之樹脂組成物、其製造方法及由其所形成之成形品。特別地，關於熱安定性良好、可得到著色少的成形品之含有鹵素原子之樹脂組成物、其製造方法及包含其之成形品。
以聚氯乙烯為代表的含有鹵素原子之樹脂，係摻合Ca-Zn系、Ba-Zn系等的安定劑而被成形加工，其成形品除了使用於一般用途，還可廣泛使用於食品用途、醫療用途等。
然而，此等安定劑由於抑制含有鹵素原子之樹脂之熱降解的能力不足，而在成形後不久的成形品上看到著色，有成形時的熱安定性不充分之缺點。因此，有提案添加抗氧化劑或添加具有羥基的化合物之含有鹵素原子之樹脂組成物作為改良此等缺點的手段。
專利文獻1(日本特開昭50-92947號公報)中揭示於含氯的樹脂中，添加鈣皂、鋅皂、多元醇或其衍生物、與中性的無機鈣鹽之方法。
專利文獻2(日本特開昭54-81359號公報)中揭示於含氯的聚合物中，添加水溶性聚合物之方法。
專利文獻3(日本特開昭57-147552號公報)中揭示於含氯樹脂中，添加二季戊四醇與二羧酸的反應縮合物、鋅化合物及水滑石之方法。
專利文獻4(日本特開昭60-238345號公報)中揭示於聚氯乙烯等的熱塑性樹脂中，添加乙烯單位的含量20~50%、醋酸乙烯酯單位的皂化度96%以上之乙烯-醋酸乙烯酯共聚物皂化物及水滑石系化合物等之方法。
專利文獻5(日本特開平1-178543號公報)中揭示於含鹵素熱塑性樹脂中，添加金屬皂、及具有乙烯含量20~75莫耳%、醋酸乙烯酯部分的皂化度50莫耳%以上之共聚合組成物的乙烯-醋酸乙烯酯共聚物皂化物之方法。
專利文獻6(日本特開平6-287387號公報)中揭示於氯乙烯系樹脂中，添加有機酸的金屬鹽、聚乙烯醇的縮醛化物之方法。
專利文獻7(日本特開平9-3286號公報)中揭示於氯乙烯系樹脂中，添加皂化度70~95莫耳%、平均聚合度300~2,000且在分子鏈末端具有巰基的部分皂化聚乙烯醇之方法。
專利文獻8(日本特開平9-31281號公報)中揭示於氯乙烯系樹脂中，添加鋅化合物、水滑石類、聚乙烯醇及聚甲基丙烯酸甲酯之方法。
非專利文獻1(高分子論文集,Vol.47,No.3,p.197(1990))中揭示於聚氯乙烯中，添加硬脂酸鋅-硬脂酸鈣複合皂、聚合度為600以上的完全皂化聚乙烯醇之方法。
非專利文獻2(高分子論文集,Vol.47,No.6,p.509(1990))中揭示於聚氯乙烯中，硬脂酸鋅-硬脂酸鈣複合皂、聚合度為500、皂化度為73.6莫耳%的部分皂化聚乙烯醇之方法。
非專利文獻3(高分子論文集,Vol.50,No.2,、p.65(1993))中揭示於聚氯乙烯中，添加硬脂酸鋅-硬脂酸鈣複合皂、乙烯含量為29莫耳%以上的乙烯-乙烯醇共聚物之方法。
非專利文獻4(Polymers & Polymer Composites,Vol.11,p.649(2003))中揭示於聚氯乙烯中，添加硬脂酸鋅-硬脂酸鈣複合皂、與聚合度為500、皂化度為98.5莫耳%的聚乙烯醇或乙烯含量為29莫耳%以上的乙烯-乙烯醇共聚物之方法。
非專利文獻5(日本接著學會誌,Vol.43,No.2,p.43(2007))中揭示於聚氯乙烯中，添加聚合度為500且皂化度為88莫耳%的聚乙烯醇或聚合度為1700且皂化度為78莫耳%以上的聚乙烯醇、聚甲基丙烯酸甲酯之方法。
然而，於專利文獻1~8及非專利文獻1~5所記載的含有鹵素原子之樹脂組成物中，有如以下的問題。
即，當添加低分子量的多元醇時，容易發生以下的困擾：於成形時低分子多元醇滲出表面，於混練時混練物黏著於擠壓機等內部的螺桿表面等。又，於所得之成形品中，容易產生多元醇的揮發、黏連之發生、透明性的降低、接著性及密著性的降低等之問題。
又，當添加高分子量的多元醇時，尤其在比較低溫下成形時，高分子多元醇在含有鹵素原子之樹脂組成物中之分散性係不充分，熱安定性不足。
專利文獻1 日本特開昭50-92947號公報
專利文獻2 日本特開昭54-81359號公報
專利文獻3 日本特開昭57-147552號公報
專利文獻4 日本特開昭60-238345號公報
專利文獻5 日本特開平1-178543號公報
專利文獻6 日本特開平6-287387號公報
專利文獻7 日本特開平9-3286號公報
專利文獻8 日本特開平9-31281號公報
非專利文獻1 高分子論文集,Vol.47,No.3,p.197(1990)
非專利文獻2 高分子論文集,Vol.47,No.6,p.509(1990)
非專利文獻3 高分子論文集,Vol.50,No.2,p.65(1993)
非專利文獻4 Polymers & Polymer Composites,Vol.11,p.649(2003)
非專利文獻5 日本接著學會誌,Vol.43,No.2,p.43(2007)
本發明之課題在於提供成形時的熱安定性優異，可得到著色少的成形品之含有鹵素原子之樹脂組成物、其製造方法及由其所形成之成形品。
本發明者們重複專心致力的檢討，結果發現：對於含有鹵素原子之樹脂，各自添加特定量的特定聚乙烯醇、特定多元醇及鋅化合物而成之含有鹵素原子之樹脂組成物，係即使特別在低溫下成形加工時，也具有充分的熱安定性，而且將該含有鹵素原子之樹脂組成物成形所得之成形品係著色少，以該知識為基礎，進一步重複檢討，而完成本發明。
即，上述問題係可藉由提供一種含有鹵素原子之樹脂組成物來解決，該樹脂組成物含有：相對於含有鹵素原子之樹脂100質量份而言，皂化度為60~99.9莫耳%且黏度平均聚合度為100~1,000的聚乙烯醇0.01~2.5質量份，分子量為2,000以下且羥基含有率為10質量%以上的多元醇0.01~2.5質量份，及鋅化合物0.01~5質量份。
上述聚乙烯醇與上述多元醇的質量比較佳為滿足(聚乙烯醇的質量)/(多元醇的質量)=30/70~90/10。
上述聚乙烯醇的黏度平均聚合度較佳為100~450。
上述含有鹵素原子之樹脂組成物較佳為藉由將聚乙烯醇、多元醇及鋅化合物加到含有鹵素原子之樹脂中而含有。
又，上述問題亦可藉由提供一種含有鹵素原子之樹脂組成物之製造方法來解決，該製造方法具有對於含有鹵素原子之樹脂100質量份，添加皂化度為60~99.9莫耳%且黏度平均聚合度為100~1,000的聚乙烯醇0.01~2.5質量份、分子量為2,000以下且羥基含有率為10質量%以上的多元醇0.01~2.5質量份、及鋅化合物0.01~5質量份之步驟。
再者，上述問題也可藉由一種由上述含有鹵素原子之樹脂組成物所形成之成形品來解決。
使用本發明的含有鹵素原子之樹脂組成物時，即使特別在低溫下成形加工時，也具有充分的熱安定性，而且在成形時，黏著物對擠壓機內部等的附著少。而且，將該含有鹵素原子之樹脂組成物成形所得之成形品係著色少。
以下，詳細說明本發明的含有鹵素原子之樹脂組成物、其製造方法及由其所形成之成形品。
就本發明所用之含有鹵素原子之樹脂而言，例如可使用聚氯乙烯、聚偏二氯乙烯、氯化聚氯乙烯、氯化聚烯烴、氯乙烯-醋酸乙烯酯共聚物等之含氯樹脂；溴化聚烯烴等之含溴樹脂等，可按照成形品的用途等，使用此等之中的1種或2種以上，從取得的容易性或物性等之觀點來看，較佳為含氯樹脂，更佳為聚氯乙烯或聚偏二氯乙烯，尤佳為聚氯乙烯。
就製造上述聚氯乙烯的原料之單體而言，可單獨使用氯乙烯單體，也可使用50質量%以上的氯乙烯單體及與其可共聚合的其它單體之混合物。再者，就與氯乙烯單體可共聚合的其它單體而言，可舉出醋酸乙烯酯、丙酸乙烯酯等的乙烯酯；丙烯酸甲酯、丙烯酸乙酯等的(甲基)丙烯酸酯；乙烯、丙烯等的烯烴；馬來酸酐、丙烯腈、苯乙烯、偏二氯乙烯等。
又，就使用此等單體來製造上述聚氯乙烯之方法而言，並沒有特別的限定，可合適地採用在聚合引發劑的存在下將該單體懸浮聚合之方法。就該情況下的分散安定劑而言，例如可採用甲基纖維素、羥乙基纖維素、羥丙基纖維素、羥丙基甲基纖維素等的水溶性纖維素醚；聚乙烯醇、明膠等的水溶性聚合物；山梨糖醇酐單月桂酸酯、山梨糖醇酐三油酸酯、甘油三硬脂酸酯、環氧乙烷環氧丙烷嵌段共聚物等的油溶性乳化劑；聚氧乙烯山梨糖醇酐單月桂酸酯、聚氧乙烯甘油油酸酯、月桂酸鈉等的水溶性乳化劑等。其中，較佳為使用聚乙烯醇。
就所使用的聚合引發劑而言，可使用以往在氯乙烯單體等的聚合中所使用的油溶性或水溶性聚合引發劑。就油溶性聚合引發劑而言，例如可舉出二異丙基過氧二碳酸酯、二-2-乙基己基過氧二碳酸酯、二乙氧基乙基過氧二碳酸酯等的過碳酸酯化合物；第三丁基過氧新癸酸酯、第三丁基過氧三甲基乙酸酯、第三己基過氧三甲基乙酸酯、α-異丙苯基過氧新癸酸酯等的過酯化合物；乙醯基環己基磺醯基過氧化物、2,4,4-三甲基戊基-2-過氧苯氧基乙酸酯、3,5,5-三甲基己醯基過氧化物、月桂醯基過氧化物等的過氧化物；偶氮雙-2,4-二甲基戊腈、偶氮雙(4-甲氧基-2,4-二甲基戊腈)等的偶氮化合物等。就水溶性聚合引發劑而言，例如可舉出過硫酸鉀、過硫酸銨、過氧化氫、氫過氧化異丙苯等。此等油溶性或水溶性聚合引發劑係可單獨或組合2種類以上使用。
於聚合時，按照需要，可在聚合反應系中添加其它各種添加劑。就添加劑而言，例如可舉出醛、鹵化烴、硫醇等的聚合調節劑，酚化合物、硫化合物、N-氧化物化合物等的聚合抑制劑，pH調整劑、交聯劑、防腐劑、防黴劑、防黏連劑、消泡劑、防結垢劑、抗靜電劑等。
於聚合時，聚合溫度係沒有特別的限制，當然可為20℃左右的溫度，亦可調整至超過90℃的高溫。又，為了提高聚合反應系的除熱效率，使用附有回流冷凝器的聚合器者亦為較佳的實施態樣之一。
於前述含有鹵素原子之樹脂中含有本發明的含有鹵素原子之樹脂組成物中所含有的聚乙烯醇(以下亦簡稱「PVA」)之方法係沒有特別的限定，較佳為藉由在形成含有鹵素原子之樹脂用的單體之聚合後，添加於含有鹵素原子之樹脂中而含有。該PVA係可為粉，或溶解在水或有機溶劑中，並添加於含有鹵素原子之樹脂中。若在形成含有鹵素原子之樹脂用的單體之聚合前或聚合中，添加該PVA，則由於該PVA係作為單體及所得之含有鹵素原子之樹脂的分散劑而作用，故會對該鹵素之樹脂的平均粒徑或可塑劑吸收性等的品質造成不利影響。又，藉由在含有鹵素原子之樹脂製造後的樹脂洗淨，該PVA係大體上被去除，含有鹵素原子之樹脂組成物中的PVA之含量變少，熱安定性有不充分之虞。
上述PVA的皂化度為60~99.9莫耳%，較佳為65~99莫耳%，更佳為70~99莫耳%。皂化度低於60莫耳%時或超過99.9莫耳%時，長期的熱安定性降低。再者，PVA的皂化度係依照JIS K6726所測定之值。
上述PVA的黏度平均聚合度(以下亦僅稱「聚合度」)為100~1,000，更佳為150~800，尤佳為200~700。從尤其即使在低溫下成形加工時，也進一步提高熱安定性，而且在成形時進一步抑制黏著物對擠壓機內部的附著之觀點來看，PVA的聚合度之上限更佳為450。PVA的聚合度若超過1,000，則長期的熱安定性降低。而且，得到聚合度低於100的PVA者係製造上困難。再者，PVA的聚合度係依照JIS K6726所測定之值。即，可將PVA再皂化成皂化度99.5莫耳%以上，進行精製後，由在30℃的水中所測定的極限黏度[η](單位：分升/g)，藉由下式來求得。
聚合度=([η]×1000/8.29)(1/0.62)
上述PVA例如可藉由採用塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合法、分散聚合法等習知的方法，使乙烯酯單體聚合，將所得之聚乙烯酯皂化而製造。從工業的觀點來看，較佳的聚合方法係溶液聚合法、乳化聚合法及分散聚合法。於聚合操作時，亦可採用分批法、半分批法及連續法中的任一種聚合方式。
就可用於聚合的乙烯酯單體而言，例如可舉出醋酸乙烯酯、甲酸乙烯酯、丙酸乙烯酯、辛酸乙烯酯、維沙迪克酸乙烯酯等，從工業的觀點來看，此等之中較佳為醋酸乙烯酯。
於乙烯酯單體的聚合時，只要是不損害本發明的宗旨之範圍，則亦可使乙烯酯單體與其它單體共聚合。就可使用的其它單體而言，例如可舉出乙烯、丙烯、正丁烯、異丁烯等的α-烯烴；丙烯酸及其鹽；丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸2-乙基己酯、丙烯酸十二酯、丙烯酸十八酯等的丙烯酸酯；甲基丙烯酸及其鹽；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十二酯、甲基丙烯酸十八酯等的甲基丙烯酸酯；丙烯醯胺；N-甲基丙烯醯胺、N-乙基丙烯醯胺、N,N-二甲基丙烯醯胺、二丙酮丙烯醯胺、丙烯醯胺丙磺酸及其鹽、丙烯醯胺丙基二甲基胺及其鹽或其四級鹽、N-羥甲基丙烯醯胺及其衍生物等的丙烯醯胺衍生物；甲基丙烯醯胺；N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、甲基丙烯醯胺丙磺酸及其鹽、甲基丙烯醯胺丙基二甲基胺及其鹽或其四級鹽、N-羥甲基甲基丙烯醯胺及其衍生物等甲基丙烯醯胺衍生物；甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚、異丁基乙烯基醚、第三丁基乙烯基醚、十二基乙烯基醚、硬脂基乙烯基醚等的乙烯基醚；丙烯腈、甲基丙烯腈等的腈；氯乙烯、氟乙烯等的鹵乙烯；偏二氯乙烯、偏二氟乙烯等的偏二鹵乙烯；醋酸烯丙酯、烯丙基氯等的烯丙基化合物；馬來酸、伊康酸、富馬酸等的不飽和二羧酸及其鹽或其酯；乙烯基三甲氧基矽烷等的乙烯基矽烷基化合物；醋酸異丙烯酯等。
於乙烯酯單體的聚合時，以調節所得之PVA的聚合度等為目的，亦可使鏈轉移劑共存。就鏈轉移劑而言，可舉出乙醛、丙醛、丁醛、苯甲醛等的醛；丙酮、甲基乙基酮、己酮、環己酮等的酮；2-羥基乙硫醇等的硫醇；硫代乙酸等的硫代羧酸；三氯乙烯、全氯乙烯等的鹵化烴等，其中較宜使用醛及酮。鏈轉移劑的添加量，係按照所添加的鏈轉移劑之鏈轉移常數及目的之PVA的聚合度來決定，一般相對於所使用的乙烯酯單體而言，宜為0.1~10質量%。此處，使用硫代羧酸類等作為鏈轉移劑時，來自鏈轉移劑的官能基係導入乙烯酯系聚合物的末端，經由皂化而得到在末端具有SH基的PVA。然而，使用如此的PVA時，所得之聚氯乙烯樹脂組成物的熱安定性提高效果係沒有那麼大。因此，宜不使用硫代羧酸類作為鏈轉移劑。又，在PVA的末端，較佳為不具有SH基。
於本發明中，亦可使用在比通常還高的溫度條件下將乙烯酯單體聚合而得之1,2-二醇結合量多的PVA。此時，PVA中的1,2-二醇結合量較佳為1.9莫耳%以上，更佳為2.0莫耳%以上，尤佳為2.1莫耳%以上。又，1,2-二醇結合量的上限例如為3.0莫耳%。
於聚乙烯酯的皂化反應中，可採用使用習知的氫氧化鈉、氫氧化鉀、甲氧化鈉等的鹼性觸媒、或對甲苯磺酸等的酸性觸媒之醇解或水解反應。就皂化反應所用的溶劑而言，可舉出甲醇、乙醇等的醇；醋酸甲酯、醋酸乙酯等的酯；丙酮、甲基乙基酮等的酮；苯、甲苯等的芳香族烴等，此等可為單獨或組合2種以上使用。其中，使用甲醇或甲醇與醋酸甲酯的混合溶液當作溶劑，在鹼性觸媒的氫氧化鈉之存在下進行皂化反應者係簡便而較佳。
含有鹵素原子之樹脂組成物中的PVA之含量，相對於含有鹵素原子之樹脂100質量份而言，為0.01~2.5質量份，較佳為0.05~2質量份。PVA之含量若低於0.01質量份，則長期的熱安定性不充分，若超過2.5質量份，則由所得之含有鹵素原子之樹脂組成物所形成的成形品係變容易著色。
所使用的PVA係可為含有25℃的pKa為3.5~5.5的酸及/或其金屬鹽之組成物的形態。如此的酸之種類係沒有特別的限制，例如可舉出醋酸(pKa4.76)、丙酸(pKa4.87)、丁酸(pKa4.63)、辛酸(pKa4.89)、己二酸(pKa5.03)、苯甲酸(pKa4.00)、甲酸(pKa3.55)、吉草酸(pKa4.63)、庚酸(pKa4.66)、乳酸(pKa3.66)、苯基醋酸(pKa4.10)、異丁酸(pKa4.63)、環己烷羧酸(pKa4.70)等。其中，較佳為醋酸、丙酸及乳酸。金屬鹽的種類係沒有特別的限制，通常使用鈉、鉀等鹼金屬的鹽，鎂、鈣等鹼土類金屬的鹽。
上述酸及/或其金屬鹽的含量，相對於PVA 100質量份而言，較佳為0.05~5質量份，更佳為0.1~3質量份，尤佳為0.15~2質量份。相對於PVA 100質量份而言，酸及/或其金屬鹽的含量若低於0.05質量份，則長期的熱安定性有降低之虞，另一方面若超過5質量份，則由所得的含有鹵素原子之樹脂組成物所形成之成形品係有變容易著色的傾向。
再者，於PVA中使含有指定量的該酸及/或其金屬鹽之方法係沒有特別的限定，例如可採用：調整上述聚乙烯酯的皂化反應所用之鹼觸媒的種類或量等之方法；於PVA製造後，追加或去除該酸及/或其金屬鹽之方法等。
於前述含有鹵素原子之樹脂中含有之本發明的含有鹵素原子之樹脂組成物中所含有的多元醇之方法係沒有特別的限定，但較佳為在形成含有鹵素原子之樹脂用的單體之聚合後，藉由添加於所得的含有鹵素原子之樹脂中而含有。該多元醇係可為粉或黏調液體，或溶解在水或有機溶劑中，並添加於含有鹵素原子之樹脂中。
本發明的含有鹵素原子之樹脂組成物中所含有的多元醇係分子量為2,000以下，較佳為1,500以下，特佳為1,000以下。分子量若超過2,000，則長期的熱安定性降低。分子量的下限係沒有特別的限制，但從抑制由含有鹵素原子之樹脂組成物中滲出或揮發的觀點來看，較佳為100以上。
本發明的含有鹵素原子之樹脂組成物中所含有的多元醇係分子中的羥基含有率為10質量%以上，較佳為15質量%以上，更佳為20質量%以上。羥基含有率少於10質量%時，會損害長期的熱安定性。另一方面，羥基含有率通常為60質量%以下。再者，多元醇的羥基含有率(質量%)係可藉由下式來求得。
(羥基含有率)={(構成多元醇1分子中所含有的羥基之氫原子及氧原子的合計原子量)/(多元醇的分子量)}×100
就本發明的含有鹵素原子之樹脂組成物中所含有的多元醇而言，可舉出甘油、二甘油、甘油單位的重複數為3以上的聚甘油、甘油的脂肪族羧酸酯、二甘油的脂肪族羧酸酯、甘油單位的重複數為3以上的聚甘油的脂肪族羧酸酯、甘油的烷基醚、二甘油的烷基醚、甘油單位的重複數為3以上的聚甘油的烷基醚、赤藻糖醇、木糖醇、山梨糖醇、甘露糖醇、季戊四醇、季戊四醇的脂肪族羧酸酯、二季戊四醇、二季戊四醇的脂肪族羧酸酯、核糖、去氧核糖、葡萄糖、果糖、半乳糖、海藻糖等。於此等多元醇之中，從維持長期優異的熱安定性之點來看，山梨糖醇、二甘油、甘油單位的重複數為3以上的聚甘油及二季戊四醇係合適，從操作的容易性之觀點來看，山梨糖醇及二季戊四醇係更合適。再者，作為多元醇的上述酯及醚，係酯化或醚化前的多元醇在分子中具有複數的羥基之一部分被酯化或醚化者，即使於酯化或醚化後，也在分子中具有複數的羥基之化合物。
含有鹵素原子之樹脂組成物中的多元醇之含量，相對於含有鹵素原子之樹脂100質量份而言，為0.01~2.5質量份，較佳為0.05~2質量份。多元醇的含量低於0.01質量份時，長期的熱安定性不充分，若超過2.5質量份，則由所得之含有鹵素原子之樹脂組成物所形成的成形品係變容易著色，或發生由該含有鹵素原子之樹脂組成物或由其所形成的成形品揮發，或對表面的滲出。
含有上述多元醇連同前述PVA係本發明的含有鹵素原子之樹脂組成物的特徵之一。藉此，即使在低溫下成形加工時，該含有鹵素原子之樹脂組成物也具有充分的熱安定性。因此，可適用的成形溫度範圍變廣。又，於前述含有鹵素原子之樹脂組成物中含有前述多元醇連同前述PVA時，成形時黏著物對擠壓機內部等的附著亦少，所得之成形品的著色也少。
前述PVA與前述多元醇的質量比係沒有特別的限定，但從尤其即使在低溫下成形加工時，也進一步提高熱安定性，而且在成形時進一步抑制黏著物對擠壓機內部的附著之觀點來看，兩者的質量比較佳為滿足(PVA的質量)/(多元醇的質量)=30/70~90/10，更佳為滿足35/65~85/15，尤佳為滿足40/60~80/20，特佳為滿足45/55~80/20，最佳為滿足50/50~80/20。
於前述含有鹵素原子之樹脂中含有本發明的含有鹵素原子之樹脂組成物中所含有的鋅化合物之方法係沒有特別的限定，較佳為藉由在形成含有鹵素原子之樹脂用的單體之聚合後，添加於所得的含有鹵素原子之樹脂中而含有。該鋅化合物係可為粉，或溶解或分散在水或有機溶劑中，並添加於含有鹵素原子之樹脂中。
就本發明的含有鹵素原子之樹脂組成物中所含有的鋅化合物而言，可舉出有機酸的鋅鹽或無機鋅鹽等。就有機酸的鋅鹽而言，例如可舉出硬脂酸鋅、月桂酸鋅、油酸鋅等的脂肪族羧酸之鋅鹽，苯甲酸鋅、對第三丁基苯甲酸鋅等的芳香族羧酸之鋅鹽；胺基酸的鋅鹽；磷酸單酯或磷酸二酯的鋅鹽等。又，就無機鋅鹽而言，例如可舉出氧化鋅、碳酸鋅等。於此等之中，較佳為脂肪族羧酸的鋅鹽，更佳為硬脂酸鋅。
含有鹵素原子之樹脂組成物中的鋅化合物之含量，相對於含有鹵素原子之樹脂100質量份而言，為0.01~5質量份，較佳為0.05~3質量份。鋅化合物的含量低於0.01質量份時，得不到充分的熱安定化效果，若超過5質量份，則由所得的含有鹵素原子之樹脂組成物所形成的成形品係黑化而不宜。
於前述含有鹵素原子之樹脂中含有前述PVA、前述多元醇及前述鋅化合物時，藉由將前述PVA、前述多元醇及前述鋅化合物加到前述含有鹵素原子之樹脂中而含有者係合適。藉此，更容易達成本發明的效果。
本發明的含有鹵素原子之樹脂組成物係可僅包含含有鹵素原子之樹脂、前述PVA、前述多元醇及前述鋅化合物，但於此等成分以外，亦可更含有通常使用的潤滑劑、安定劑、塑化劑、酚系抗氧化劑、磷系抗氧化劑、紫外線吸收劑、光安定劑、防霧劑、抗靜電劑、阻燃劑、改質劑、強化劑、顏料、發泡劑等。又，於本發明的含有鹵素原子之樹脂組成物中，亦可含有上述以外的其它樹脂。
於本發明的含有鹵素原子之樹脂組成物中，前述含有鹵素原子之樹脂、前述PVA、前述多元醇及前述鋅化合物之合計的佔有比例，較佳為50~100質量%的範圍內，更佳為70~100質量%的範圍內，尤佳為80~100質量%的範圍內。
作為上述滑劑，可舉出流動石蠟、天然石蠟、微晶蠟、聚乙烯蠟等的烴；硬脂酸、月桂酸等的脂肪酸；硬脂酸醯胺、棕櫚酸醯胺、亞甲基雙硬脂醯胺、乙烯雙硬脂醯胺等的脂肪酸醯胺；硬脂酸丁酯等的一元醇之脂肪酸酯；硬化蓖麻油、乙二醇單硬脂酸酯、甘油單硬脂酸酯、三乙二醇二-2-乙基己酸酯等、多元醇的脂肪酸酯中之羥基含有率低於10質量%者；鯨蠟醇、硬脂醇等的醇等。其中，較佳為使用多醇的脂肪酸酯中之羥基含有率低於10質量%者。此時，該化合物較佳為多元醇的脂肪酸單酯，更佳為甘油的脂肪酸單酯。又，多元醇的脂肪酸酯中之脂肪酸較佳為碳數為8~22者，更佳為硬脂酸。於上述化合物之中，甘油單硬脂酸酯係特別合適。上述潤滑劑的含量，相對於含有鹵素原子之樹脂100質量份而言，較佳為0.001~10質量份，更佳為0.05~5質量份。
就上述安定劑而言，可使用周知者，具體地可舉出鈣皂、鋇皂等的鹼土類金屬之皂或鋁皂、有機磷酸金屬鹽等的有機金屬鹽、金屬氧化物、金屬氫氧化物、金屬碳酸鹽、沸石等的無機複合金屬鹽等之無機金屬鹽、氯酸鋇、過氯酸鋇、過氯酸鈉等的鹵氧酸鹽、β-二酮、環氧化合物等的非金屬安定劑等。
就上述塑化劑而言，例如可舉出由如苯二甲酸、偏苯三酸、苯均四酸、己二酸、癸二酸、壬二酸等的酸與正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇、正戊醇、異戊醇、第三戊醇、正己醇、異己醇、正庚醇、異庚醇、正辛醇、異辛醇、2-乙基己醇、正壬醇、異壬醇、正癸醇、異癸醇、月桂醇、肉豆蒄醇、棕櫚醇、硬脂基醇等的直鏈或支鏈之烷基一元醇單獨或混合物所成的酯，或丁二醇與己二酸之酯的酯系塑化劑；如環氧化大豆油、環氧化亞麻仁油、環氧化蓖麻油、環氧化亞麻仁油脂肪酸丁酯、環氧硬脂酸辛酯、環氧三甘油酯、環氧六氫苯二甲酸二異癸酯或環氧氯丙烷與雙酚A之低分子量反應生成物樹脂的環氧系塑化劑；磷酸三癸酯、磷酸三(二甲苯)酯、磷酸單丁基二(二甲苯)酯、磷酸三辛酯等的磷酸酯系塑化劑等。
就上述酚系抗氧化劑而言，只要是通常使用者，則可為任何者，例如可舉出2,6-二第三丁基-對甲酚、2,6-二苯基-4-十八氧基苯酚、硬脂基(3,5-二第三丁基-4-羥基苯基)-丙酸酯、二硬脂基(3,5-二第三丁基-4-羥基苄基)膦酸酯、硫二甘醇雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、1,6-六亞甲基雙[(3,5-二第三丁基-4-羥基苯基)丙酸酯]、1,6-六亞甲基雙[(3,5-二第三丁基-4-羥基苯基)丙酸醯胺]、4,4’-硫代雙(6-第三丁基-間甲酚)、2,2’-亞甲基雙(4-甲基-6-第三丁基苯酚)、2,2’-亞甲基雙(4-乙基-6-第三丁基苯酚)、雙[3,3-雙(4-羥基-3-第三丁基苯基)丁酸]甘醇酯、2,2’-亞乙基雙(4,6-二第三丁基苯酚)、2,2’-亞乙基雙(4-第二丁基-6-第三丁基苯酚)、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、雙[2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯基]對苯二甲酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-參[(3,5-二第三丁基-4-羥基苯基)丙醯氧基乙基]異三聚氰酸酯、肆[亞甲基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]甲烷、2-第三丁基-4-甲基-6-(2-丙烯醯氧基-3-第三丁基-5-甲基苄基)苯酚、3,9-雙[1,1-二甲基-2-{(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、三乙二醇雙[(3-第三丁基-4-羥基-5-甲基苯基)丙酸酯]等。上述酚系抗氧化劑的含量，相對於含有鹵素原子之樹脂100質量份而言，較佳為0.01~5質量份，更佳為0.1~3質量份。
就上述磷系抗氧化劑而言，只要是通常使用者，則可為任何者，例如可舉出亞磷酸參壬基苯酯、參(2,4-二第三丁基苯基)亞磷酸酯、參[2-第三丁基-4-(3-第三丁基-4-羥基-5-甲基苯硫基)-5-甲基苯基]亞磷酸酯、亞磷酸十三酯、亞磷酸辛基二苯酯、亞磷酸二(癸基)單苯酯、二(十三基)季戊四醇二亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三第三丁基苯基)季戊四醇二亞磷酸酯、四(十三基)異亞丙基二苯酚二亞磷酸酯、四(十三基)-4,4’-正亞丁基雙(2-第三丁基-5-甲基苯酚)二亞磷酸酯、六(十三基)-1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷三亞磷酸酯、肆(2,4-二第三丁基苯基)伸聯苯基二亞膦酸酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、2,2’-亞甲基雙(4-甲基-6-第三丁基苯基)-2-乙基己基亞磷酸酯等。上述磷系抗氧化劑的含量，相對於含有鹵素原子之樹脂100質量份而言，較佳為0.001~5質量份，更佳為0.005~3質量份。
就上述紫外線吸收劑而言，例如可舉出2,4-二羥基二苯基酮、2-羥基-4-甲氧基二苯基酮、2-羥基-4-辛氧基二苯基酮、5,5’-亞甲基雙(2-羥基-4-甲氧基二苯基酮)等之2-羥基二苯基酮；2-(2-羥基-5-第三辛基苯基)苯并***、2-(2-羥基-3,5-二第三丁基苯基)-5-氯苯并***、2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并***、2-(2-羥基-3,5-二異丙苯基苯基)苯并***、2,2’-亞甲基雙(4-第三辛基-6-苯并***基)苯酚、2-(2-羥基-3-第三丁基-5-羧基苯基)苯并***的聚乙二醇酯等之2-(2-羥基苯基)苯并***；苯基水楊酸酯間苯二酚單苯甲酸酯、2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯、十六基-3,5-二第三丁基-4-羥基苯甲酸酯等之苯甲酸酯；2-乙基-2’-乙氧基草醯替苯胺、2-乙氧基-4’-十二基草醯替苯胺等之取代草醯替苯胺；乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(對甲氧基苯基)丙烯酸酯等之氰基丙烯酸酯等。上述紫外線吸收劑的含量，相對於含有鹵素原子之樹脂100質量份而言，較佳為0.005~10質量份，更佳為0.01~5質量份。
就上述光安定劑而言，例如可舉出2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、肆(2,2,6,6-四甲基-4-哌啶基)丁烷四羧酸酯、肆(1,2,2,6,6-五甲基-4-哌啶基)丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)‧二(十三基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-羥基苄基)丙二酸酯、1-(2-羥乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯聚縮合物、1,6-雙(2,2,6,6-四乙基-4-哌啶基胺基)己烷/二溴乙烷聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-啉基-s-三聚縮合物、1,6-雙(2,2,6,6-四甲基-4-胡椒基胺基)己烷/2,4-二氯-6-第三辛基胺基-s-三聚縮合物、1,5,8,12-肆[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三-6-基]-1,5,8,12-四氮雜十二烷、1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三-6-基胺基]十一烷、1,6,11-參[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌基)胺基)-s-三-6-基胺基]十一烷等的受阻胺化合物等。上述光安啶劑的含量，相對於含有鹵素原子之樹脂100質量份而言，較佳為0.001~5質量份，更佳為0.05~3質量份。
就本發明的含有鹵素原子之樹脂組成物的成形加工方法而言，可舉出擠出加工、壓延加工、吹塑成形、加壓加工、粉體成形、射出成形等。
本發明的成形品係由上述含有鹵素原子之樹脂組成物所形成。該成形品的形狀係沒有特別的限制，例如可舉出丸粒、薄膜、片、管子、細管或其它各種立體成形品等。
以下，藉由實施例來更詳細說明本發明。再者，於以下的實施例及比較例中，沒有特別預先指明時，份及%各自表示質量份及質量%。
只要沒有特別預先指明，則PVA之分析係依照JIS K6726記載的方法來進行。
使聚合度850、皂化度72莫耳%的聚乙烯醇，以相對於氯乙烯而言相當於600ppm之量，溶解於去離子水中，以調製分散安定劑。將如此所得之分散安定劑投入於經刻度附著防止劑NOXOL WSW(CIRS公司製)以固體成分為0.3g/m2所塗佈之玻璃襯裏製高壓釜中。接著，於玻璃襯裏製高壓釜中投入0.04份的二異丙基過氧二碳酸酯的70%甲苯溶液，排氣直到高壓釜內的壓力成為0.0067MPa為止而去除氧後，投入30份的氯乙烯，將高壓釜內的內容物升溫至57℃，於攪拌下開始聚合。聚合開始時的高壓釜內之壓力為0.83MPa。開始聚合後，經過7小時後，在高壓釜內的壓力成為0.44MPa的時間點停止聚合，去除未反應的氯乙烯後，取出聚合反應物，在65℃進行一夜乾燥，而得到聚氯乙烯(PVC)。
於具備攪拌機、氮導入口、添加劑導入口及引發劑添加口的6L反應槽中，投入900g醋酸乙烯酯、2,100g甲醇，升溫至60℃後，藉由30分鐘的氮氣冒泡而將系統中氮氣置換。將上述反應槽內溫調整至60℃，添加2.3g 2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)以引發聚合。聚合中將聚合溫度維持在60℃，5小時後當聚合率達到70%時，冷卻而停止聚合。接著，於減壓下去除未反應的醋酸乙烯酯，而得到聚醋酸乙烯酯(PVAc)的甲醇溶液。於濃度經調整至30%的PVAc溶液中，以鹼莫耳比(NaOH之莫耳數/PVAc中的乙烯酯單位之莫耳數)成為0.006的方式，添加NaOH甲醇溶液(10%濃度)而進行皂化。所得之PVA係用甲醇洗淨。藉由以上的操作，得到聚合度320、皂化度80莫耳%的PVA。
於瓷製燒杯中，分別添加100份的上述所得之聚氯乙烯、0.75份的上述所得之PVA、0.25份的市售之山梨糖醇、1份的市售之硬脂酸鋅及0.5份的市售之硬脂酸鈣，混合而得到聚氯乙烯組成物。
藉由試驗輥，將所得之聚氯乙烯組成物在160℃混練5分鐘，而製作厚度0.45mm的薄片。
將上述薄片切割成50×70mm，將所得之薄片置入吉爾(Geer)烘箱中，測定在180℃的溫度下完全變成黑色為止的時間(黑化時間)，當作熱安定性的指標。表1中顯示評價結果。
將上述薄片切割成複數的45×30mm，疊合12~14片的所得之薄片，在185℃加壓5分鐘以製作厚度5mm的試驗片，藉由目視來比較著色性，依照以下的基準來判定。表1中顯示評價結果。
A：幾乎沒有著色。
B：稍微看到著色。
C：黃色。
D：黃褐色。
為了在上述聚氯乙烯組成物的混練時，評價黏著物對擠壓機內部等的附著之產生程度，藉由目視來觀察聚氯乙烯組成物之混練時所使用的上述試驗輥之表面，依照以下的基準來判定黏著物對試驗輥表面的附著之產生程度。表1中顯示評價結果。
A：完全沒有附著。
B：稍微看到附著。
C：看到大量的附著。
除了如表1中所示，變更所使用的多元醇之種類、PVA、多元醇及硬脂酸鋅之含量以外，與實施例1同樣地得到聚氯乙烯，與實施例1同樣地形成薄片。然後，與實施例1同樣地進行熱安定性試驗、著色性試驗及黏著物的附著產生評價。表1中顯示評價結果。
除了如表1中所示，變更所使用的多元醇之種類、PVA、多元醇及硬脂酸鋅之含量以外，與實施例1同樣地得到聚氯乙烯，與實施例1同樣地形成薄片。然後，與實施例1同樣地進行熱安定性試驗、著色性試驗及黏著物的附著產生評價。表1中顯示評價結果。
於實施例1~8中，顯示同時含有皂化度為80莫耳%且聚合度為320的PVA、與作為多元醇的山梨糖醇、二甘油、聚甘油(甘油的10聚物或20聚物)或二季戊四醇之聚氯乙烯組成物的評價結果。聚氯乙烯組成物皆具有充分的熱安定性，而且黏著物對試驗輥表面的附著少。又，將此等聚氯乙烯組成物成形而得之各薄片係著色少。
另一方面，於比較例1~2中，顯示不含有多元醇的聚氯乙烯組成物之評價結果。不含有多元醇時，黑化時間短而熱安定性不充分。
比較例3係顯示不含有PVA，而含有1份當作多元醇的山梨糖醇之聚氯乙烯組成物的評價結果。不含有PVA時，黑化時間短而熱安定性不充分，薄片係著色成黃色，更且亦看到大量的黏著物對試驗輥表面的附著。
比較例4係顯示含有3份的PVA、1份當作多元醇的山梨糖醇之聚氯乙烯組成物的評價結果。若含有3份的PVA，則黑化時間係十分長，但薄片係著色成黃色。
比較例5係顯示含有1份的PVA、3份當作多元醇的山梨糖醇之聚氯乙烯組成物的評價結果。若含有3份的多元醇，則黑化時間係十分長，但薄片係著色成黃褐色，亦看到大量的黏著物對試驗輥表面的附著。
比較例6係顯示含有0.005份的PVA、1份當作多元醇的山梨糖醇之聚氯乙烯組成物的評價結果。PVA為0.005份時，黑化時間短而熱安定性不充分，薄片係著色成黃色，更且亦看到大量的黏著物對試驗輥表面的附著。
比較例7係顯示含有1份的PVA、0.005份當作多元醇的山梨糖醇之聚氯乙烯組成物的評價結果。山梨糖醇為0.005份時，黑化時間短而熱安定性不充分。
比較例8~10係顯示不含有PVA，而含有作為多元醇的二甘油(比較例8)、聚甘油(甘油的10聚物、比較例9)或二季戊四醇(比較例10)之聚氯乙烯組成物的評價結果。不含有PVA時，皆黑化時間短而熱安定性不充分。
比較例11係顯示含有1份的PVA、1份當作多元醇的甘油單硬脂酸酯之聚氯乙烯組成物的評價結果。甘油單硬脂酸酯係羥基含有率為9質量%。如此地，多元醇的羥基含有率低時，黑化時間短而熱安定性不充分。
比較例12係顯示含有1份的PVA、1份當作多元醇的聚甘油(甘油的約50聚物)之聚氯乙烯組成物的評價結果。聚甘油(甘油的約50聚物)係分子量約3,700。如此地，多元醇的分子量大時，黑化時間短而熱安定性不充分。
比較例13係顯示含有0.75份的PVA、0.25份當作多元醇的山梨糖醇、0.005份的硬脂酸鋅之聚氯乙烯組成物的評價結果。硬脂酸鋅的含量為0.005份時，黑化時間短而熱安定性不充分。
比較例14係顯示含有0.75份的PVA、0.25份當作多元醇的山梨糖醇、10份的硬脂酸鋅之聚氯乙烯組成物的評價結果。硬脂酸鋅的含量為10份時，黑化時間短而熱安定性不充分。
除了於實施例1中，在PVA的製造時之皂化時，將鹼莫耳比由0.006變更為0.003以外，藉由與實施例1同樣的方法，得到表1中所示的PVA。使用此PVA，與實施例1同樣地得到聚氯乙烯組成物，與實施例1同樣地形成薄片。然後，與實施例1同樣地進行熱安定性試驗、著色性試驗及黏著物的附著產生評價。表1中顯示評價結果。
比較例15係顯示含有皂化度為55莫耳%且聚合度為320的PVA與作為多元醇的山梨糖醇之聚氯乙烯組成物的評價結果。PVA的皂化度為55莫耳%時，黑化時間短而熱安定性不充分。
如上述實施例所示，若使用本發明的含有鹵素原子之樹脂組成物，則由於即使在比較低溫下成形時也具有充分的熱安定性，故可適用的成形溫度範圍廣。再者，於成形時亦可抑制黏著物對擠壓機內部等的附著之產生，可得到著色少的成形品，故非常有意義。
Claims (5)
- 一種含有鹵素原子之樹脂組成物，其含有：相對於含有鹵素原子之樹脂100質量份而言，皂化度為60~99.9莫耳%且黏度平均聚合度為100~450的聚乙烯醇0.01~2.5質量份，分子量為2,000以下且羥基含有率為10質量%以上的多元醇0.01~2.5質量份，及鋅化合物0.01~5質量份；該多元醇為山梨糖醇、二甘油、甘油單位的重複數為3以上的聚甘油或二季戊四醇。
- 如申請專利範圍第1項之含有鹵素原子之樹脂組成物，其中聚乙烯醇與多元醇的質量比係滿足(聚乙烯醇的質量)/(多元醇的質量)=30/70~90/10。
- 如申請專利範圍第1或2項之含有鹵素原子之樹脂組成物，其中藉由將聚乙烯醇、多元醇及鋅化合物加到含有鹵素原子之樹脂中而含有。
- 一種含有鹵素原子之樹脂組成物之製造方法，其具有對於含有鹵素原子之樹脂100質量份，添加皂化度為60~99.9莫耳%且黏度平均聚合度為100~450的聚乙烯醇0.01~2.5質量份、分子量為2,000以下且羥基含有率為10質量%以上的多元醇0.01~2.5質量份、及鋅化合物0.01~5質量份之步驟；該多元醇為山梨糖醇、二甘油、甘油單位的重複數為3以上的聚甘油或二季戊四醇。
- 一種成形品，其係由如申請專利範圍第1或2項之含有鹵素原子之樹脂組成物所形成。
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| US5070128A (en) * | 1989-04-04 | 1991-12-03 | Rhone-Poulenc Chimie | Heat-stabilized/non-yellowing chloropolymers |
| TW201006882A (en) * | 2008-06-16 | 2010-02-16 | Kuraray Co | Poly (vinyl chloride) resin composition and method for producing the same |
| CN101827895A (zh) * | 2007-11-28 | 2010-09-08 | 株式会社艾迪科 | 含氯树脂用稳定剂及含氯树脂组合物 |
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| US5070128A (en) * | 1989-04-04 | 1991-12-03 | Rhone-Poulenc Chimie | Heat-stabilized/non-yellowing chloropolymers |
| CN101827895A (zh) * | 2007-11-28 | 2010-09-08 | 株式会社艾迪科 | 含氯树脂用稳定剂及含氯树脂组合物 |
| TW201006882A (en) * | 2008-06-16 | 2010-02-16 | Kuraray Co | Poly (vinyl chloride) resin composition and method for producing the same |
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